A method for hydro-purification of the vapour of a wastewater containing phenols and / or aromatic hydrocarbons

Abstract

A method for hydrogenating and purifying the evaporated gas of wastewater containing phenols and / or aromatics is suitable for converting wastewater containing phenols and aromatics produced by direct coal liquefaction. This method can combine a hydrogenation modification reaction process with a hydrogenation purification reaction process, eliminating most to all of the difficulties in the biochemical treatment of wastewater containing phenols and aromatics produced by direct coal liquefaction. The effluent from the hydrogenation modification reaction is separated into hot high-pressure gas and hot high-pressure oil in a thermal high-pressure separation process. The phenol-containing wastewater comes into contact with the hot high-pressure gas to complete the evaporation process, yielding a first gas rich in water and hydrogen containing phenols and aromatics, as well as the usually present dust-containing condensate oil. The first gas is washed with washing oil to remove dust, becoming a second gas. The second gas, with an operating temperature higher than the dew point, undergoes a hydrogenation purification reaction process to complete a deep hydrogenation refining reaction of organic matter, transforming it into a hydrogenation purification reaction effluent with low organic pollutant content. This effluent is then mixed with a quenched stream and cooled to below the dew point before being separated into cold high-pressure water.

Description

Technical Field

[0001] This invention relates to a method for hydrogenating and purifying the vapors of wastewater containing phenols and / or aromatics. It can be a combination of a hydrocarbon hydrogenation reaction process and a hydrogenation purification reaction process for the vapors of phenol-containing wastewater. This method is suitable for purifying wastewater containing phenols and aromatics produced by direct coal liquefaction. It can be a combination of a hydrogenation modification reaction process and a hydrogenation purification reaction process, eliminating most to all of the difficulties in the biochemical treatment of wastewater containing phenols and aromatics produced by direct coal liquefaction. Background Technology

[0002] Document A01: ① Publication title: Coal Direct Liquefaction Technology and Engineering, pages 767-768; ② ISBN: 9-78703-04308-23; ③ Authors: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin; ④ Publisher: Science Press, which describes in detail the composition of coal direct liquefaction and hydrogenation-modified acidic water, as well as some biochemical treatment methods.

[0003] Table 1 shows the analysis results of acidic water from direct coal liquefaction and hydrogenation modification at China Shenhua Ordos Coal-to-Oil Branch. Table 2 shows the sources, quantities, and pollutants of acidic water from the direct coal hydrogenation liquefaction unit at China Shenhua Ordos Coal-to-Oil Branch. The data are from literature A01, "Direct Coal Liquefaction Technology and Engineering," pages 767-768. Tables 1 and 2 show the characteristics of organic pollutants in acidic water from direct coal liquefaction and hydrogenation modification: from the perspective of recovering pure water, all other components are pollutants. The pollutants contain various organic impurities that cannot be treated by a single biochemical method. If a biochemical method is chosen to treat organic matter, a combination of multiple biochemical processes with different functions is required. Furthermore, phenols and aromatic hydrocarbons with two or more rings are difficult to digest and transform by bacteria. In addition, the presence of chloride ions and metal ions inevitably leads to a complex and inefficient biochemical treatment process.

[0004] Table 3 shows the concentration limits for some metals, inorganic substances, and organic substances that inhibit nitrification in high-concentration wastewater from coal liquefaction, as disclosed in document A02. Document A02: ① Publication title: *Shenhua Science & Technology* (Vol. 14, No. 5, September 2016), pages 72-76; ② Article title: Experimental study on the influence of BAF method on nitrification reaction of high-concentration wastewater from coal liquefaction in Shenhua's direct coal liquefaction project; ③ Author: Su Zhiqiang. This document describes an experimental study on the influence of the BAF method on nitrification reaction of high-concentration wastewater from direct coal liquefaction in Shenhua's direct coal liquefaction project. It describes the concentration limits for some inhibitors that have a strong inhibitory effect on nitrifying bacteria. Once the content of these inhibitors reaches the concentration listed in Table 3 (this concentration threshold is very low), it will have a toxic or strong inhibitory effect on nitrifying bacteria, terminating the expected nitrification reaction of high-concentration wastewater from coal liquefaction. This indicates that even a small amount of special pollutants can severely inhibit the biochemical reaction; that is, even slight fluctuations in these special pollutants can seriously affect the biochemical reaction effect.

[0005] Taking the high-concentration wastewater from coal liquefaction shown in Table 1 as an example, it contains multiple pollutants. Since no single bacterium can digest so many pollutants simultaneously, the adoption of a biochemical treatment process inevitably leads to the use of multiple biochemical bacteria in series. For example, reference A03: ① Publication title: "Coal Engineering" (Vol. 49, No. 5, 2017), pp. 72-76; ② Article title: Development and application of high-concentration wastewater treatment technology from direct coal liquefaction; ③ Authors: Fan Shujun, Yu Liangyong, Liu Chunhui. This reference describes the high-concentration wastewater treatment system of the Shenhua Coal Direct Liquefaction Project, which adopts a combination of technologies including "double-tower stripping + phenol recovery + high-efficiency catalytic oxidation pretreatment + immobilized high-efficiency aerated biological filter + ozone oxidation + membrane bioreactor technology + ultrafiltration + reverse osmosis". The disadvantages of this technology are "complex process path, large fluctuation range of operating effect, and large land area". "High investment"; at the same time, in order to improve the efficiency of oil and coal powder removal, demulsifiers are added; in order to improve the ammonia removal rate, alkali is added to adjust the pH value of the water; in order to recover phenols, extractants are added; in order to meet the normal survival of bacteria, a variety of other treatment processes are adopted to protect the normal survival of bacteria and foreign chemical substances are added: acids and alkalis are added to adjust the pH value; coagulants such as polyaluminum or polyacrylamide are added in the air flotation process; hydroxyl oxidants are used to destroy the aromatic ring structure; bacterial nutrients such as carbon sources are added; ozone is used to destroy the polycyclic aromatic hydrocarbon structure and generate new organic species quinones; the activated carbon adsorbent used remains in the water. The addition of these foreign materials is essentially adding new pollutant species to the water. The result is inevitably inefficient conversion of the biochemical conversion process and multiple non-intrinsic purification processes, resulting in too many series of links in the purification process of high-concentration coal liquefaction wastewater and unstable conversion effect.

[0006] Table 1. Analysis results of acidic water from direct coal liquefaction and hydrogenation modification at China Shenhua Ordos Coal-to-Oil Branch (Unit: mg / L, except pH).

[0007]

[0008] Table 2. Statistics on the Sources, Quantities, and Pollutants of Acidic Water from the Coal Hydrogenation Direct Liquefaction Unit of China Shenhua Ordos Coal-to-Oil Branch

[0009]

[0010] Table 3. Concentration limits for some metals, inorganic substances, and organic substances that inhibit nitrification in high-concentration wastewater from coal liquefaction, as disclosed in document A02.

[0011]

[0012] However, analysis of the data in Tables 1 and 2 also reveals the following characteristics of pollutants in the acidic water from direct coal liquefaction and hydrogenation modification: From the perspective of recovering pure water, in 86.5 t / h of wastewater, the amount of volatile phenols is 486.8 kg / h (0.563 wt%), and the amount of oil is 1912.5 kg / h (2.211 wt%). Considering biochemical purification, the amount is enormous. However, if hydrogenation purification is considered, the absolute amount of the reaction task is extremely small, and a single reaction process can convert all organic matter and toxic inorganic matter, achieving the ideal goal of deep purification with a simple process. Table 6 shows the desulfurization and hydrogen removal of the first wastewater (high-concentration wastewater from coal liquefaction). The pollutant composition of the pretreated wastewater (after ammonia removal and before phenol removal) is shown in Table 6, which strongly supports the above view. Hydrogenation of wastewater can naturally separate solids from evaporating components, but requires the liquid phase to carry and flush away solids to prevent solid accumulation and blockage of the flow channels. Hydrogenation of wastewater ideally requires the wastewater to be vaporized into a dry water-gas state; therefore, the heat consumed in wastewater vaporization needs to be recovered at a high rate to reduce energy consumption. Of course, to reduce the difficulty of the direct coal liquefaction and hydrogenation purification reactions of acidic water modified by hydrogenation, it is best to pre-treat the raw wastewater: removing solids, free oil, hydrogen sulfide, carbon dioxide, ammonia, phenols, and high-boiling hydrocarbons, or one or more of these processes.

[0013] Because chloride and fluoride ions have strong interactions with water molecules or hydrogen ions in water molecules, the dechlorination and fluoride removal steps (such as reverse osmosis) are usually the last step in the direct coal liquefaction and hydrogenation modification of acidic water to remove pollutants. All steps before this are pretreatment steps for the dechlorination and fluoride removal steps. A large portion of the pollutants such as hydrogen sulfide, ammonia, and carbon dioxide can be removed through stripping evaporation and fractionation tower processes. Thus, the main targets of the biochemical treatment steps are phenols, bicyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, and other trace components coexisting in the wastewater of the biochemical treatment steps. These are both the target components of bacterial biochemical treatment and the toxins of bacteria.

[0014] For wastewater containing organic heteroatom hydrocarbons (especially aromatic hydrocarbons), the purification of water components is essentially a process of eliminating or significantly reducing the electrical conductivity of these organic heteroatom hydrocarbons (especially aromatic hydrocarbons). This is because only in this way can the interaction between organic heteroatom hydrocarbons (especially aromatic hydrocarbons) and water molecules be eliminated. This requires removing heteroatoms and breaking down benzene ring structures. However, in the biochemical processes of hydrocarbons containing organic oxygen, organic nitrogen, organic sulfur, and organic metals, long carbon-carbon chains are broken into short carbon chains or even single-carbon molecules such as methane and carbon dioxide. Organic oxygen atoms are converted into smaller molecules such as water and carbon dioxide. In this process, organic nitrogen atoms are converted into small molecules such as nitrogen gas and ammonia, and organic sulfur atoms are converted into small molecules such as hydrogen sulfide and sulfur dioxide. It can be seen that a large number of carbon-carbon bond breaking and carbon-heteroatom bond breaking reactions occur. Therefore, it is a large-scale chemical reaction process. Furthermore, because biochemical processes are usually carried out at room temperature and high-temperature methods, which are commonly used and effective conditions for breaking chemical bonds, are not available, the reaction efficiency is extremely low. Moreover, toxic components can only begin to be digested after being inhaled by bacteria, resulting in very low reaction selectivity. This leads to long biochemical reaction times, low efficiency, and large system size. In addition, the biochemical products of organic heteroatom hydrocarbons have extremely low reuse value.

[0015] In the biochemical processes of hydrocarbons containing organic oxygen, organic nitrogen, organic sulfur, and organometallic compounds, long carbon-carbon chains are broken into short-chain molecules or even single-carbon atom molecules such as methane and carbon dioxide. Organic oxygen atoms are transformed into small molecules such as water and carbon dioxide, organic nitrogen atoms are transformed into small molecules or ionic groups such as nitrogen gas and nitro groups, and organic sulfur atoms are transformed into small molecules such as hydrogen sulfide and sulfur dioxide. It can be seen that a large number of carbon-carbon bond breaking reactions and carbon-heterobond breaking reactions occur. On the other hand, for organic matter mainly composed of carbon and hydrogen elements, the effect of wastewater biochemical treatment can be mainly classified as the elimination of electrical reactions, that is, the separation of electrical elements from carbon and hydrogen elements or the deep saturation of carbon-carbon unsaturated bonds.

[0016] Heteroatom organics and aromatic hydrocarbons in wastewater are all organics that can supply electricity.

[0017] Compared to the target of wastewater purification, the hydrogenation conversion process involving deep hydrogenation refining can eliminate or significantly reduce the electrical charging ability of organic heteroatom hydrocarbons (especially aromatic hydrocarbons containing organic heteroatoms) in wastewater. It has the following characteristics: the hydrogenation refining catalyst has the ability to selectively adsorb and react with pollutants that have electrical charging ability, resulting in high reaction efficiency and high impurity removal rate. Furthermore, the number of carbon-carbon bond breaking reactions can be minimized, thus maintaining the carbon-carbon bond length as much as possible and increasing the utilization value of carbon-carbon bond groups. Therefore, from the above perspective, the deep hydrogenation refining reaction purification method for wastewater has higher purification efficiency, higher removal rate, and higher value of purification products.

[0018] For the purification target of high-concentration wastewater from direct coal liquefaction, based on the characteristics that almost all impurity elements contained in these pollutants can be almost completely converted by hydrogenation in the deep hydrogenation refining process, and that all kinds of unsaturated chemical bonds can be saturated by deep hydrogenation in the deep hydrogenation refining process, this invention proposes that high-concentration wastewater from direct coal liquefaction (preferably pre-treated wastewater containing phenols and aromatics) be converted into dry gaseous water, and then purified through a deep hydrogenation purification process. The resulting cold high-concentration water has biochemical treatment characteristics that are close to or equivalent to the easy biochemical treatment characteristics of hydrogenated cold high-concentration water.

[0019] Dry gas refers to a gas whose operating temperature is higher than the dew point temperature of water, and which contains no liquid water.

[0020] A wet gas is a gas whose operating temperature is lower than the dew point temperature of water, and which contains liquid water.

[0021] The hydrogenation purification of high-concentration wastewater from direct coal liquefaction requires that the wastewater entering the hydrogenation purification reaction process be in the gas phase, preferably a dry water gas. This is because suitable reaction conditions for the hydrogenation purification of pollutants typically require a certain hydrogen partial pressure, a relatively high reaction temperature, and the presence of hydrogen sulfide. If the main component is water, the following major problems arise: ① The aqueous phase dissolves hydrogen sulfide, hydrogen chloride, and hydrogen fluoride, becoming acidic substances that corrode the catalyst, reactor internals, and reactor walls; ② The aqueous phase soaks the hydrogenation purification catalyst, weakening its structural strength and causing it to pulverize; ③ The vaporization of liquid water absorbs a large amount of heat, lowering the reaction temperature; ④ The hydrogenation purification catalyst... When the liquid water adsorbed by the catalyst vaporizes, its volume expands dramatically, which can cause it to explode and shatter the hydropurification catalyst. Therefore, the operating temperature of the hydropurification reaction feed, the hydropurification reaction process, and the hydropurification reaction products is usually as much higher as possible than the water dew point temperature of the reactants. When the operating temperature of the hydropurification reaction products is close to or lower than the dew point temperature, they are usually subjected to a rapid cooling process to enter an aqueous phase containing suitable alkaline substances such as ammonia molecules that can neutralize acidic substances such as hydrogen sulfide, hydrogen chloride, and hydrogen fluoride. These alkaline substances, such as ammonia molecules, can be products of the hydropurification reaction and / or products of the hydrocarbon hydrogenation reaction process R1 and / or externally injected substances.

[0022] To reduce the energy consumption of the hydrogenation purification process for high-concentration wastewater from direct coal liquefaction, it is essential to ensure a high recovery rate of the heat absorbed during the vaporization process (latent heat of vaporization of water), such as above 75-85%. Due to the strong hydrogen bonds between liquid water molecules, the attractive force between water molecules increases rapidly as the temperature decreases, leading to a rapid drop in the saturated vapor pressure of liquid water. This characteristic of water provides the necessary conditions for this process.

[0023] Table 4 shows the saturated vapor pressure of water at 20–250℃ and the water condensation ratio in the saturated vapor condensation process of water at 250℃.

[0024] As can be seen from Table 4, for a total pressure of 170 kg / cm² 2 A. For water-saturated gas at 250℃, when its condensation process reaches the conventional temperature condition of 160℃, which can be achieved by a heat exchanger that recovers heat, the water condensation ratio reaches 84.46%. This means that approximately 84.46% of the total latent heat of the total water component in the water-saturated gas at 250℃ is recovered.

[0025] Table 4 uses a total pressure of 170 kg / cm². 2 A. Using the water-to-condensation ratio in the condensation process of water-saturated gas at 250℃ to illustrate the problem is because this is close to conventional operating conditions. However, if the total pressure is 170 kg / cm², the problem would be different. 2 A. Water-saturated gas at 275℃ will increase the saturated water content by an astonishing 49.56%. Therefore, this invention has huge potential to increase the amount of high-concentration wastewater that can be treated from direct coal liquefaction. Of course, as the saturated volume concentration of the water component increases from 23.86% to 35.682%, the hydrogen partial pressure will decrease. This also shows that by reducing the number of macromolecules in the R2 feed in the hydrogenation purification reaction process, the required hydrogen partial pressure for organic matter can be reduced, which can significantly increase the amount of high-concentration wastewater that can be treated from direct coal liquefaction.

[0026] To reduce the investment and energy consumption of the hydrogenation purification system for the evaporation gas from coal direct liquefaction wastewater containing phenols and aromatics, it is necessary to reduce the number of dedicated systems. This requires constructing a combined method of hydrocarbon hydrogenation reaction and hydrogenation purification reaction of the evaporation gas from phenol-containing wastewater. For example, a combined method of hydrogenation modification reaction and hydrogenation purification reaction could be used. Utilizing the hydrogen, hydrocarbon oil gases, temperature, and pressure conditions of the hot high-density gas separated from the hydrogenation modification reaction products, the wastewater is first injected to achieve wastewater gasification. Simultaneously, the hot high-density gas from the hydrogenation modification reaction products cools down to produce condensate oil, which washes the gas, rinses the solids, and absorbs large molecular weight phenols and hydrocarbons from the feed of the hydrogenation purification reaction, forming condensate from the wastewater vaporization process. This reduces the boiling point and amount of external washing oil used in the dedicated oil washing step. The condensate containing solids, high-boiling-point phenols, and high molecular weight aromatics obtained from the wastewater gasification process then enters a system capable of treating solid hydrocarbon feedstocks. Classified recycling: For example, the high-boiling-point oil entering the hydromodification reaction product FRAC80 is separated into narrow-range distillates with different boiling ranges. Solid particles enter the highest-boiling-point bottom oil FRAC80-DV of the FRAC80 separation process. Typically, the bottom oil FRAC80-DV is used as a solvent to prepare coal-oil slurry for use as feedstock in the direct coal hydrolysis reaction. In this way, the high-boiling-point pollutants (solids, macromolecular phenols, macromolecular hydrocarbons) contained in the condensate from wastewater are ultimately classified and recycled as products of the "direct coal hydrolysis reaction fractionation system," eliminating the problems of biochemical conversion and hydrogenation purification of these pollutants. Therefore, the method of this invention is an optimization technology for the overall process properties of wastewater, achieving the effect of "hydrogenation conversion of low-boiling-point organic components, fractionation of high-boiling-point organic components, and return of solid components to the direct coal hydrolysis reaction fractionation system, ultimately entering the liquefaction residue."

[0027] Table 4. Saturated vapor pressure of water at 20–250℃ and water condensation ratio during the saturated vapor condensation process at 250℃.

[0028]

[0029]

[0030] When hydrocarbon hydrogenation reaction process R1 performs a hydrogenation modification reaction, combining hydrogenation modification reaction process R1 with hydrogenation purification reaction process R2 has the following advantages:

[0031] ① The effluent R1P from the hydrogenation modification reaction process is itself a stream containing phenols, aromatics, water, and hydrogen. Its hot high-temperature gas or deoiling hot high-temperature gas undergoes a hydrogenation purification reaction process, which simultaneously purifies pollutants such as phenols and aromatics. This purifies the condensate of the water component in the hydrogenation modification reaction effluent R1P, reducing the production of wastewater containing phenols and aromatics.

[0032] According to conventional processes, when the effluent R1P from the hydrogenation modification reaction is condensed and separated separately, it is also necessary to add clean washing water to prevent crystals such as hydrosulfide amine and ammonium chloride from depositing and clogging the flow channel, thus generating more wastewater containing phenols and aromatics.

[0033] ②The phenol- and aromatic wastewater from the direct liquefaction products of coal hydrogenation exists in the effluent of the hydrogenation purification reaction after the hydrogenation purification reaction process. During the rapid cooling process, it is reused as washing water to prevent the deposition and blockage of the flow channel by crystals such as hydrosulfide amine and ammonium chloride, thereby saving the external input of clean washing water and reducing the overall acidic water production.

[0034] ③ Essentially, the liquid phenol- and aromatic wastewater from the direct liquefaction products of coal hydrogenation, after vaporization, belongs to the same category of substances as the water component (which coexists with the phenol and aromatic components) in the effluent R1P of the hydrogenation modification reaction. The hot high-pressure separation process of the effluent R1P of the hydrogenation modification reaction is a separation process to remove heavy aromatic components and any solid particles that may be present. Furthermore, some of the hydrocarbon oil contained in the hot high-pressure gas R1P-S1V of the effluent R1P of the hydrogenation modification reaction can be used as gas-phase washing oil during the cooling and condensation process of the first wastewater vaporization process. This oil adheres to and carries solid particles in the gas phase, achieving a purification effect by removing solid particles.

[0035] The wastewater containing phenols and aromatics from direct coal liquefaction is purified and converted into cold high-resolution acidic water KSW after passing through the hydrogenation purification and conversion reaction process of this invention. The treatment process of cold high-resolution acidic water KSW01 can be any suitable method, such as the same treatment method as that for hydrogenated acidic water, that is, after filtration, oil removal, and dissolved gas removal, it goes through the acidic water stripping process U700 to remove hydrogen sulfide and ammonia, and then obtains preliminary purified water KSW05 containing chloride and fluoride ions. Then, after simple biochemical treatment, the preliminary purified water KSW05 goes through ultrafiltration and reverse osmosis processes to obtain qualified purified water KSW08, which can be used to replace fresh water or demineralized water.

[0036] Thus, the basic concept of this invention has been presented.

[0037] The basic concept of this invention is: a method for hydrogenating and purifying the evaporated gas of wastewater containing phenols and / or aromatics. This method can be combined with a hydrocarbon hydrogenation reaction process and a hydrogenation and purification reaction process for the evaporated gas of phenol-containing wastewater. It is suitable for converting wastewater containing phenols and aromatics produced by direct coal liquefaction. This method can be combined with a hydrogenation modification reaction process and a hydrogenation purification reaction process, which can eliminate most to all of the difficulties in the biochemical treatment of wastewater containing phenols and aromatics produced by direct coal liquefaction. The effluent from the hydrogenation modification reaction is separated into hot high-pressure gas and hot high-pressure oil in a hot high-pressure separation process. The phenol-containing wastewater comes into contact with the hot high-pressure gas to complete the evaporation process and obtains a first gas containing phenols and aromatics, water-rich gas, and hydrogen-rich gas, as well as the dust-containing condensate oil that is usually present. The first gas is washed and dust-reduced by washing oil and becomes a second gas. The second gas, with an operating temperature higher than the dew point, undergoes a hydrogenation purification reaction process to complete a deep hydrogenation refining reaction of organic matter and is converted into a hydrogenation purification reaction effluent with low organic pollutant content. It is then mixed with a quenched stream and cooled to a temperature below the dew point before being separated into cold high-pressure water.

[0038] In a broad sense, this invention belongs to the category of chemical reaction separation methods for wastewater containing phenols and aromatic hydrocarbons.

[0039] As described above, the basic concept of this invention is: first, wastewater is gasified to obtain dry gas, and then the dry gas undergoes a deep hydrogenation purification reaction to obtain a clean water gas stream. Of course, in order to ensure the continuous and stable operation of the "deep hydrogenation purification reaction of dry gas", pretreatment is required before the gasification of high-concentration wastewater from direct coal liquefaction. This includes one or more of the following steps: solid removal (ash, unliquefied coal, etc.), oil removal, hydrogen sulfide removal, ammonia removal, phenol recovery, preheating, and pressurization. Before the dry gas enters the hydrogenation purification reaction process, it needs to be oil-washed to remove solid dust and cooled to separate high-boiling-point hydrocarbons and high-boiling-point phenols.

[0040] The hydrogenation purification of evaporated gas from phenol- and aromatic hydrocarbon-containing wastewater described in this invention refers to the process of converting organic and inorganic substances in phenol- and aromatic hydrocarbon-containing wastewater into a process that can be deeply purified using conventional processes, especially reducing the difficulty of the biochemical treatment process. The main features are one or more of the following: converting heteroatoms in organic matter into inorganic matter; converting organic matter with high hydrogen unsaturation into organic matter with high hydrogen saturation to reduce its electrical conductivity and biochemical toxicity; converting difficult-to-separate inorganic matter into easily separable inorganic matter; and reducing the solubility of hydrocarbons in water.

[0041] Traditional biochemical treatment methods directly introduce various organic compounds, such as organic oxides (phenols, etc.), organic nitrogen compounds, organic sulfur compounds, cyanides, organic chlorides, organic fluorides, dicyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, and organometallic compounds, from the high-concentration wastewater of direct coal liquefaction into the biochemical process. The result is inevitably an inefficient and complex process.

[0042] In wastewater gasification for solid removal, if carried out at low operating pressures, the volume of the evaporated wastewater gas is too large, leading to a significant increase in the spatial entropy of solid particles (i.e., they are dispersed in a huge space). Washing these highly dispersed solid particles requires a massive amount of washing oil. The method of this invention, particularly the combined process with the hydrogenation reaction R1, simply achieves high water vapor partial pressure conditions, thereby significantly reducing the operating volume of the evaporated wastewater gas, reducing the dispersion of solid particles, significantly reducing the amount of washing oil, and utilizing hydrocarbon oil in the process stream as washing oil. The washing oil that adsorbs solid particles enters the fractionation system for co-processing other hydrocarbon oils containing solid particles, thus simplifying the overall process.

[0043] In contrast, this invention argues that the fundamental reason for the complexity and inefficiency of existing coal direct liquefaction high-concentration wastewater organic matter treatment processes lies in the fact that, due to the lack of discovery of the advantages of hydrogenation, the biochemical treatment path of light oily wastewater from the petroleum industry is adopted. This approach "assumes" that the difficult-to-treat, simple and efficient coal direct liquefaction high-concentration wastewater is suitable for biochemical treatment, inevitably leading to inherent logical flaws in the process path. This directly introduces various organic compounds from the coal direct liquefaction high-concentration wastewater, which are difficult for bacteria to digest in the biochemical process, such as organic oxides (phenols, etc.), organic nitrogen compounds, organic sulfides, cyanides, organic chlorides, organic fluorides, dicyclic aromatic hydrocarbons, polycyclic aromatic hydrocarbons, and organometallic compounds, into the biochemical process. The result is inevitably inefficient biochemical conversion and complex cascade applications of multiple processes, with unstable conversion effects.

[0044] Compared with the treatment method for phenol- and aromatic hydrocarbon-containing wastewater from direct coal liquefaction described in document A03, the gasification hydrogenation method for phenol-containing wastewater of this invention utilizes the strong adsorption capacity of the hydrogenation refining catalyst for pollutants to improve reaction selectivity and purification reaction depth. Under conditions of high hydrogen partial pressure and low liquid hourly space velocity, it can achieve the effect of deep conversion of multiple pollutants in a single conversion step. Therefore, the process is simple and the conversion efficiency is high. When combined with the hydrocarbon hydrogenation reaction process, the investment is low and the energy consumption is low. Thus, it has significant technical advantages and is a new method that can replace the biochemical treatment process.

[0045] The evaporation method for phenol- and aromatic hydrocarbon-containing wastewater used in this invention can be any reasonable method. For example, the phenol- and aromatic hydrocarbon-containing wastewater can first absorb heat and evaporate into saturated water vapor, and then mix with hydrogen-containing gas to become dry water gas. Alternatively, the phenol- and aromatic hydrocarbon-containing wastewater can be preheated and then injected into high-temperature hydrogen-containing gas for stripping and evaporation, mixing into the gas phase to become dry water gas. The above-mentioned mixing process can be used. The number of nozzles for injecting phenol- and aromatic hydrocarbon-containing wastewater into high-temperature hydrogen-containing gas can be one, two, or more injection points.

[0046] The hydrogenation purification reaction process of this invention can be configured with multiple sub-reaction zones using hydrogenation purification catalysts, and can adopt a working mode of switching between parallel branch reaction zones, or a working mode of receiving fresh wastewater gas feedstock in time periods by using series sub-reaction zones, thereby extending the continuous operation cycle.

[0047] More broadly, this invention can treat wastewater containing phenols and / or aromatics from various sources, and depending on the source, it can simultaneously treat some or all of the following organic components that can be detoxified by hydrogenation purification reactions:

[0048] ① Organic compounds containing heteroatoms, which can be oxygen, nitrogen, sulfur, or metal atoms;

[0049] Oxygen-containing organic compounds, including one or more of phenols, aldehydes, alcohols, ethers, ketones, fluorene, and carboxylic acids;

[0050] Sulfur-containing organic compounds, including one or more of thiophenols, thiols, thioethers, thiophenes, thioindene, and thiofluorene;

[0051] Nitrogen-containing organic compounds include one or more of the following: nitriles, fentanyl, amides, pyrroles, pyridines, anilines, indoles, organic cyanides, quinolines, carbazoles, acridines, acrylonitriles, fluoranthene, azafluorene, and azacarbazoles;

[0052] Heteroatomic metal atoms can be nickel, vanadium, iron, copper, aluminum, lead, etc.;

[0053] Phenol extractant;

[0054] ②Inorganic substances, such as hydrogen cyanide, carbon monoxide, and carbon dioxide.

[0055] This invention is suitable for building new devices or modifying existing devices.

[0056] The method described in this invention has not been reported before.

[0057] Therefore, the first objective of this invention is to provide a method for hydrogenating and purifying the evaporated gas from wastewater containing phenols and / or aromatics.

[0058] The second objective of this invention is to propose a method for combining a hydrocarbon hydrogenation reaction process with a hydrogenation purification reaction process for the evaporated gas from phenol- and aromatic wastewater.

[0059] The third objective of this invention is to propose a purification method suitable for wastewater containing phenols and aromatics produced from direct coal liquefaction.

[0060] The fourth objective of this invention is to propose a method that combines the hydrogenation modification reaction process with the hydrogenation purification reaction process. Summary of the Invention

[0061] This invention discloses a method for hydrogenating and purifying the evaporated gas from wastewater containing phenols and / or aromatics, characterized by comprising the following steps:

[0062] The first wastewater contains pollutant component KC, including phenols and / or aromatics, including or excluding solid particles, including or excluding other pollutant components that can undergo hydrogenation conversion reaction to reduce their molecular electrical conductivity during the hydrogenation purification reaction process R2.

[0063] The heteroatom-containing organic compounds include oxygen-containing organic compounds, and may or may not include nitrogen-containing organic compounds, sulfur-containing organic compounds, and chlorine-containing organic compounds;

[0064] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0065] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0066] The operation method of this invention is generally as follows:

[0067] (1) Primary source of sewage

[0068] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0069] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0070] (2) Wastewater gasification process U2

[0071] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0072] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0073] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil;

[0074] (3) Hydrogenation purification reaction process R2

[0075] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0076] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0077] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0078] The general operating method of this invention is as follows:

[0079] (1) Primary source of sewage

[0080] The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing.

[0081] The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0082] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0083] (2) Wastewater gasification process U2

[0084] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0085] The first wastewater vaporized gas, U2V-1, is a dry gas of water.

[0086] The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil;

[0087] (3) Hydrogenation purification reaction process R2

[0088] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the dry water stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0089] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0090] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0091] The operation method of this invention is generally as follows:

[0092] (1) Primary source of sewage

[0093] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0094] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0095] (2) Wastewater gasification process U2

[0096] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0097] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0098] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil;

[0099] (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2

[0100] The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2.

[0101] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0102] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0103] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content.

[0104] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0105] In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB.

[0106] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0107] The operation method of this invention is generally as follows:

[0108] (1) Primary source of sewage

[0109] The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing.

[0110] The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0111] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0112] (2) Wastewater gasification process U2

[0113] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0114] The first wastewater vaporized gas, U2V-1, is a dry gas of water.

[0115] The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil;

[0116] (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2

[0117] The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2.

[0118] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0119] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0120] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content.

[0121] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0122] In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB.

[0123] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0124] In this invention, typically, the effluent R1P from the hydrocarbon hydrogenation reaction process R1 is a stream containing phenols, aromatics, water, and hydrogen.

[0125] In this invention, typically, the effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1.

[0126] The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1, which is either dry or wet.

[0127] In this invention, typically, (3) a wastewater spray vaporization process WDV is set up;

[0128] In the wastewater spray vaporization process WDV, a liquid water-containing stream of the first wastewater is sprayed into a gas-containing stream based on hot high-density gas R1P-S1V and vaporized to form a stream containing water-dry first wastewater vaporized gas U2-2. The operating temperature of the water-dry first wastewater vaporized gas U2-2 is lower than the operating temperature of the stream R1P-S1V, and condensed oil WDV-L may or may not be generated.

[0129] In this invention, typically, during the wastewater spray vaporization process (WDV), condensed oil (WDV-L) is generated;

[0130] Condensed oil WDV-L, with or without solid particles from primary wastewater.

[0131] In this invention, typically, (3) during the wastewater spray gasification process WDV, condensed oil WDV-L is separated so that it does not undergo the hydrogenation purification reaction process R2.

[0132] In this invention, typically, (3) in the cold high-pressure separation process S7, water-containing and hydrogen-containing gas streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure water separation S7-W.

[0133] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0134] At least a portion of the hydrogen-rich gas stream based on the cold high-density gas S7-V is returned to the hydrogenation purification reaction effluent R2P for recycling.

[0135] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0136] At least a portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling.

[0137] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0138] A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling;

[0139] A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is recycled back to the hydrogenation purification reaction effluent R2P without going through the hydrocarbon hydrogenation reaction process R1.

[0140] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0141] The hydrogen concentration in the cold high-density gas S7-V is 75-98% by volume.

[0142] In this invention, the reaction parameters of R2 in the hydrogenation purification reaction process (3) are generally as follows:

[0143] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic oxygen in the feed hydrocarbon to water is higher than 80%.

[0144] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 80%.

[0145] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 80%.

[0146] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 60%.

[0147] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 70%.

[0148] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0149] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 35% by weight.

[0150] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 15% by weight.

[0151] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 10% by weight.

[0152] In general, the reaction parameters of R2 in the hydrogenation purification reaction process (3) are as follows:

[0153] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic oxygen in the feed hydrocarbon to water is higher than 90%.

[0154] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 90%.

[0155] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 90%.

[0156] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 70%.

[0157] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0158] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 90%.

[0159] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 17.5% by weight.

[0160] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 7.5% by weight;

[0161] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 5.0% by weight.

[0162] In the present invention, preferably, the reaction parameters of R2 in the hydrogenation purification reaction process are as follows:

[0163] In the hydrogenation purification reaction process R2, the organic oxygen in the feed hydrocarbon is hydrogenated to water with a hydrogenation conversion rate of over 98%.

[0164] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 98%.

[0165] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 98%.

[0166] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0167] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 90%.

[0168] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 95%.

[0169] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 9% by weight.

[0170] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 6% by weight.

[0171] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 3% by weight.

[0172] In this invention, the purification index of R2 in the hydrogenation purification reaction process (3) is generally as follows:

[0173] The organic oxygen content in hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight;

[0174] The organic nitrogen content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight;

[0175] The organic sulfur content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 2 ppm by weight.

[0176] In general, the purification index of R2 in the hydrogenation purification reaction process (3) is as follows:

[0177] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 5% by weight.

[0178] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 2% by weight.

[0179] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 1% by weight.

[0180] In this invention, the typical operating conditions for the hydrogenation purification reaction R2 are: pressure of 6–25 MPa, temperature of 220–440 °C, and hydrogen-to-oil ratio of 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

[0181] In general, the operating conditions for the hydrogenation purification reaction R2 in this invention are: pressure of 12-20 MPa, temperature of 270-390°C, and hydrogen-to-oil ratio of 2000-20000 Nm. 3 / t, the liquid hourly space velocity of the hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

[0182] In this invention, the raw material hydrocarbon for the hydrocarbon hydrogenation reaction process R1 is typically a hydrocarbon containing phenols or aromatics, including hydrocarbons with a conventional boiling point higher than 350°C.

[0183] The operating conditions for hydrocarbon hydrogenation reaction R1 are typically: pressure 6–25 MPa, temperature 220–460 °C, and hydrogen-to-oil ratio 100–3000 Nm. 3 / t;

[0184] The operating conditions for the hydrotreating process R2 are typically: pressure 6–25 MPa, temperature 220–440 °C, and hydrogen-to-oil ratio 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

[0185] In this invention, generally, the hydrocarbon feedstock for the hydrocarbon hydrogenation reaction process R1 is a hydrocarbon containing phenols or aromatics, including hydrocarbons with a conventional boiling point higher than 350°C.

[0186] The operating conditions for hydrocarbon hydrogenation reaction R1 are generally: pressure 12–20 MPa, temperature 320–440 °C, and hydrogen-to-oil ratio 200–2000 Nm. 3 / t;

[0187] (3) The operating conditions for the hydrogenation purification reaction R2 are generally: pressure 12-20 MPa, temperature 270-390℃, and hydrogen-to-oil ratio 2000-20000 Nm. 3 / t, the liquid hourly space velocity of the hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

[0188] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0189] Cold high-water fraction S7-W has a phenol content of less than 10 ppm and an aromatic hydrocarbon content of less than 200 ppm.

[0190] In general, in the present invention, (3) in the cold high-pressure separation process S7, hydrogen-containing gas, water-containing and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W and cold high-pressure oil S7-L.

[0191] Cold high-water fraction S7-W has a phenol content of less than 5 ppm and an aromatic hydrocarbon content of less than 50 ppm.

[0192] In this invention, generally, (2) in the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V;

[0193] In the first oil washing process U3, the material U2V-1VB based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil U3-AL at least once to obtain the first post-wash gas U3-PV and the first post-wash oil U3-PL.

[0194] The amount of solids in the gas phase U3-V after the first wash is less than the amount of solids in the gas phase of the stream U2V-1VB.

[0195] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0196] At least a portion of the logistics based on cold high-separation oil S7-L is recycled as washing oil U3-AL.

[0197] In this invention, typically, (3) the gas-containing stream R2P-VB based on the hydrogenation purification reaction effluent R2P is mixed with the quenched stream KS and cooled to a temperature below the water dew point to form a mixed-phase material R2P-VB-2 containing gas and liquid phases.

[0198] The mixed-phase material R2P-VB-2 contains an aqueous phase with dissolved ammonia components.

[0199] In this invention, typically, (3) the quenched stream KS is quenched hydrogen-rich gas and / or quenched oil and / or quenched water.

[0200] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0201] The quenched logistics KS is based on quenched hydrogen-rich gas from the high-density gas separator S7-V, and / or quenched oil from the high-density oil separator S7-L, and / or quenched water from the high-density water separator S7-W.

[0202] In this invention, generally, (3) the hydrocarbon hydrogenation reaction process R1, the feedstock hydrocarbon R1F is obtained by separating coal hydrogenation and direct liquefaction to produce distilled oil, the hydrocarbon hydrogenation reaction process R1 undergoes partial hydrogenation saturation reaction of bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons, and the hydrogen supply index of hydrocarbons with conventional boiling points above 200℃ in the reaction effluent R1P of the hydrocarbon hydrogenation reaction process R1 is higher than the hydrogen supply index of hydrocarbons with conventional boiling points above 200℃ in the feedstock hydrocarbon R1F;

[0203] Hydrogen-rich hydrocarbon oil obtained from the hydrotreating effluent R1P is used as a hydrogen-donating solvent to prepare coal oil slurry with coal powder. This slurry is then converted into coal hydrotreating direct liquefaction effluent through the coal hydrotreating direct liquefaction reaction process.

[0204] The effluent from the direct liquefaction reaction of coal hydrogenation is separated to obtain distillate oil based on the oil produced by direct liquefaction of coal hydrogenation, which is used as feedstock oil R1F for the hydrocarbon hydrogenation reaction process R1.

[0205] The process of separating the effluent from the direct liquefaction reaction of coal hydrogenation yields initial wastewater containing phenols and aromatics.

[0206] Based on the initial phenol- and aromatic-containing wastewater, the first wastewater was obtained.

[0207] In this invention, typically, (1) the first source of wastewater

[0208] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone a wastewater pretreatment process;

[0209] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal.

[0210] In this invention, (1) the first wastewater is an aqueous solution containing phenols and aromatic hydrocarbons, and contains chloride ions and / or fluoride ions.

[0211] In this invention, typically, (2) the wastewater gasification process U2

[0212] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0213] During the cooling and condensation process U203, the first wastewater vaporized gas U2V-1 is separated into dry water gas U203-V and condensed oil U203-L.

[0214] In this invention, typically, during the heating process U204, the dry water gas U203-V absorbs heat and heats up to become the preheated gas U203-V2;

[0215] After preheating, the gas U203-V2 enters the hydrogenation purification reaction process R2.

[0216] In this invention, typically, (2) the wastewater gasification process U2

[0217] The first wastewater vaporized gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics.

[0218] In the oil washing process KU52, the gas based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil KU52-LF at least once to obtain the washing gas KU52-VP and the washing oil KU52-LP with lower dust content and / or lower high-boiling phenol content and / or lower high-boiling aromatic content. The washing gas then enters the hydrogenation purification reaction process R2.

[0219] At least a portion of the wash oil KU52-LF comes from the condensate oil separated during the separation process before the washed gas KU52-VP enters the hydropurification reaction process R2, or from the hydrocarbon oil obtained from the separation of the hydropurification reaction effluent R2P.

[0220] In this invention, (3) in the hydrogenation purification reaction process R2, two parallel-operating first-branch hydrogenation purification reaction processes R2B1 and second-branch hydrogenation purification reaction processes R2B2 can be set up.

[0221] When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, most to all of the material entering the first branch hydrogenation purification reaction process R2B1 will be introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction, so as to extend the continuous operation cycle.

[0222] In this invention, (3) in the hydrogenation purification reaction process R2, two parallel-operating first-branch hydrogenation purification reaction processes R2B1 and second-branch hydrogenation purification reaction processes R2B2 can be set up.

[0223] When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, all the material entering the first branch hydrogenation purification reaction process R2B1 is introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction. The first branch hydrogenation purification reaction process R2B1 is isolated from the feed system of the upstream material U2V-1B, but hot hydrogen-rich gas is introduced for flow to maintain the operating temperature of the first branch hydrogenation purification reaction process R2B1 within a reasonable range.

[0224] In this invention, (3) in the hydrogenation purification reaction process R2, two and / or more catalyst beds operating in series can be set to form two or more sub-region hydrogenation purification reaction processes operating in series.

[0225] According to the timeline, in the first stage, the logistics U2V-1B undergoes the first sub-zone hydrogenation purification reaction process R201, while ensuring that each other sub-zone has at least hot hydrogen-rich gas flowing through to maintain the operating temperature within a reasonable range.

[0226] According to the timeline, in the second stage, when the catalyst operating conditions of the first sub-region hydrogenation purification reaction process R201 are in the final stage, part of the total flow U2V-1B entering the first hydrogenation purification reaction process R201 is introduced into the second sub-region hydrogenation purification reaction process R202 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the first sub-region hydrogenation purification reaction process R201 to maintain the temperature of the first hydrogenation purification reaction process R201 within a reasonable range.

[0227] When the hydrogenation purification reaction process R2 is set with three or more catalyst beds operating in series, according to the time progress, in the third stage, when the catalyst operating conditions of the second sub-region hydrogenation purification reaction process R202 are in the final state, part of the total flow U2V-1B entering the second hydrogenation purification reaction process R202 is introduced into the third sub-region hydrogenation purification reaction process R203 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the second sub-region hydrogenation purification reaction process R202 to maintain the temperature of the second hydrogenation purification reaction process R202 within a reasonable range.

[0228] This process continues until the catalyst operating conditions of the final sub-region hydrogenation purification reaction process R209 are in the final stage, at which point a complete operating cycle is completed. The hydrogenation purification reaction process R2 then enters a shutdown step or a low-load operation step that reduces the first wastewater treatment volume.

[0229] In this invention, typically, (3) during the hydrogenation purification reaction process R2, when the processing stream U2V-1B is processed in the sub-region hydrogenation purification reaction process R20M, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged from the hydrogenation purification reaction process R2 as the hydrogenation purification reaction product R2P without passing through other sub-region hydrogenation purification reaction processes.

[0230] Meanwhile, the hydrogenation purification reaction processes of other hydrogenation purification reaction processes R2, except for the sub-region hydrogenation purification reaction process R20M, do not receive either the stream U2V-1B or the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M. Only other hot, water-poor hydrogen-rich gas flows through.

[0231] In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell and connected in the gas phase space.

[0232] The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

[0233] In this invention, typically, (3) in the first stage of the hydrogenation purification reaction process R2, when the first sub-region hydrogenation purification reaction process R201 processes the stream U2V-1B, the reaction product R201P of the first sub-region hydrogenation purification reaction process R201 is discharged from the hydrogenation purification reaction process R2 after passing through all the other sub-region hydrogenation purification reaction processes located downstream, and is used as the hydrogenation purification reaction product R2P.

[0234] When the sub-region hydrogenation purification reaction process R20M processes the stream U2V-1B, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged after passing through the downstream sub-region hydrogenation purification reaction process R2, and is used as the hydrogenation purification reaction product R2P.

[0235] Meanwhile, all sub-region hydrogenation and purification reaction processes located upstream of sub-region hydrogenation and purification reaction process R20M do not receive stream U2V-1B; only other hot, water-deficient, hydrogen-rich gas flows through them. Sub-region hydrogenation and purification reaction process R20M receives the effluent from the upstream sub-region hydrogenation and purification reaction process.

[0236] In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell.

[0237] The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

[0238] In this invention, typically, the hydrocarbon feed for the hydrogenation reaction process R1 (3) contains one or more of the following fractions:

[0239] ① Hydrocarbons with a conventional boiling point of 200–350℃, including phenols and / or aromatics;

[0240] ② Hydrocarbons with a conventional boiling point of 350–450℃, including phenols and / or aromatics;

[0241] ③ Hydrocarbons with a conventional boiling point of 450–550℃, including phenols and / or aromatics;

[0242] The hydrogenation reaction process R1 is either a fluidized bed hydrogenation reaction process or a suspended bed hydrogenation reaction process.

[0243] The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

[0244] In this invention, the hydrocarbon feed for the hydrogenation reaction process R1 is typically a hydrocarbon stream obtained from the direct liquefaction reaction product of coal hydrogenation, mainly composed of hydrocarbons with conventional boiling points of 150-550℃, including phenols and aromatics.

[0245] The hydrogenation reaction process R1 is a fluidized bed hydrogenation reaction process and a suspended bed hydrogenation reaction process.

[0246] The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

[0247] In this invention, typically, the operating temperature of the first wastewater vaporized gas U2V-1 obtained from the wastewater vaporization process U2 is at least 30°C higher than the water dew point;

[0248] (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 50°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 6.0~18.0MPa.

[0249] In general, the operating temperature of the first wastewater vaporized gas U2V-1 obtained from the wastewater vaporization process U2 in the present invention is at least 30°C higher than the water dew point;

[0250] (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 70°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 9.0~14.0MPa.

[0251] In this invention, typically, (3) in the hot high-pressure separation process S1, the reaction effluent R1P of the hydrogenation reaction process R1 is separated to obtain hot high-pressure gas S1-V and hot high-pressure oil S1-L.

[0252] The hydrocarbon stream S1-L-TOR2 obtained from separating the hot high-density oil S1-L enters the hydropurification reaction process R2;

[0253] Hydrocarbon stream S1-L-TOR2 is mainly composed of hydrocarbons with conventional boiling points below 250℃ and / or hydrocarbons with boiling points between 250℃ and 320℃.

[0254] In this invention, typically, a clean hydrocarbon stream KEYS containing hydrocarbon components with a conventional boiling point of 300-350°C undergoes a hydrogenation purification reaction process R2, during which at least a portion of the clean hydrocarbon stream KEYS remains in a liquid phase.

[0255] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0256] The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX for heat recovery and becomes the stream K-HX-HP. The weight flow rate of the liquid water component in the stream K-HX-HP is not less than 85% of the weight flow rate of the water component in the cold high-pressure water S7-W.

[0257] After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

[0258] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0259] The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX for heat recovery and becomes the stream K-HX-HP. The temperature of the stream K-HX-HP is not higher than 150-170℃.

[0260] After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

[0261] In this invention, (2) the washing oil U3-AL can be a component of heavy diesel oil with a conventional boiling point of 250-350℃.

[0262] In this invention, (2) the washing oil KU52-LF can be a component of heavy diesel oil with a conventional boiling point of 250-350℃.

[0263] The operation method of this invention can be: (1) a first source of wastewater

[0264] The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It is wastewater that has undergone or has not undergone wastewater pretreatment.

[0265] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0266] (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

[0267] The operation method of this invention can be: (1) a first source of wastewater

[0268] The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It is wastewater that has undergone or has not undergone wastewater pretreatment.

[0269] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0270] (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

[0271] The operation method of this invention can be: (1) a first source of wastewater

[0272] The first type of wastewater, which may or may not contain solid particles, is the initial wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0273] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0274] (2) Wastewater gasification process U2

[0275] In the first wastewater light oil desolidification process, the first wastewater is mixed and contacted with the first desolidified hydrocarbon oil feedstock, and then separated into the first desolidified rich oil and the first desolidified wastewater.

[0276] The solid content in the first desolidified rich oil is higher than the solid content in the first desolidified hydrocarbon oil feedstock;

[0277] The solid content in the first wastewater with reduced solids is lower than the solid content in the first wastewater.

[0278] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first solids-degrading wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0279] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0280] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil.

[0281] The operation mode of the present invention may be as follows: (2) In the first wastewater light oil desolidification process, the first desolidified hydrocarbon oil feedstock is hydrocarbon oil based on the condensed oil of the wastewater gasification process U2, and / or is hydrocarbon oil obtained by separating the hydrogenation purification reaction effluent R2P.

[0282] The first step is to remove solids from the oil, which is a process of removing solids before entering the desulfurization and deammoniation process.

[0283] In the pre-solids removal process before the desulfurization and deammoniation process, the oil-rich stream based on the first solids removal process is mixed and contacted with the pre-sewage stream based on the initial wastewater, and then separated into pre-solids-rich oil-rich stream and pre-solids-reducing wastewater.

[0284] The solid content in the pre-desolidation rich oil is higher than that in the first desolidation rich oil;

[0285] The solid content in the pre-treatment solids-reducing wastewater is lower than the solid content in the pre-treatment wastewater stream;

[0286] Based on the logistics of pre-treated solid wastewater, it undergoes the first wastewater light oil desolidification process.

[0287] In this invention, the operation method can be as follows: (3) The effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1; the hot high-pressure oil R1P-S1L contains solid particles.

[0288] The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1, which is either dry or wet.

[0289] During the separation and fractionation process of FRAC80, the hot high-separation oil R1P-S1L is separated into gas, narrow-separation oil, and separation bottom oil FRAC80-DV containing solid particles;

[0290] Based on the pre-solidification rich oil stream, it enters the separation and fractionation process FRAC80 and is mixed and separated with the hot high-separation oil stream R1P-S1L to form narrow-separation oil products. The solid particles contained in the pre-solidification rich oil stream enter the separation bottom oil FRAC80-DV.

[0291] The operation mode of this invention can be: (3) In the hydrogenation purification reaction process R2, other hydrocarbons P600, which mainly contain phenols and / or aromatics with conventional boiling points below 350°C, are processed together.

[0292] Hydrocarbons P600, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

[0293] The operation mode of this invention can be: (3) In the hydrogenation purification reaction process R2, other hydrocarbons P700, mainly composed of phenols and / or aromatics with conventional boiling points below 250°C, are processed together.

[0294] Hydrocarbons P700, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

[0295] In this invention, the operation method can be as follows: (3) The reaction effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1.

[0296] The main hydrocarbons obtained from the separation of hot high-temperature oil R1P-S1L are phenolic and / or aromatic hydrocarbons with conventional boiling points below 250℃, which are then processed in the hydrogenation purification reaction process R2.

[0297] The operation mode of this invention can be as follows: (1) The first source of wastewater is wastewater with low chloride ion content, selected from the top water of the fractionation tower and the vacuum tower of the coal hydrogenation direct liquefaction to produce oil, the top water of the fractionation tower of the coal hydrogenation direct liquefaction to produce oil through hydrogenation modification, and acidic water from gas fractionation.

[0298] The operation mode of this invention can be: (3) Hydrocarbon hydrogenation reaction process R1 is a hydrogenation and upgrading reaction process of direct coal liquefaction oil or hydrogenated modified oil of direct coal liquefaction oil.

[0299] The operation mode of this invention can be: (2) wastewater gasification process U2

[0300] The first wastewater vaporization gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics. Based on the gas of the first wastewater vaporization gas U2V-1, after cooling, condensation, separation and deliquescence process KU51 and / or oil washing and deliquescence process KU52, a gas with lower dust content and / or lower high-boiling-point phenol content and / or lower high-boiling-point aromatic content is obtained and enters the hydrogenation purification reaction process R2. Detailed Implementation

[0301] The present invention will now be described in detail.

[0302] The pressure described in this invention is equivalent to the standard physical term pressure, which refers to absolute pressure.

[0303] The conventional boiling point mentioned in this invention refers to the vapor-liquid equilibrium temperature of a substance under one atmosphere of pressure.

[0304] The conventional boiling range mentioned in this invention refers to the conventional boiling point range of the distillate.

[0305] Unless otherwise specified, the specific gravity mentioned in this invention refers to the ratio of the density of the liquid at normal pressure and 15.6°C to the density of water at normal pressure and 15.6°C.

[0306] Unless otherwise specified, the composition, concentration, content, or yield of the components described in this invention are all weight-based values.

[0307] The conventional gaseous hydrocarbons mentioned in this invention refer to hydrocarbons that are in a gaseous state under normal conditions, including methane, ethane, propane, and butane.

[0308] The conventional liquid hydrocarbons described in this invention refer to hydrocarbons that are liquid under normal conditions, including pentane and hydrocarbons with higher boiling points.

[0309] The impurity elements mentioned in this invention refer to non-hydrogen, non-carbon, and non-metallic components in the raw oil, such as oxygen, sulfur, nitrogen, and chlorine.

[0310] The impurity components mentioned in this invention refer to the hydrogenation conversion products of non-hydrocarbon components in the feedstock oil, such as water, ammonia, hydrogen sulfide, and hydrogen chloride.

[0311] The light hydrocarbons mentioned in this invention are naphtha components, referring to conventional liquid hydrocarbons with a boiling point below 200°C.

[0312] The medium-quality hydrocarbons mentioned in this invention are diesel fuel components, referring to hydrocarbons with a conventional boiling point of 200–350°C.

[0313] The wax oil component described in this invention refers to hydrocarbons with a conventional boiling point of 350–530°C.

[0314] The hydrogen-oil volume ratio mentioned in this invention refers to the ratio of the standard state volumetric flow rate of hydrogen to the volumetric flow rate of a specified oil stream at atmospheric pressure and 20°C.

[0315] The coal direct liquefaction reaction process AR described in this invention refers to a one-step process for producing oil products from raw coal. It can be a coal direct liquefaction reaction process with high hydrogen consumption, such as higher than 5.0% by weight (to the raw coal), like the coal hydrogenation direct liquefaction reaction process, or a coal direct liquefaction reaction process with low hydrogen consumption, such as lower than 2.5% by weight (to the raw coal), like the coal thermal liquefaction reaction process or the coal thermal cracking reaction process. The coal direct liquefaction reaction process AR uses ferrous coal direct liquefaction catalysts or non-ferrous coal direct liquefaction catalysts, and its operating pressure can be as high as 17-25 MPa or only 1.0-2.5 MPa. The operating temperature of the reaction process R100 can typically reach 400-465℃.

[0316] The coal direct liquefaction reaction process (AR) described in this invention, regardless of the chemical hydrogen consumption during the reaction, results in the distillate oil of conventional liquid hydrocarbons obtained from the separation of the oil produced by the coal direct liquefaction reaction. This oil is referred to as coal direct liquefaction oil, and all of it belongs to hydrocarbon oils with a high aromatic carbon content (typically higher than 0.40, generally higher than 0.66, and even higher than 0.8), i.e., high aromatic hydrocarbon oils. Due to the wide distribution of carbon numbers in the hydrocarbon products of the coal direct liquefaction reaction, depending on the selected distillation range, the coal direct liquefaction oil can be a conventional boiling range below 560℃, i.e., containing conventional aromatic hydrocarbons. Coal direct liquefaction oil typically contains six-ring aromatics with a boiling point of 500–560℃. It can also contain polycyclic aromatic hydrocarbons with seven or more rings, typically with a boiling point of 560–650℃. Hydrocarbons with a boiling point above 650℃ in coal direct liquefaction oil usually belong to heavy residue oil components, and typically constitute the bottom oil of distillation in the unevaporated oil during the fractionation process.

[0317] Since coal powder can participate in the reaction in the form of coal-oil slurry, the basic conditions for direct coal liquefaction, such as coal powder dispersion, hydrocarbon molecule diffusion, hydrogen molecule dissolution, and catalyst dispersion, can be achieved. Therefore, the direct coal liquefaction process AR is also called the direct coal-oil slurry liquefaction process R100.

[0318] The coal direct liquefaction reaction process (AR) described in this invention refers to a reaction process in which coal and potentially present molecular hydrogen are used as raw materials, and a specific oil (usually coal direct liquefaction oil or hydrotreated coal direct liquefaction oil) is used as a solvent oil. Under certain operating conditions (such as operating temperature, operating pressure, solvent oil / coal weight ratio, hydrogen / solvent oil volume ratio, and a suitable hydrogenation catalyst), coal directly undergoes carbon-carbon bond thermal cracking, free radical hydrogenation modification, hydrocarbon oil hydrorefining, and hydrocarbon oil hydrocracking, resulting in hydrogenation liquefaction.

[0319] The coal direct liquefaction oil described in this invention refers to the distillate oil obtained by separating the oil produced in the direct coal hydrogenation liquefaction reaction. It exists in the effluent of the direct coal hydrogenation liquefaction reaction and is a comprehensive reaction product based on solvent oil, coal consumed in the reaction, and hydrogen transferred in the reaction. It can be a mixture of at least two of the following: a conventional boiling point <195℃ fraction, a boiling point between 195℃ and 280℃, a boiling point between 280℃ and 560℃, and a boiling point between 560℃ and 650℃. It can be any boiling point within the range of 195℃ to 650℃, but is usually any boiling point within the range of 195℃ to 560℃.

[0320] Depending on the source of the raw coal and the conditions of the direct coal liquefaction reaction, the hydrogen content, aromatic carbon content, organic nitrogen content, organic oxygen content, and yield of the fraction above 350℃ vary considerably from source to source. Typically, the hydrogen content is 5.0–11.2 wt%, the aromatic carbon content is 0.23–0.98 mol%, the organic nitrogen content is 0.20–1.5 wt%, the organic oxygen content is 0.40–6.30 wt%, the yield of the fraction above 350℃ is 15–65 wt%, and the yield of the fraction above 500℃ is 5–25 wt%.

[0321] The hydromodification reaction process BR of direct coal liquefaction oil described in this article refers to the hydromodification reaction process that converts direct coal liquefaction oil into hydrocarbons with lower aromatic carbon content and lower impurity element content. Examples include the production of hydrotreated feedstock oil, hydrogen-donating solvent oil, hydromodified oil with specific impurity content, hydromodified oil with specific aromatic carbon content, and hydromodified oil with specific boiling range fractions. The hydromodification reaction produces oils with different boiling range fractions, which are then blended to obtain oils for different applications, such as the hydrogen-donating solvent oil entering the direct coal liquefaction reaction process AR. This hydrogen-donating solvent oil typically has a hydrogen supply index (PDQI) greater than 22 mg / g and generally greater than 24 mg / g. The hydrogen-donating solvent oil is usually used as a solvent oil for coal slurry blending, flushing oil for the plunger rod stuffing box of a plunger-type feedstock coal slurry pump, flushing oil for high-pressure instruments, and flushing oil for pipelines, and passes through at least a portion of the reaction space in the direct coal hydrochemical liquefaction reaction process R100.

[0322] The hydrotreating and upgrading process (CR) of direct coal liquefaction oil described in this article refers to the process of using narrow-fraction oils from direct coal liquefaction oil and / or hydrotreating and upgrading reaction products of direct coal liquefaction oil as raw materials, and carrying out at least a deep hydrorefining reaction, possibly followed by a selective hydroring-opening reaction, or even a hydrocracking reaction. The quality indicators of the hydrotreated oil produced are determined as needed, typically with an organic nitrogen content of less than 3-10 ppm by weight, an organic sulfur content of less than 5-20 ppm by weight, and an aromatic content determined as needed.

[0323] The aromatic carbon ratio of hydrocarbons refers to the ratio of the number of aromatic carbon atoms to the total number of carbon atoms in a hydrocarbon molecule.

[0324] The hydrogen supply index (PDQI) of hydrocarbons refers to the number of milligrams of active hydrogen at the β-position of cycloalkyl groups in each gram of cycloalkyl aromatic hydrocarbons.

[0325] For mixtures of aromatic hydrocarbons composed of various hydrocarbons with different boiling points, such as direct coal liquefaction oil or oil produced by the hydrotreating reaction of direct coal liquefaction oil, there is a macroscopic correspondence between the hydrogen supply index (PDQI) of hydrocarbons and their aromatic carbon content.

[0326] The gas holdup of the stream in the hydrogenation modification reactor refers to the volume ratio of the gas phase in the stream.

[0327] The liquid holdup of the stream in the hydrogenation modification reactor refers to the volume ratio of the liquid phase in the stream.

[0328] The hydrogen-to-oil ratio described in this invention can be the ratio of the standard-state volumetric flow rate of the hydrogen-rich gas stream to the weight of the feedstock oil, expressed in standard cubic meters per ton (Nm³). 3 / t.

[0329] The hydrogen / oil volume ratio in the hydrotreating reactor described in this invention refers to the ratio of the standard-state volumetric flow rate of the hydrogen-rich gas stream to the standard-state volume of the feed oil, expressed in standard cubic meters per cubic meter (Nm³). 3 / m 3 .

[0330] The hydrogen / oil volume ratio at a certain point in the hydrotreating reactor described in this invention refers to the ratio of the standard state volumetric flow rate of the gas phase to the standard state volume of the liquid, expressed in standard cubic meters per cubic meter (Nm³). 3 / m 3 .

[0331] The liquid hourly space velocity (LHSV) of the catalyst in the hydrotreating reactor described in this invention refers to the ratio of the volumetric flow rate of the fresh feedstock at 0.1 MPaA and 20°C to the static stacked volume of the hydrotreating catalyst, expressed in hours (h). -1 .

[0332] A common direct coal liquefaction reaction process (AR) can be the direct coal hydrogenation liquefaction reaction process (R100).

[0333] The hydrogenation modification process BR of coal direct liquefaction oil can be the hydrogenation modification process of the solvent oil used to produce high aromatic oil from coal hydrogenation direct liquefaction, also known as the solvent oil hydrogenation modification process.

[0334] For coal direct liquefaction oil with shallow hydrogenation depth and low chemical hydrogen consumption, the polarity and viscosity of the coal direct liquefaction oil are stronger, resulting in more entrained solid particles. Therefore, a fluidized bed hydrogenation modification reaction method must be adopted. At the same time, its aromatic carbon content and heteroatom content are higher. When the hydrogenation modification reaction process (BR) produces hydrogenated oil with a low aromatic carbon content, the chemical hydrogen consumption is higher and the amount of heteroatom hydrogenation products is higher. Its operation method is completely different from the conventional hydrogenation modification reaction process (BR) of coal direct liquefaction with high hydrogen consumption and low impurity hydride production to produce high aromatic oil. It requires a multi-stage or multi-stage hydrogenation modification reaction process (BR).

[0335] The hydrogen-donating hydrocarbons described in this invention refer to partially saturated bicyclic aromatic hydrocarbons and partially saturated polycyclic aromatic hydrocarbons (PAHs), hydrocarbon components with hydrogen-donating functions in the direct coal hydrogenation to oil production process. These hydrogen-donating hydrocarbons, including partially saturated bicyclic aromatic hydrocarbons and partially saturated PAHs, are ideal components for hydrogen-donating solvent oils used in the direct coal hydrogenation liquefaction process. Among the hydrogen-donating hydrocarbons, the hydrogen-donating rate of dihydrogenases is generally greater than that of tetrahydrogenases. The hydrogen-donating rates of dihydrogenases of tricyclic aromatic hydrocarbons and bicyclic aromatic hydrocarbons vary. Experiments have shown that although PAHs do not have hydrogen-donating capabilities, they do have hydrogen-transfer capabilities.

[0336] The hydrogen-donating solvent oil mentioned in this article refers to a hydrocarbon oil rich in hydrogen-donating hydrocarbons that has hydrogen-donating capacity in the direct liquefaction reaction process of coal hydrogenation (R100).

[0337] The coal hydrogenation direct liquefaction reaction process R100 described in this invention refers to a method for the direct hydrogenation liquefaction of coal through hydrogenation in the presence of solvent oil. Depending on the solvent oil, catalyst, and hydrogenation process conditions, there are various different processes, such as the following:

[0338] ① Solvent hydrogenation extraction liquefaction method: such as solvent refining coal method I and II (SRC-I and SRC-II), hydrogen-supplying solvent oil method EDS, Japan New Energy Development Organization liquefaction method (NEDOL), etc., use hydrogen, but the pressure is not very high, and solvent oil has a significant effect;

[0339] ② High-pressure catalytic hydrogenation: such as the old and new liquefaction processes in Germany (IG and NewIG) and the hydrogen coal process in the United States (H-Coal) belong to this category;

[0340] ③ Coal and residual oil co-processing: Residual oil is used as a solvent oil and passed through the reactor together with coal in one pass, without the need for circulating oil; the residual oil undergoes hydrocracking to convert it into light oil. Different processes exist in the United States, Canada, Germany, and the Soviet Union, among others.

[0341] ④ China Shenhua Group's direct coal liquefaction method;

[0342] ⑤ Patent CN100547055C discloses a thermal dissolution catalytic method for producing liquid fuel from lignite, belonging to the medium-pressure hydrogenation direct liquefaction process of lignite, including two processes: the coal hydrogenation direct liquefaction reaction process R100 and the coal direct liquefaction oil hydrogenation modification process. In order to improve the conversion rate of direct coal liquefaction and to enable the coal feedstock to enter the coal hydrogenation direct liquefaction reactor, the coal is usually made into coal powder before entering the coal hydrogenation direct liquefaction reactor, and then mixed with solvent oil with good hydrogen supply capacity to form an oil-coal slurry. The oil-coal slurry is pressurized and heated before entering the coal hydrogenation direct liquefaction reactor.

[0343] In the process of direct coal hydrogenation liquefaction, regardless of the specific type of direct coal hydrogenation process, the goal is to obtain oil products, and the desired function is "coal-to-oil conversion." The necessary chemical change is "coal hydrogenation." Currently, these technologies share the common characteristics of using solvent oil and catalysts. The typical boiling range of the solvent oil is generally 195–530℃, with most ranging from 195–450℃. Most solvent oils are distilled oils or their hydrogenated modified forms, and the aromatics they contain are mostly 2–4 ring structures, with a small amount of 5-ring structures. Therefore, regardless of the type of direct coal hydrogenation process, the resulting effluent oil, direct coal liquefaction oil (usually light oil from direct coal hydrogenation liquefaction), or stabilized direct coal liquefaction oil, as long as its composition possesses the characteristics of the raw material composition described in this invention, can be processed using the method of this invention.

[0344] In a macroscopic sense, the coal hydrogenation direct liquefaction reaction process R100 is not only a direct liquefaction reaction process of coal carried by coal slurry, but also a hydrogen supply process (or dehydrogenation process) of hydrogen-donating solvent oil carried by coal slurry, and a hydrocracking reaction process that reduces the carbon number of hydrocarbon components (such as conventional hydrocarbons with a boiling point above 290℃) in the net product oil of coal hydrogenation direct liquefaction.

[0345] The coal direct liquefaction oil refers to the distillate obtained by separating the oil produced in the coal hydrogenation direct liquefaction reaction. It exists in the effluent of the coal hydrogenation direct liquefaction reaction and is a comprehensive reaction product based on hydrogen-donating solvent oil, coal consumption in the reaction, and hydrogen transfer in the reaction. According to the number of aromatic ring structures, it includes the fraction with a conventional boiling point <195℃ (the most abundant aromatic ring is monocyclic aromatic hydrocarbon), the fraction with a boiling point of 195℃ to 280℃ (the most abundant aromatic ring is dicyclic aromatic hydrocarbon), and the fraction with a boiling point of 280℃ to 540℃ (the most abundant aromatic ring is polycyclic aromatic hydrocarbon). It can be a mixture of oil products with one, two, or more different properties.

[0346] The fraction of coal direct liquefaction oil with a conventional boiling point below 195℃, or the oil produced by its hydromodification reaction, is generally not considered a candidate solvent oil for coal slurry or a hydrogen donor in the R100 distillate of the coal hydromodification reaction process. This is because the proportion of R100 distillate oil evaporating into the gas phase during the coal hydromodification reaction is too high. The fraction of coal direct liquefaction oil with a conventional boiling point below 195℃ generally does not contain aromatic rings with two-ring structures, such as tetrahydronaphthalene, dihydronaphthalene, and naphthalene. Therefore, it does not possess the aromatic ring structure required for hydromodification to produce hydrogen-donating hydrocarbons.

[0347] The conventional boiling point range of direct coal liquefaction oil is 280℃ to 540℃, and the aromatics it contains are mainly polycyclic aromatic hydrocarbons.

[0348] The conventional boiling point of coal direct liquefaction oil is the 280℃~370℃ distillation range, which contains tricyclic aromatic hydrocarbons.

[0349] The conventional boiling point of coal direct liquefaction oil is the 370℃~470℃ distillation range, which contains tetracyclic aromatic hydrocarbons.

[0350] The conventional boiling point of coal direct liquefaction oil is the 470℃~525℃ distillation range, which contains pentacyclic aromatic hydrocarbons.

[0351] The conventional boiling point of coal direct liquefaction oil is the 525℃~550℃ fraction, which contains hexacyclic aromatic hydrocarbons.

[0352] Typically, direct coal liquefaction oil contains a certain amount of aromatics with five or more rings and gums. These exist in fractions with a conventional boiling point >470℃. In order to prevent the deterioration of the properties of the feedstock oil in the hydromodification reaction process, their content is generally controlled at a low value, usually 4 to 9% by weight of the total feedstock oil. The presence of these substances will accelerate the coking rate of the hydromodification catalyst in the BR process.

[0353] After the coal hydrogenation direct liquefaction process R100 is operating normally, the hydrogen supply solvent oil is usually a hydrogenated modified oil of the coal direct liquefaction oil (usually a distillate oil with a conventional boiling range above 200℃) produced by the coal hydrogenation direct liquefaction process R100 itself. The main goal of the coal direct liquefaction oil hydrogenation modification process BR is to produce a slurry solvent oil for the coal slurry used as feedstock in the coal hydrogenation direct liquefaction reaction. Specifically, it is to increase the content of "components with good hydrogen supply function" in the oil, such as increasing the content of cycloalkylbenzenes and bicycloalkylbenzenes. Based on the fact that coal direct liquefaction oil contains a large amount of bicyclic aromatics and a large amount of polycyclic aromatics, the coal direct liquefaction oil hydrogenation modification process BR is a "moderate aromatic hydrogenation saturation reaction process" of bicyclic aromatics and polycyclic aromatics.

[0354] The ultimate goal of the coal hydrotreating direct liquefaction process R100 is to produce petroleum products for external supply. Typically, the hydromodified oil produced by the coal hydrotreating process BR is divided into two parts: one part is used as the hydrogen-donating solvent oil for the coal hydrotreating process R100, and the other part is used as waste oil from the coal hydrotreating process. Generally, at least a portion of the coal hydrotreating light oil produced by the coal hydrotreating process R100 is used as waste oil A in the coal-to-oil process. The remaining coal hydrotreating oil is used as feedstock for the coal hydrotreating process BR to produce hydrogen-donating solvent oil and waste oil B for the coal hydrotreating process R100. At this point, there are two waste oil streams, A and B. The final destination of both streams is usually to undergo the hydrotreating process CR to produce high-quality petroleum products such as diesel fractions and naphtha fractions.

[0355] The following describes the general principles for controlling the concentration of gaseous hydrogen sulfide in the hydrogenation reaction process of the present invention.

[0356] For heavy oil suspended bed hydrocracking processes with high nitrogen and low sulfur content, in order to maintain the minimum hydrogen sulfide partial pressure at the start of the reaction, any supplementary sulfur can be added to any hydrocracking reaction process as needed. However, it is usually added to the inlet of the most upstream hydrocracking reaction process to ensure the minimum required hydrogen sulfide concentration, such as 500 ppm(v), 1000 ppm(v), or 3000 ppm(v), etc., is maintained. This ensures that the required hydrogen sulfide partial pressure of the catalyst is not lower than the minimum specified value, thus guaranteeing the required sulfidation form of the catalyst. The supplementary sulfur can be a material containing hydrogen sulfide or that can be converted to hydrogen sulfide without adverse effects on the hydrocracking process, such as hydrogen sulfide-containing gases or oils, or liquid sulfur, carbon disulfide, or dimethyl disulfide that generates hydrogen sulfide upon contact with high-temperature hydrogen.

[0357] The general principles of the high-pressure separation process of the hydrogenation reaction effluent of the present invention are described in detail below.

[0358] The high-pressure separation process of hydrotreating effluents typically includes a cold high-pressure separator. When the hydrocarbon oil in the hydrotreating effluent has a high density (e.g., close to that of water), high viscosity, is difficult to separate from water emulsions, or contains solid particles, a hot high-pressure separator, typically operating at 150–450°C, is also required. In this case, the hydrotreating effluent enters the hot high-pressure separator and is separated into a hot high-pressure gas component, primarily composed of hydrogen, and a hot high-pressure oil component, primarily composed of conventional liquid hydrocarbons and any solids present. The hot high-pressure gas component then enters a cold high-pressure separator, typically operating at 20–80°C, where it is separated into a cold high-pressure oil component and a cold high-pressure gas component. Because a large amount of high-boiling-point components enter the hot high-pressure oil component, the following objectives are achieved: the density or viscosity of the cold high-pressure oil component decreases, or it becomes easier to separate from water. Using a hot high-pressure separator in the high-pressure separation process of the hydrotreating effluent also has the advantage of reducing heat loss, as the hot high-pressure oil component avoids the cooling process required by air or water coolers for the hot high-pressure gas component. Meanwhile, a portion of the hot high-grade oil liquid can be returned to the upstream hydrogenation reaction process for recycling, in order to improve the overall feedstock properties of the hydrogenation reaction process receiving the recycled oil, or the recycled hot high-grade oil can be recycled for hydrogenation.

[0359] Between the hot high-pressure separation section and the cold high-pressure separation section, a warm high-pressure separation section can be set up as needed. At this time, the hot high-pressure gas is cooled into a gas-liquid two-phase material. In the warm high-pressure separator, it is separated into a warm high-pressure gas mainly composed of hydrogen in volume and a warm high-pressure oil liquid mainly composed of conventional liquid hydrocarbons and possible solids. The warm high-pressure gas enters the cold high-pressure separation section for cooling and gas-liquid separation.

[0360] Before the hydrogenation reaction effluent, hot high-pressure gas, or warm high-pressure gas enters the cold high-pressure separation process, its temperature is typically lowered (usually due to heat exchange with the feed material) to approximately 220–100°C (this temperature should be higher than the crystallization temperatures of ammonia hydrosulfide and ammonia chloride in the gas phase of the hydrogenation reaction effluent). Then, washing water is typically injected to form a post-water-injected hydrogenation reaction effluent. Two or more water injection points may be required. The washing water is used to absorb ammonia and other possible impurities such as hydrogen chloride and hydrogen sulfide. The aqueous solution after ammonia absorption will inevitably absorb hydrogen chloride and hydrogen sulfide. In the cold high-pressure separation process, the post-water-injected hydrogenation reaction effluent is separated into: a cold high-pressure gas mainly composed of hydrogen in volume, a cold high-pressure oil mainly composed of conventional liquid hydrocarbons and dissolved hydrogen, and a cold high-pressure water mainly composed of water and containing dissolved ammonia and hydrogen sulfide. The ammonia content in the cold high-pressure water is generally 0.5–15% (w), preferably 1–8% (w). One purpose of injecting wash water is to absorb ammonia and hydrogen sulfide in the hydrogenation reaction effluent, preventing the formation of ammonium hydrosulfide or polysulfide ammonia crystals that could clog heat exchanger channels and increase system pressure drop. The amount of wash water injected should be determined according to the following principles: Firstly, after being injected into the hydrogenation reaction effluent, the wash water separates into vapor and liquid phases; the liquid phase water volume must be greater than zero, preferably 30% or more of the total wash water volume. Secondly, the wash water is used to absorb ammonia in the hydrogenation reaction effluent, preventing excessively high ammonia concentration in the high-density gas, which could reduce catalyst activity. Generally, the lower the ammonia volume concentration in the high-density gas, the better; typically, it should not exceed 200 ppm(v), and preferably not exceed 50 ppm(v). The operating pressure of the cold high-pressure separator is the hydrogenation reaction process pressure minus the actual pressure drop. The difference between the cold high-pressure separation process operating pressure and the hydrogenation reaction pressure should not be too low or too high, generally 0.35–3.2 MPa, typically 0.5–1.5 MPa. The hydrogen volume concentration of the cold high-pressure gas should not be too low (leading to an increase in the unit's operating pressure), generally not lower than 70% (v), preferably not lower than 80% (v), and most preferably not lower than 85% (v). As mentioned above, at least one process, typically 85-100% of the cold high-pressure gas, is recycled in the hydrogenation reaction process to provide the necessary amount and concentration of hydrogen for the hydrogenation reaction. To improve the efficiency of the unit's investment, the circulating hydrogen concentration must be ensured not to be lower than the aforementioned lower limit. Therefore, depending on the specific properties of the feedstock, reaction conditions, and product distribution, a portion of the cold high-pressure gas can be excluded to remove methane and ethane produced in the reaction. For the discharged cold high-pressure gas, conventional membrane separation, pressure swing adsorption, or oil washing processes can be used to separate hydrogen and non-hydrogen gas components, and the recovered hydrogen can be used as fresh hydrogen.

[0361] For the hydrocarbon feedstock upflow expanded bed staged hydrogenation reaction process of this invention, when the yield of conventional non-hydrogen gas products is high, usually part or all of the cold high-grade gas, such as about 30% to 100% of the cold high-grade gas, is purified by membrane separation process. The resulting permeate hydrogen is then pressurized and returned to the hydrogenation reaction process, while the unpermeate gas is discharged to control the volume concentration of non-hydrogen components in the circulating gas. After the unpermeate gas is discharged, it can be subjected to PSA hydrogen extraction or "steam reforming hydrogen production + PSA hydrogen extraction" to obtain high-purity hydrogen, which is then pressurized and returned to the hydrogenation reaction process for recycling.

[0362] Fresh hydrogen is introduced into the hydrogenation section to replenish the hydrogen consumed in the hydrogenation reaction process. The higher the concentration of the fresh hydrogen, the better; it should generally not be lower than 95% (v), and preferably not lower than 99% (v). All the fresh hydrogen can be introduced into any hydrogenation reaction section, but it is best to introduce it into the first hydrogenation reactor.

[0363] In any reaction process, the hydrogen stream used in this invention can be entirely fresh hydrogen, entirely recycled hydrogen, or a mixture of fresh and recycled hydrogen.

[0364] In the feeding process of the hydropurification reaction process R2 described in this invention, in order to remove pollutants such as dust, phenols, and aromatics that are difficult to purify by hydropurification so that they do not pass through the hydropurification reaction process R2, the feed containing dust, large molecular weight phenols, and large molecular weight aromatics in the hydropurification reaction process R2 undergoes a cooling and condensation separation and dehydration process or an oil washing and dehydration process. Then, the resulting gas phase is heated and enters the hydropurification reaction process R2. The washing oil of the feed gas phase of the hydropurification reaction process R2 comes from the condensed oil separated in the separation process after the feed gas phase of the hydropurification reaction process R2 is washed but before entering the hydropurification reaction process R2, or from the hydrocarbon oil obtained from separating the hydropurification reaction effluent R2P. The above-mentioned oil washing process also has the effect of lowering the boiling point and density of the total hydrocarbons in the reaction products of the hydropurification reaction process R2, which is beneficial to reducing the equilibrium dissolved amount of hydrocarbons in the cold high-density water. Reducing the dissolved hydrocarbons in the cold high-density water also has the effect of lowering the boiling point and density.

[0365] In other words, the goal of the hydrogenation purification reaction process R2 of this invention is to ensure the purification of the hydrogenation purification reaction effluent R2P, which is why it is called the hydrogenation purification reaction process R2.

[0366] The following describes the feature parts of the present invention.

[0367] This invention discloses a method for hydrogenating and purifying the evaporated gas from wastewater containing phenols and / or aromatics, characterized by comprising the following steps:

[0368] The first wastewater contains pollutant component KC, including phenols and / or aromatics, including or excluding solid particles, including or excluding other pollutant components that can undergo hydrogenation conversion reaction to reduce their molecular electrical conductivity during the hydrogenation purification reaction process R2.

[0369] The heteroatom-containing organic compounds include oxygen-containing organic compounds, and may or may not include nitrogen-containing organic compounds, sulfur-containing organic compounds, and chlorine-containing organic compounds;

[0370] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0371] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0372] The operation method of this invention is generally as follows:

[0373] (1) Primary source of sewage

[0374] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0375] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0376] (2) Wastewater gasification process U2

[0377] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0378] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0379] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil;

[0380] (3) Hydrogenation purification reaction process R2

[0381] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0382] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0383] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0384] The general operating method of this invention is as follows:

[0385] (1) Primary source of sewage

[0386] The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing.

[0387] The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0388] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0389] (2) Wastewater gasification process U2

[0390] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0391] The first wastewater vaporized gas, U2V-1, is a dry gas of water.

[0392] The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil;

[0393] (3) Hydrogenation purification reaction process R2

[0394] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the dry water stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0395] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0396] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0397] The operation method of this invention is generally as follows:

[0398] (1) Primary source of sewage

[0399] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0400] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0401] (2) Wastewater gasification process U2

[0402] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0403] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0404] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil;

[0405] (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2

[0406] The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2.

[0407] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0408] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0409] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content.

[0410] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0411] In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB.

[0412] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0413] The operation method of this invention is generally as follows:

[0414] (1) Primary source of sewage

[0415] The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing.

[0416] The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0417] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal;

[0418] (2) Wastewater gasification process U2

[0419] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0420] The first wastewater vaporized gas, U2V-1, is a dry gas of water.

[0421] The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil;

[0422] (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2

[0423] The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2.

[0424] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction.

[0425] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0426] In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content.

[0427] In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds and metal sulfides, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio.

[0428] In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB.

[0429] The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

[0430] In this invention, typically, the effluent R1P from the hydrocarbon hydrogenation reaction process R1 is a stream containing phenols, aromatics, water, and hydrogen.

[0431] In this invention, typically, the effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1.

[0432] The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1, which is either dry or wet.

[0433] In this invention, typically, (3) a wastewater spray vaporization process WDV is set up;

[0434] In the wastewater spray vaporization process WDV, a liquid water-containing stream of the first wastewater is sprayed into a gas-containing stream based on hot high-density gas R1P-S1V and vaporized to form a stream containing water-dry first wastewater vaporized gas U2-2. The operating temperature of the water-dry first wastewater vaporized gas U2-2 is lower than the operating temperature of the stream R1P-S1V, and condensed oil WDV-L may or may not be generated.

[0435] In this invention, typically, during the wastewater spray vaporization process (WDV), condensed oil (WDV-L) is generated;

[0436] Condensed oil WDV-L, with or without solid particles from primary wastewater.

[0437] In this invention, typically, (3) during the wastewater spray gasification process WDV, condensed oil WDV-L is separated so that it does not undergo the hydrogenation purification reaction process R2.

[0438] In this invention, typically, (3) in the cold high-pressure separation process S7, water-containing and hydrogen-containing gas streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure water separation S7-W.

[0439] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0440] At least a portion of the hydrogen-rich gas stream based on the cold high-density gas S7-V is returned to the hydrogenation purification reaction effluent R2P for recycling.

[0441] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0442] At least a portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling.

[0443] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0444] A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling;

[0445] A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is recycled back to the hydrogenation purification reaction effluent R2P without going through the hydrocarbon hydrogenation reaction process R1.

[0446] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0447] The hydrogen concentration in the cold high-density gas S7-V is 75-98% by volume.

[0448] In this invention, the reaction parameters of R2 in the hydrogenation purification reaction process (3) are generally as follows:

[0449] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic oxygen in the feed hydrocarbon to water is higher than 80%.

[0450] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 80%.

[0451] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 80%.

[0452] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 60%.

[0453] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 70%.

[0454] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0455] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 35% by weight.

[0456] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 15% by weight.

[0457] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 10% by weight.

[0458] In general, the reaction parameters of R2 in the hydrogenation purification reaction process (3) are as follows:

[0459] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic oxygen in the feed hydrocarbon to water is higher than 90%.

[0460] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 90%.

[0461] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 90%.

[0462] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 70%.

[0463] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0464] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 90%.

[0465] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 17.5% by weight.

[0466] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 7.5% by weight;

[0467] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 5.0% by weight.

[0468] In the present invention, preferably, the reaction parameters of R2 in the hydrogenation purification reaction process are as follows:

[0469] In the hydrogenation purification reaction process R2, the organic oxygen in the feed hydrocarbon is hydrogenated to water with a hydrogenation conversion rate of over 98%.

[0470] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 98%.

[0471] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 98%.

[0472] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 80%.

[0473] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 90%.

[0474] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 95%.

[0475] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 9% by weight.

[0476] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 6% by weight.

[0477] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 3% by weight.

[0478] In this invention, the purification index of R2 in the hydrogenation purification reaction process (3) is generally as follows:

[0479] The organic oxygen content in hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight;

[0480] The organic nitrogen content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight;

[0481] The organic sulfur content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 2 ppm by weight.

[0482] In general, the purification index of R2 in the hydrogenation purification reaction process (3) is as follows:

[0483] The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydropurification reaction effluent R2P is less than 5% by weight.

[0484] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 2% by weight.

[0485] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 1% by weight.

[0486] In this invention, the typical operating conditions for the hydrogenation purification reaction R2 are: pressure of 6–25 MPa, temperature of 220–440 °C, and hydrogen-to-oil ratio of 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

[0487] In general, the operating conditions for the hydrogenation purification reaction R2 in this invention are: pressure of 12-20 MPa, temperature of 270-390°C, and hydrogen-to-oil ratio of 2000-20000 Nm. 3 / t, the liquid hourly space velocity of the hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

[0488] In this invention, the raw material hydrocarbon for the hydrocarbon hydrogenation reaction process R1 is typically a hydrocarbon containing phenols or aromatics, including hydrocarbons with a conventional boiling point higher than 350°C.

[0489] The operating conditions for hydrocarbon hydrogenation reaction R1 are typically: pressure 6–25 MPa, temperature 220–460 °C, and hydrogen-to-oil ratio 100–3000 Nm. 3 / t;

[0490] The operating conditions for the hydrotreating process R2 are typically: pressure 6–25 MPa, temperature 220–440 °C, and hydrogen-to-oil ratio 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

[0491] In this invention, generally, the hydrocarbon feedstock for the hydrocarbon hydrogenation reaction process R1 is a hydrocarbon containing phenols or aromatics, including hydrocarbons with a conventional boiling point higher than 350°C.

[0492] The operating conditions for hydrocarbon hydrogenation reaction R1 are generally: pressure 12–20 MPa, temperature 320–440 °C, and hydrogen-to-oil ratio 200–2000 Nm. 3 / t;

[0493] (3) The operating conditions for the hydrogenation purification reaction R2 are generally: pressure 12-20 MPa, temperature 270-390℃, and hydrogen-to-oil ratio 2000-20000 Nm. 3 / t, the liquid hourly space velocity of the hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

[0494] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0495] Cold high-water fraction S7-W has a phenol content of less than 10 ppm and an aromatic hydrocarbon content of less than 200 ppm.

[0496] In general, in the present invention, (3) in the cold high-pressure separation process S7, hydrogen-containing gas, water-containing and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W and cold high-pressure oil S7-L.

[0497] Cold high-water fraction S7-W has a phenol content of less than 5 ppm and an aromatic hydrocarbon content of less than 50 ppm.

[0498] In this invention, generally, (2) in the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V;

[0499] In the first oil washing process U3, the material U2V-1VB based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil U3-AL at least once to obtain the first post-wash gas U3-PV and the first post-wash oil U3-PL.

[0500] The amount of solids in the gas phase U3-V after the first wash is less than the amount of solids in the gas phase of the stream U2V-1VB.

[0501] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0502] At least a portion of the logistics based on cold high-separation oil S7-L is recycled as washing oil U3-AL.

[0503] In this invention, typically, (3) the gas-containing stream R2P-VB based on the hydrogenation purification reaction effluent R2P is mixed with the quenched stream KS and cooled to a temperature below the water dew point to form a mixed-phase material R2P-VB-2 containing gas and liquid phases.

[0504] The mixed-phase material R2P-VB-2 contains an aqueous phase with dissolved ammonia components.

[0505] In this invention, typically, (3) the quenched stream KS is quenched hydrogen-rich gas and / or quenched oil and / or quenched water.

[0506] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0507] The quenched logistics KS is based on quenched hydrogen-rich gas from the high-density gas separator S7-V, and / or quenched oil from the high-density oil separator S7-L, and / or quenched water from the high-density water separator S7-W.

[0508] In this invention, generally, (3) the hydrocarbon hydrogenation reaction process R1, the feedstock hydrocarbon R1F is obtained by separating coal hydrogenation and direct liquefaction to produce distilled oil, the hydrocarbon hydrogenation reaction process R1 undergoes partial hydrogenation saturation reaction of bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons, and the hydrogen supply index of hydrocarbons with conventional boiling points above 200℃ in the reaction effluent R1P of the hydrocarbon hydrogenation reaction process R1 is higher than the hydrogen supply index of hydrocarbons with conventional boiling points above 200℃ in the feedstock hydrocarbon R1F;

[0509] Hydrogen-rich hydrocarbon oil obtained from the hydrotreating effluent R1P is used as a hydrogen-donating solvent to prepare coal oil slurry with coal powder. This slurry is then converted into coal hydrotreating direct liquefaction effluent through the coal hydrotreating direct liquefaction reaction process.

[0510] The effluent from the direct liquefaction reaction of coal hydrogenation is separated to obtain distillate oil based on the oil produced by direct liquefaction of coal hydrogenation, which is used as feedstock oil R1F for the hydrocarbon hydrogenation reaction process R1.

[0511] The process of separating the effluent from the direct liquefaction reaction of coal hydrogenation yields initial wastewater containing phenols and aromatics.

[0512] Based on the initial phenol- and aromatic-containing wastewater, the first wastewater was obtained.

[0513] In this invention, typically, (1) the first source of wastewater

[0514] The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone a wastewater pretreatment process;

[0515] The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal.

[0516] In this invention, (1) the first wastewater is an aqueous solution containing phenols and aromatic hydrocarbons, and contains chloride ions and / or fluoride ions.

[0517] In this invention, typically, (2) the wastewater gasification process U2

[0518] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0519] During the cooling and condensation process U203, the first wastewater vaporized gas U2V-1 is separated into dry water gas U203-V and condensed oil U203-L.

[0520] In this invention, typically, during the heating process U204, the dry water gas U203-V absorbs heat and heats up to become the preheated gas U203-V2;

[0521] After preheating, the gas U203-V2 enters the hydrogenation purification reaction process R2.

[0522] In this invention, typically, (2) the wastewater gasification process U2

[0523] The first wastewater vaporized gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics.

[0524] In the oil washing process KU52, the gas based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil KU52-LF at least once to obtain the washing gas KU52-VP and the washing oil KU52-LP with lower dust content and / or lower high-boiling phenol content and / or lower high-boiling aromatic content. The washing gas then enters the hydrogenation purification reaction process R2.

[0525] At least a portion of the wash oil KU52-LF comes from the condensate oil separated during the separation process before the washed gas KU52-VP enters the hydropurification reaction process R2, or from the hydrocarbon oil obtained from the separation of the hydropurification reaction effluent R2P.

[0526] In this invention, (3) in the hydrogenation purification reaction process R2, two parallel-operating first-branch hydrogenation purification reaction processes R2B1 and second-branch hydrogenation purification reaction processes R2B2 can be set up.

[0527] When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, most to all of the material entering the first branch hydrogenation purification reaction process R2B1 will be introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction, so as to extend the continuous operation cycle.

[0528] In this invention, (3) in the hydrogenation purification reaction process R2, two parallel-operating first-branch hydrogenation purification reaction processes R2B1 and second-branch hydrogenation purification reaction processes R2B2 can be set up.

[0529] When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, all the material entering the first branch hydrogenation purification reaction process R2B1 is introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction. The first branch hydrogenation purification reaction process R2B1 is isolated from the feed system of the upstream material U2V-1B, but hot hydrogen-rich gas is introduced for flow to maintain the operating temperature of the first branch hydrogenation purification reaction process R2B1 within a reasonable range.

[0530] In this invention, (3) in the hydrogenation purification reaction process R2, two and / or more catalyst beds operating in series can be set to form two or more sub-region hydrogenation purification reaction processes operating in series.

[0531] According to the timeline, in the first stage, the logistics U2V-1B undergoes the first sub-zone hydrogenation purification reaction process R201, while ensuring that each other sub-zone has at least hot hydrogen-rich gas flowing through to maintain the operating temperature within a reasonable range.

[0532] According to the timeline, in the second stage, when the catalyst operating conditions of the first sub-region hydrogenation purification reaction process R201 are in the final stage, part of the total flow U2V-1B entering the first hydrogenation purification reaction process R201 is introduced into the second sub-region hydrogenation purification reaction process R202 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the first sub-region hydrogenation purification reaction process R201 to maintain the temperature of the first hydrogenation purification reaction process R201 within a reasonable range.

[0533] When the hydrogenation purification reaction process R2 is set with three or more catalyst beds operating in series, according to the time progress, in the third stage, when the catalyst operating conditions of the second sub-region hydrogenation purification reaction process R202 are in the final state, part of the total flow U2V-1B entering the second hydrogenation purification reaction process R202 is introduced into the third sub-region hydrogenation purification reaction process R203 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the second sub-region hydrogenation purification reaction process R202 to maintain the temperature of the second hydrogenation purification reaction process R202 within a reasonable range.

[0534] This process continues until the catalyst operating conditions of the final sub-region hydrogenation purification reaction process R209 are in the final stage, at which point a complete operating cycle is completed. The hydrogenation purification reaction process R2 then enters a shutdown step or a low-load operation step that reduces the first wastewater treatment volume.

[0535] In this invention, typically, (3) during the hydrogenation purification reaction process R2, when the processing stream U2V-1B is processed in the sub-region hydrogenation purification reaction process R20M, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged from the hydrogenation purification reaction process R2 as the hydrogenation purification reaction product R2P without passing through other sub-region hydrogenation purification reaction processes.

[0536] Meanwhile, the hydrogenation purification reaction processes of other hydrogenation purification reaction processes R2, except for the sub-region hydrogenation purification reaction process R20M, do not receive either the stream U2V-1B or the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M. Only other hot, water-poor hydrogen-rich gas flows through.

[0537] In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell and connected in the gas phase space.

[0538] The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

[0539] In this invention, typically, (3) in the first stage of the hydrogenation purification reaction process R2, when the first sub-region hydrogenation purification reaction process R201 processes the stream U2V-1B, the reaction product R201P of the first sub-region hydrogenation purification reaction process R201 is discharged from the hydrogenation purification reaction process R2 after passing through all the other sub-region hydrogenation purification reaction processes located downstream, and is used as the hydrogenation purification reaction product R2P.

[0540] When the sub-region hydrogenation purification reaction process R20M processes the stream U2V-1B, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged after passing through the downstream sub-region hydrogenation purification reaction process R2, and is used as the hydrogenation purification reaction product R2P.

[0541] Meanwhile, all sub-region hydrogenation and purification reaction processes located upstream of sub-region hydrogenation and purification reaction process R20M do not receive stream U2V-1B; only other hot, water-deficient, hydrogen-rich gas flows through them. Sub-region hydrogenation and purification reaction process R20M receives the effluent from the upstream sub-region hydrogenation and purification reaction process.

[0542] In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell.

[0543] The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

[0544] In this invention, typically, the hydrocarbon feed for the hydrogenation reaction process R1 (3) contains one or more of the following fractions:

[0545] ① Hydrocarbons with a conventional boiling point of 200–350℃, including phenols and / or aromatics;

[0546] ② Hydrocarbons with a conventional boiling point of 350–450℃, including phenols and / or aromatics;

[0547] ③ Hydrocarbons with a conventional boiling point of 450–550℃, including phenols and / or aromatics;

[0548] The hydrogenation reaction process R1 is either a fluidized bed hydrogenation reaction process or a suspended bed hydrogenation reaction process.

[0549] The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

[0550] In this invention, the hydrocarbon feed for the hydrogenation reaction process R1 is typically a hydrocarbon stream obtained from the direct liquefaction reaction product of coal hydrogenation, mainly composed of hydrocarbons with conventional boiling points of 150-550℃, including phenols and aromatics.

[0551] The hydrogenation reaction process R1 is a fluidized bed hydrogenation reaction process and a suspended bed hydrogenation reaction process.

[0552] The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

[0553] In this invention, typically, the operating temperature of the first wastewater vaporized gas U2V-1 obtained from the wastewater vaporization process U2 is at least 30°C higher than the water dew point;

[0554] (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 50°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 6.0~18.0MPa.

[0555] In general, the operating temperature of the first wastewater vaporized gas U2V-1 obtained from the wastewater vaporization process U2 in the present invention is at least 30°C higher than the water dew point;

[0556] (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 70°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 9.0~14.0MPa.

[0557] In this invention, typically, (3) in the hot high-pressure separation process S1, the reaction effluent R1P of the hydrogenation reaction process R1 is separated to obtain hot high-pressure gas S1-V and hot high-pressure oil S1-L.

[0558] The hydrocarbon stream S1-L-TOR2 obtained from separating the hot high-density oil S1-L enters the hydropurification reaction process R2;

[0559] Hydrocarbon stream S1-L-TOR2 is mainly composed of hydrocarbons with conventional boiling points below 250℃ and / or hydrocarbons with boiling points between 250℃ and 320℃.

[0560] In this invention, typically, a clean hydrocarbon stream KEYS containing hydrocarbon components with a conventional boiling point of 300-350°C undergoes a hydrogenation purification reaction process R2, during which at least a portion of the clean hydrocarbon stream KEYS remains in a liquid phase.

[0561] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0562] The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX for heat recovery and becomes the stream K-HX-HP. The weight flow rate of the liquid water component in the stream K-HX-HP is not less than 85% of the weight flow rate of the water component in the cold high-pressure water S7-W.

[0563] After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

[0564] In this invention, typically, (3) in the cold high-pressure separation process S7, hydrogen-containing, water-containing, and hydrocarbon-containing streams based on the hydrogenation purification reaction effluent R2P are separated to obtain cold high-pressure gas S7-V, cold high-pressure water S7-W, and cold high-pressure oil S7-L.

[0565] The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX for heat recovery and becomes the stream K-HX-HP. The temperature of the stream K-HX-HP is not higher than 150-170℃.

[0566] After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

[0567] In this invention, (2) the washing oil U3-AL can be a component of heavy diesel oil with a conventional boiling point of 250-350℃.

[0568] In this invention, (2) the washing oil KU52-LF can be a component of heavy diesel oil with a conventional boiling point of 250-350℃.

[0569] The operation method of this invention can be: (1) a first source of wastewater

[0570] The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It is wastewater that has undergone or has not undergone wastewater pretreatment.

[0571] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0572] (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

[0573] The operation method of this invention can be: (1) a first source of wastewater

[0574] The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It is wastewater that has undergone or has not undergone wastewater pretreatment.

[0575] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0576] (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

[0577] The operation method of this invention can be: (1) a first source of wastewater

[0578] The first type of wastewater, which may or may not contain solid particles, is the initial wastewater that has undergone or has not undergone a wastewater pretreatment process;

[0579] The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process;

[0580] (2) Wastewater gasification process U2

[0581] In the first wastewater light oil desolidification process, the first wastewater is mixed and contacted with the first desolidified hydrocarbon oil feedstock, and then separated into the first desolidified rich oil and the first desolidified wastewater.

[0582] The solid content in the first desolidified rich oil is higher than the solid content in the first desolidified hydrocarbon oil feedstock;

[0583] The solid content in the first wastewater with reduced solids is lower than the solid content in the first wastewater.

[0584] In the wastewater gasification process U2, at least a portion of the vaporizable pollutant component KCM in the first solids-degrading wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V.

[0585] The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas.

[0586] The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil.

[0587] The operation mode of the present invention may be as follows: (2) In the first wastewater light oil desolidification process, the first desolidified hydrocarbon oil feedstock is hydrocarbon oil based on the condensed oil of the wastewater gasification process U2, and / or is hydrocarbon oil obtained by separating the hydrogenation purification reaction effluent R2P.

[0588] The first step is to remove solids from the oil, which is a process of removing solids before entering the desulfurization and deammoniation process.

[0589] In the pre-solids removal process before the desulfurization and deammoniation process, the oil-rich stream based on the first solids removal process is mixed and contacted with the pre-sewage stream based on the initial wastewater, and then separated into pre-solids-rich oil-rich stream and pre-solids-reducing wastewater.

[0590] The solid content in the pre-desolidation rich oil is higher than that in the first desolidation rich oil;

[0591] The solid content in the pre-treatment solids-reducing wastewater is lower than the solid content in the pre-treatment wastewater stream;

[0592] Based on the logistics of pre-treated solid wastewater, it undergoes the first wastewater light oil desolidification process.

[0593] In this invention, the operation method can be as follows: (3) The effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1; the hot high-pressure oil R1P-S1L contains solid particles.

[0594] The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1, which is either dry or wet.

[0595] During the separation and fractionation process of FRAC80, the hot high-separation oil R1P-S1L is separated into gas, narrow-separation oil, and separation bottom oil FRAC80-DV containing solid particles;

[0596] Based on the pre-solidification rich oil stream, it enters the separation and fractionation process FRAC80 and is mixed and separated with the hot high-separation oil stream R1P-S1L to form narrow-separation oil products. The solid particles contained in the pre-solidification rich oil stream enter the separation bottom oil FRAC80-DV.

[0597] The operation mode of this invention can be: (3) In the hydrogenation purification reaction process R2, other hydrocarbons P600, which mainly contain phenols and / or aromatics with conventional boiling points below 350°C, are processed together.

[0598] Hydrocarbons P600, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

[0599] The operation mode of this invention can be: (3) In the hydrogenation purification reaction process R2, other hydrocarbons P700, mainly composed of phenols and / or aromatics with conventional boiling points below 250°C, are processed together.

[0600] Hydrocarbons P700, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

[0601] In this invention, the operation method can be as follows: (3) The reaction effluent R1P from the hydrocarbon hydrogenation reaction process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1.

[0602] The main hydrocarbons obtained from the separation of hot high-temperature oil R1P-S1L are phenolic and / or aromatic hydrocarbons with conventional boiling points below 250℃, which are then processed in the hydrogenation purification reaction process R2.

[0603] The operation mode of this invention can be as follows: (1) The first source of wastewater is wastewater with low chloride ion content, selected from the top water of the fractionation tower and the vacuum tower of the coal hydrogenation direct liquefaction to produce oil, the top water of the fractionation tower of the coal hydrogenation direct liquefaction to produce oil through hydrogenation modification, and acidic water from gas fractionation.

[0604] The operation mode of this invention can be: (3) Hydrocarbon hydrogenation reaction process R1 is a hydrogenation and upgrading reaction process of direct coal liquefaction oil or hydrogenated modified oil of direct coal liquefaction oil.

[0605] The operation mode of this invention can be: (2) wastewater gasification process U2

[0606] The first wastewater vaporization gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics. Based on the gas of the first wastewater vaporization gas U2V-1, after cooling, condensation, separation and deliquescence process KU51 and / or oil washing and deliquescence process KU52, a gas with lower dust content and / or lower high-boiling-point phenol content and / or lower high-boiling-point aromatic content is obtained and enters the hydrogenation purification reaction process R2.

[0607] Example

[0608] This embodiment includes a hydrocarbon hydrogenation reaction process R1, a hot high-pressure separation process R1P-S1 of the reaction effluent R1P from the hydrocarbon hydrogenation reaction process R1, a wastewater spray gasification process WDV, a first oil washing process U3, a hydrogenation purification reaction process R2, a heat recovery and cooling process of the hydrogenation purification reaction effluent R2P including a heat exchanger K-HX for heat recovery, a heat dissipation and cooling process, and a cold high-pressure separation process S7.

[0609] The following details each step.

[0610] The effluent from the direct liquefaction reaction of the coal hydrogenation unit is separated into high-temperature coal liquefaction gas and high-temperature coal liquefaction oil through a high-pressure separation process. The high-temperature coal liquefaction gas is then separated into high-temperature coal liquefaction gas and high-temperature coal liquefaction oil through a high-pressure separator. An oil washing section is set in the upper part of the high-pressure separator, where light diesel oil fraction is used to wash the high-temperature coal liquefaction gas. After being condensed and cooled by water injection, the high-temperature coal liquefaction gas is separated into low-temperature coal liquefaction gas, low-temperature coal liquefaction oil, and low-temperature coal liquefaction water through a high-pressure separator. In the low-pressure flash tank of the low-temperature coal liquefaction water, the depressurized low-temperature coal liquefaction water is degassed to remove dissolved gases and entrained oil, yielding the initial phenol- and aromatic-containing wastewater.

[0611] Table 5 shows the pollutant composition of the initial phenol- and aromatic wastewater.

[0612] The initial phenol and aromatic wastewater with the composition shown in Table 5 was treated to obtain the first wastewater. The wastewater pretreatment process included the following functions: solid removal by filter, free oil removal by hydrocyclone, solid removal and oil extraction by oil washing pretreatment, hydrogen sulfide and carbon dioxide removal by stripping tower, and ammonia removal by stripping tower. It did not undergo the extraction and phenol removal process.

[0613] Table 5. Pollutant Composition of Initial Phenolic and Aromatic Hydrocarbon-Containing Wastewater

[0614]

[0615] Table 6. Pollutant Composition of the First Wastewater (Wastewater after desulfurization and deammoniation of high-concentration coal liquefaction wastewater, and pretreated wastewater without phenol removal)

[0616]

[0617] The hydrocarbon feed F01 of the hydrogenation reaction process R1 is a hydrocarbon stream of 436.628 tons / hour obtained from the direct liquefaction reaction of coal hydrogenation. It mainly consists of hydrocarbons with conventional boiling points of 50-550℃, containing phenols and aromatics, and carrying about 250 ppm of solid particles. The hydrogenation reaction process R1 is a fluidized bed hydrogenation modification reaction process. The reaction effluent R1P of the hydrogenation reaction process R1 is a material containing phenols, aromatics, water vapor, and solid particles.

[0618] The operating conditions for the hydrocarbon hydrogenation reaction process R1 are as follows: reactor outlet pressure is 16.60 MPa, hydrogen partial pressure is not less than 11.4 MPaA, and temperature is 383.8℃. The hydrogen donation index of hydrocarbons with a conventional boiling point above 200℃ in the effluent R1P is 24.5 mgHnβ / g solvent, which is 7.5 mgHnβ / g higher than the hydrogen donation index of hydrocarbons with a conventional boiling point above 200℃ in the feed hydrocarbon R1F, which is 17.0 mgHnβ / g solvent.

[0619] The operating conditions for the hydrotreating process R2 are: pressure 16.26 MPa, hydrogen partial pressure not less than 9.56 MPaA, temperature 380℃, and all-gas feed volumetric flow rate 217973 Nm³. 3 / t, high-temperature high-grade oil production is 18.941 tons / hour, cold high-grade oil production is 10.487 tons / hour, and the hydrogen-to-oil ratio is 7406 Nm 3 / t, the liquid hourly space velocity of all four hydrotreating catalysts was 0.20 h⁻¹. -1 The liquid hourly space velocity (LHSV) of each hydrotreating catalyst bed is 0.80 h⁻¹. -1 .

[0620] The effluent R1P from the hydrocarbon hydrogenation reaction R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1. The hot high-pressure separation process R1P-S1 is carried out in the hot high-pressure separator S1E (not shown), and its operating conditions are: pressure of 16.60 MPa and temperature of 383.8℃.

[0621] The hot high-temperature gas R1P-S1V contains ammonia, hydrogen sulfide, hydrogen chloride, water, phenols, and aromatics. According to conventional processes, it needs to be washed with water and then cooled by a high-pressure air cooler before entering a hydrogenation-modified cold high-temperature separator to separate hydrogenation-modified cold high-temperature water. This hydrogenation-modified cold high-temperature water is also acidic wastewater containing phenols, aromatics, and chloride ions. According to this invention, this portion of acidic wastewater containing phenols and aromatics can be eliminated, transforming it into acidic water with low organic toxicity that is easy to treat with simple biochemical methods.

[0622] The hot high-temperature gas R1P-S1V, after being heated to 430℃ in the heating furnace GF1, becomes the furnace-after hot high-temperature gas MSV1. The furnace-after hot high-temperature gas MSV1 enters the wastewater gasification oil washing tower T1, serving as a heat carrier and a carrier gas for the gasified water. It heats and vaporizes the first wastewater injected into the gas stream in three batches, forming the vaporized gas U2V-1 of the first wastewater in a water-dry state. The process simulation calculation is based on single-stage mixed flash evaporation treatment. At the same time, the condensed oil WDV-L generated by the cooling of the furnace-after hot high-temperature gas MSV1 is used as an adsorbent and carrier for the solid dust remaining after the vaporization of the first wastewater, and is discharged from the bottom of the wastewater gasification oil washing tower T1.

[0623] The wastewater gasification oil washing tower T1 can be disassembled into several gas-liquid contactors for operation, and the temperature difference between the inlet and outlet temperatures of a single unit should be limited to a certain extent.

[0624] The first wastewater, with a pressure of 17.0 MPa and a temperature of 145℃, is divided into three parallel wastewater streams, FW02, FW03, and FW04, which enter the wastewater gasification section of the wastewater gasification oil washing tower T1 and are injected into the gas flow from different positions.

[0625] The wastewater gasification oil washing tower T1 is equipped with five layers of anti-clogging packing material, namely INC01, INC02, INC03, INC04, and INC05, to disperse the liquid and gas, increase the outer surface area of ​​the liquid phase, and provide the gas-liquid contact area. The anti-clogging packing material itself also has the heat transfer function of a heat exchanger.

[0626] The packing layers INC01, INC02, and INC03 are used to receive wastewater from three channels FW02, FW03, and FW04.

[0627] The filler layer INC04 is used to receive circulating washing oil WDV-L3.

[0628] The packing layer INC05 is used to receive the sprayed and dispersed washing oil U3-AL entering the sewage gasification oil washing tower T1, and to have countercurrent contact with the vaporized gas U2V-1 of the first sewage to obtain the first post-wash gas U3-PV and the first post-wash oil U3-PL.

[0629] After the first wash, the oil U3-PL flows downwards and can be discharged from the wastewater gasification oil washing tower T1. However, it usually enters the packing layer INC04 and mixes with the circulating washing oil WDV-L3 for reuse.

[0630] The condensed oil WDV-L is divided into parallel WDV-L1 and WDV-L2. WDV-L1 enters the separation and distillation process FRAC80. WDV-L2 is pressurized by pump T1 and then used as material WDV-L3 to enter the sewage gasification oil washing tower T1 and is sprayed and dispersed into the packing layer INC04.

[0631] Table 7 is a table showing the composition of water-containing logistics.

[0632] In Table 7, in order to conservatively design the hydrogenation purification reaction process R2, it is assumed that all CO and CO2 in the hydrocarbon feed F01 of the hydrogenation reaction process R1 are not converted by hydrogenation. To simplify the calculation, the first wastewater is considered as pure water for process simulation.

[0633] The first washing oil can be heavy diesel oil DIES100 fractionated from the hydrotreating reaction product of "coal-hydrogenated direct liquefaction oil and / or hydrotreated oil modified from coal-hydrogenated direct liquefaction oil", or it can be a rich absorption oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

[0634] After the first wash, the gas U3-PV is heated to 370℃ in the heating furnace GF1 and then becomes the stream U2V-1B, which enters the hydrogenation purification reaction process R2.

[0635] Table 7 Composition of Aquatic Streams

[0636]

[0637] The hydrogenation purification reaction process R2 is carried out in the hydrogenation purification reactor R2E.

[0638] In order to extend the operating cycle, the hydrotreating reactor R2E is equipped with four hydrotreating catalyst beds operating in series, all with the same type, quantity, and configuration of hydrotreating catalyst. These constitute four sub-region hydrotreating reaction processes R201, R202, R203, and R204, which operate as follows:

[0639] ① In the first stage, when the first sub-region hydrogenation purification reaction process R201 processes the stream U2V-1B, the reaction product R201P of the first sub-region hydrogenation purification reaction process R201 is discharged from the hydrogenation purification reaction process R2 after passing through all the other sub-region hydrogenation purification reaction processes R202, R203, and R204 located downstream, and is used as the hydrogenation purification reaction product R2P.

[0640] Logistics U2V-1B is transported as logistics U2V-1B1 into the hydrogenation purification reaction process R2;

[0641] ② In the second stage, when the catalyst operating conditions of the first sub-region hydrogenation purification reaction process R201 are in the final stage, part of the total flow U2V-1B entering the first hydrogenation purification reaction process R201 is introduced into the second sub-region hydrogenation purification reaction process R202 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the first sub-region hydrogenation purification reaction process R201 to maintain the temperature of the first hydrogenation purification reaction process R201 within a reasonable range.

[0642] The reaction product R202P of the second sub-region hydrogenation purification reaction process R202 is discharged after passing through all other sub-region hydrogenation purification reaction processes located downstream, and is used as the hydrogenation purification reaction product R2P.

[0643] Logistics U2V-1B is transported as logistics U2V-1B2 into the hydrogenation purification reaction process R2;

[0644] ③ In the third stage, when the catalyst operating conditions of the second sub-region hydrogenation purification reaction process R202 are in the final stage, part of the total flow U2V-1B entering the second sub-region hydrogenation purification reaction process R202 is introduced into the third sub-region hydrogenation purification reaction process R203 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the second sub-region hydrogenation purification reaction process R202 to maintain the temperature of the second hydrogenation purification reaction process R202 within a reasonable range.

[0645] The reaction product R203P of the third sub-region hydrogenation purification reaction process R203 is discharged from the hydrogenation purification reaction process R2 after passing through the downstream fourth sub-region hydrogenation purification reaction process R204, and is used as the hydrogenation purification reaction product R2P.

[0646] Logistics U2V-1B is transported as logistics U2V-1B3 into the hydrogenation purification reaction process R2;

[0647] ④ In the fourth stage, when the catalyst operating conditions of the third sub-region hydrogenation purification reaction process R203 are in the final stage, part of the total flow U2V-1B entering the third sub-region hydrogenation purification reaction process R203 is introduced into the fourth sub-region hydrogenation purification reaction process R204 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the third sub-region hydrogenation purification reaction process R203 to maintain the temperature of the third hydrogenation purification reaction process R202 within a reasonable range.

[0648] The reaction product R204P of the fourth sub-region hydrogenation purification reaction process R204 is discharged from the hydrogenation purification reaction process R2 and becomes the hydrogenation purification reaction product R2P.

[0649] Logistics U2V-1B is transported as logistics U2V-1B4 into the hydrogenation purification reaction process R2;

[0650] ⑤ When the catalyst operating conditions of the fourth sub-region hydrogenation purification reaction process R204 are in the final stage, a complete operation cycle is completed, and the hydrogenation purification reaction process R2 is switched to the shutdown step or the first wastewater low-load operation step with reduced first wastewater treatment volume.

[0651] The purging hydrogen BH03 is used in four parallel lines: purging hydrogen BH031, purging hydrogen BH03, purging hydrogen BH033, and purging hydrogen BH034. Purging hydrogen BH03 is used to replace the medium and can also be used to maintain the temperature of the purged catalyst bed.

[0652] Valves are used to cut off or regulate the flow rate of materials.

[0653] The reaction parameters of R2 in the hydrogenation purification process are as follows:

[0654] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic oxygen in the feed hydrocarbon to water is higher than 99.5%.

[0655] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic nitrogen in the feed hydrocarbon to ammonia is higher than 98.5%.

[0656] In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 99.8%.

[0657] The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 70%.

[0658] The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 90%.

[0659] The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon ratio by more than 97%.

[0660] The weight content of hydrocarbon components with conventional boiling points above 280°C in the hydropurification reaction effluent R2P is less than 25% by weight.

[0661] The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydropurification reaction effluent R2P is less than 7% by weight.

[0662] The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 3% by weight.

[0663] The hydrogenation purification reaction effluent R2P passes through heat exchangers HX31AB, HX32, HX33, HX34, K-HX, and HX36 in sequence for cooling before entering the cold high-pressure separator S7E.

[0664] The hydrogenation purification reaction effluent R2P is cooled to 270°C by heat exchanger HX31AB and becomes material R2P1. At the same time, the hydrocarbon feed F01 from the hydrogenation reaction process R1 at 260.5°C is heated to 307.0°C by heat exchanger HX31AB and becomes hot hydrocarbon feed F02.

[0665] The circulating high-temperature water at a flow rate of 20t / h is rapidly cooled to a temperature below the water dew point of 252.5℃, forming a liquid water phase of 17.516t / h. Then, it is cooled to 200℃ through a heat exchanger and enters a high-temperature high-pressure separator to be separated into high-temperature high-pressure gas, high-temperature high-pressure oil, and high-temperature high-pressure water.

[0666] After material R2P1 is mixed with 20t / h of circulating high-temperature water, its temperature is rapidly cooled from 270℃ to 252.5℃, becoming material R2P2 containing 17.516t / h of liquid water. Material R2P2 releases heat and cools down to 252.5℃ through heat exchanger HX32, becoming material R2P3. At the same time, mixed hydrogen gas MH2 at 164.8℃ absorbs heat and rises to 226.4℃ through heat exchanger HX32, becoming mixed hydrogen gas MH4.

[0667] Material R2P3 is cooled to 200.0℃ by heat exchanger HX33 and becomes material R2P4. At the same time, the deoxygenated water is heated by steam generator HX33 (heat load 16.96MW) and produces 1.0Ma saturated steam.

[0668] The high-temperature high-pressure separation process (WHPS) is carried out in the cold high-pressure separator (WHPS-E) under the following operating conditions: pressure 16.07 MPa and temperature 200 °C. The separated material R2P4 yields high-temperature high-pressure gas separator (WHPS-V), high-temperature high-pressure oil separator (WHPS-L), and high-temperature high-pressure water separator (WHPS-W).

[0669] The high-temperature water separation WHPS-W shown is divided into two streams. One stream, as a 20t / h circulating high-temperature water separation WHPS-WRLR1, is pressurized by the circulating pump W-PUMP and then sent as the flow WHPS-WR2 to the cooling flow R2P1. The other stream, as a 28.714t / h high-temperature water separation net product WHPS-W1, enters the heat exchanger K-HX.

[0670] The high-temperature oil WHPS-L undergoes depressurization and degassing processes before being sent to the fractionation tower.

[0671] After being mixed, the high-temperature gas WHPS-V and the high-temperature water WHPS-W1 become the material R2P7. After passing through the heat exchanger K-HX, the temperature is reduced to 160.0℃ and becomes the material K-HX-HP. At the same time, the mixed hydrogen gas MH1 at 75.8℃ passes through the heat exchanger K-HX and is heated to 164.8℃, becoming the mixed hydrogen gas MH2.

[0672] Material K-HX-HP is mixed with quenched material WW2 (for emergency water injection, not used during normal operation) to become material R2P9. Material R2P9 is cooled to 54°C by air cooler HX35 (heat load 16.34MW) to become material R2P10.

[0673] The cold high-pressure separation process S7 is carried out in the cold high-pressure separator S7E. Its operating conditions are: pressure of 15.87MPa and temperature of 54℃. The separated material R2P9 is obtained as cold high-pressure gas S7V, cold high-pressure oil S7L, and 45.010t / h cold high-pressure water S7W (containing 42.331t / h of water).

[0674] After passing through the last heat exchanger K-HX used for heat recovery, the hydrogenation purification reaction effluent R2P becomes the stream K-HX-HP at a temperature of 160℃. The weight flow rate of the liquid water component in the stream K-HX-HP is 37.342 t / h, which is 88.2% of the weight flow rate of the water component in the cold high-separation water S7W, which is 42.320 t / h.

[0675] The cold high-temperature gas S7V is compressed by the circulating hydrogen compressor CE2 to become circulating hydrogen S7V1; the fresh hydrogen FH1 is compressed by the fresh hydrogen compressor CE1 to become fresh hydrogen FH2; the fresh hydrogen FH2 and the circulating hydrogen S7V1 are mixed to become mixed hydrogen MH1.

[0676] The mixed hydrogen MH4 is used in three parallel circuits: mixed hydrogen MH41, mixed hydrogen MH42, and mixed hydrogen MH43.

[0677] Mixed hydrogen gas MH41 and hot hydrocarbon feed F02 are mixed to form mixed feed MF1. Mixed feed MF1 is mixed with liquid sulfur to form mixed feed MF2. Mixed feed MF is heated by heater GF2 to become hot mixed feed MF3, which enters the first reaction section of the hydrocarbon hydrogenation reaction process R1D.

[0678] The mixed hydrogen gas MH42, after being heated in the furnace GF2, becomes hot mixed hydrogen R1INH and enters the second reaction stage of the hydrocarbon hydrogenation reaction process R1.

[0679] The mixed hydrogen gas MH43 is heated by the heating furnace GF2 to become hot mixed hydrogen BH00. The hot mixed hydrogen BH00 is used in three parallel circuits: stripped hydrogen BH01, stripped hydrogen BH02, and purging hydrogen BH03.

[0680] During the separation and fractionation process FRAC80, the hot high-grade oil R1P-S1L and the condensate oil WDV-L1 are separated into narrow-range oil products: naphtha 80L1, mainly composed of conventional liquid hydrocarbons with a conventional boiling point below 140℃; crude diesel 80L2, mainly composed of conventional liquid hydrocarbons with a conventional boiling point of 140-330℃; middle-range hydrogen-supplying solvent oil 80L3, mainly composed of conventional liquid hydrocarbons with a conventional boiling point of 230-400℃; and heavy-range hydrogen-supplying solvent oil 80L4, mainly composed of conventional liquid hydrocarbons with a conventional boiling point of 280-550℃.

[0681] The heavy distillate hydrogen supply solvent oil 80L4 is divided into two routes: the first route, heavy distillate hydrogen supply solvent oil 80L42, exits the unit to prepare coal slurry; the second route, heavy distillate hydrogen supply solvent oil 80L41, is pressurized by a pump and returned to the hydrocarbon hydrogenation reaction process R1 for cyclic hydrogenation reaction to improve the hydrogen supply index of the externally supplied heavy distillate hydrogen supply solvent oil 80L42.

[0682] Table 8 shows the flash phase equilibrium data curves for the effluent R2P from the hydrogenation purification reaction.

[0683] As shown in Table 8, the oil dew point temperature of the hydrotreating reaction effluent R2P is approximately 293.41℃, and the water dew point temperature is approximately 249.78℃. To prevent the formation of a high-concentration chloride ion aqueous phase or to avoid or reduce the area where a high-concentration chloride ion aqueous phase exists, it is necessary to mix the material R2P with the quenched material XF to lower the temperature below the water dew point and form a large amount of liquid water. The source of the quenched material XF is not limited. This invention uses a circulating high-temperature water separation method to change the phase equilibrium and increase the dew point temperature, thus solving this problem and making the temperature drop of the material R2P very small, thereby economically recovering heat.

[0684] Table 9 shows the flash phase equilibrium data curves for the dew point temperature of the R2P2 stream after high-temperature water separation during the injection of circulating water.

[0685] Table 10 shows the distillation curves of WHPS-L (warm high-temperature distillate) and S7L (cold high-temperature distillate).

[0686] According to the method of the present invention, the dew point temperature of the stream after the high-temperature water separation in the circulating water injection is increased to 266.84℃, which is 17.06℃ higher than the dew point temperature in Table 8.

[0687] As can be seen from Tables 7 and 10, using clean heavy diesel wash oil U3-AL to wash vaporized gas U2V-1, the heavy diesel wash oil U3-AL, as an absorbent oil, absorbs some of the high-boiling-point hydrocarbons containing pollutants in the washed vaporized gas U2V-1, thereby purifying the vaporized gas U2V-1. This is equivalent to replacing some of the high-boiling-point hydrocarbons containing pollutants in the vaporized gas U2V-1 with clean heavy diesel oil, which is beneficial for reducing the hydrogen partial pressure of R2 in the hydropurification reaction process, increasing the liquid space velocity of the hydropurification catalyst, and reducing the amount of catalyst used.

[0688] As can be seen from Table 10, the main functions of the high-temperature and high-pressure separator are as follows:

[0689] ① Condensation produces high-temperature high-temperature oil purified products, thereby reducing the content of high-boiling-point hydrocarbon components in cold high-temperature oil, which is beneficial to reducing the distillation dry point of cold high-temperature water, reducing the oil removal task in the subsequent purification process of cold high-temperature water, and reducing the digestion load of the biochemical process.

[0690] ② Retain the heat energy of the purified oil products at high temperature, reduce the heat dissipation load of the high-pressure air cooler, and improve the heat recovery rate.

[0691] Table 8 Flash phase equilibrium data curves of R2P effluent from the hydrotreating reaction.

[0692]

[0693]

[0694] Table 9 shows the flash phase equilibrium data curves for the dew point temperature of the R2P2 stream after high water separation at circulating temperature.

[0695]

[0696]

[0697] Table 10 Distillation curves of high-temperature oil WHPS-L and cold-temperature high-temperature oil S7L

[0698]

Claims

1. A method for hydrogenating and purifying the evaporated gas from wastewater containing phenols and / or aromatics, characterized in that... Includes the following steps: The first wastewater contains pollutant component KC, including phenols and / or aromatics, including or excluding solid particles, including or excluding other pollutant components that can undergo hydrogenation conversion reaction to reduce their molecular electrical conductivity during the hydrogenation purification reaction process R2. Organic compounds containing heteroatoms, including oxygen-containing organic compounds, including or excluding nitrogen-containing organic compounds, including or excluding sulfur-containing organic compounds, including or excluding chlorine-containing organic compounds; (1) Primary source of sewage The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process; (2) Wastewater vaporization process U2 In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas. The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil; (3) Hydrogenation purification reaction process R2 In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

2. The method according to claim 1, characterized in that: (1) Primary source of sewage The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing. The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal; (2) Wastewater vaporization process U2 In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. The first wastewater vaporized gas, U2V-1, is a dry gas of water. The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil; (3) Hydrogenation purification reaction process R2 In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the dry water stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

3. The method according to claim 1, characterized in that: (1) Primary source of sewage The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone or has not undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal; (2) Wastewater vaporization process U2 In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas. The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil; (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2 The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2. In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB. The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

4. The method according to claim 2, characterized in that: (1) Primary source of sewage The primary sources of wastewater include one or more of the following processes: direct coal hydrogenation liquefaction, coal gasification, coal dry distillation, and coal tar processing. The first type of wastewater contains solid particles and is wastewater that has undergone or has not undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal; (2) Wastewater vaporization process U2 In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. The first wastewater vaporized gas, U2V-1, is a dry gas of water. The first wastewater vaporized gas, U2V-1, contains liquid hydrocarbon oil; (3) Hydrocarbon hydrogenation reaction process R1 and hydrogenation purification reaction process R2 The hydrogen-containing gaseous stream R1P-VB, which is the effluent R1P from the hydrocarbon hydrogenation reaction process R1, is purified by hydrogenation reaction process R2. In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream U2V-1B containing the first wastewater vaporization gas U2V-1 undergoes at least a portion of the pollutant KC to be converted into hydrogenation purification effluent R2P with low organic pollutant content through a hydrogenation purification reaction reaction. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in the U2V-1B stream undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in the U2V-1B stream undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. In the hydrogenation purification reaction process R2, under the conditions of hydrogen, hydrogen sulfide and hydrogenation purification catalyst, the stream R1P-VB undergoes at least a portion of the pollutant components to be converted into hydrogenation purification effluent R2P with low organic pollutant content. In the hydrogenation purification reaction process R2, at least a portion of the heteroatom-containing organic compounds in stream R1P-VB undergoes a hydrogenation impurity removal reaction to generate heteroatom-free organic compounds, and / or at least a portion of the aromatic ring-containing components in stream U2V-1B undergoes an aromatic ring hydrogenation saturation reaction to generate aromatic hydrocarbons with a lower aromatic carbon ratio. In the hydrogenation purification reaction process R2, the component based on stream U2V-1B or the intermediate hydrogenation product based on stream U2V-1B is mixed and contacted with stream R1P-VB or the intermediate hydrogenation product of stream R1P-VB. The aqueous phase stream was obtained by separating and purifying the hydrogenation reaction effluent R2P.

5. The method according to claim 3, characterized in that: (3) The effluent R1P from the hydrocarbon hydrogenation reaction R1 is a stream containing phenols, aromatics, water, and hydrogen.

6. The method according to claim 4, characterized in that: (3) The effluent R1P from the hydrocarbon hydrogenation reaction R1 is a stream containing phenols, aromatics, water, and hydrogen.

7. The method according to claim 3, characterized in that: (3) The effluent R1P from the hydrocarbon hydrogenation process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1. The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1 in a dry or wet state.

8. The method according to claim 7, characterized in that: (3) Set up the wastewater spray vaporization process WDV; In the wastewater spray vaporization process WDV, a liquid water-containing stream of the first wastewater is sprayed into a gas-containing stream based on the hot high-pressure gas R1P-S1V and vaporized to form a stream containing water-dry first wastewater vaporized gas U2-2. The operating temperature of the water-dry first wastewater vaporized gas U2-2 is lower than the operating temperature of the hot high-pressure gas R1P-S1V, and condensed oil WDV-L may or may not be generated.

9. The method according to claim 8, characterized in that: (3) During the wastewater spray vaporization process, WDV condensate oil WDV-L is generated; Condensed oil WDV-L, with or without solid particles from primary wastewater.

10. The method according to claim 9, characterized in that: (3) During the wastewater spray vaporization process WDV, condensed oil WDV-L is separated, so that it does not need to go through the hydrogenation purification reaction process R2.

11. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high-pressure separation process S7, separating water-containing and hydrogen-containing gas streams based on hydrogenation purification reaction effluent R2P to obtain cold high-pressure water separation S7-W.

12. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; At least a portion of the hydrogen-rich gas stream based on the cold high-density gas S7-V is returned to the hydrogenation purification reaction effluent R2P for recycling.

13. The method according to any one of claims 3 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; At least a portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling.

14. The method according to any one of claims 3 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrocarbon hydrogenation reaction process R1 for recycling; A portion of the hydrogen-rich gas stream based on the cold high-pressure gas S7-V is returned to the hydrogenation purification reaction effluent R2P for recycling without going through the hydrocarbon hydrogenation reaction process R1.

15. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; The hydrogen concentration in the cold high-density gas S7-V is 75-98% by volume.

16. The method according to any one of claims 1 to 10, characterized in that: (3) The reaction parameters of R2 in the hydrogenation purification process are as follows: In the hydrogenation purification reaction process R2, the organic oxygen in the feed hydrocarbon is hydrogenated to water with a hydrogenation conversion rate of over 80%. In the hydrogenation purification reaction process R2, the organic nitrogen in the feed hydrocarbon is hydrogenated to ammonia with a hydrogenation conversion rate of over 80%. In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 80%. In the hydrogenation purification reaction process R2, the hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons reduces the aromatic carbon content by more than 60%. In the hydrogenation purification reaction process, the hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 reduces the aromatic carbon content by more than 70%. In the hydrogenation purification reaction process, the total amount of polycyclic aromatic hydrocarbons in the feed hydrocarbons of R2 is reduced by more than 80% due to the hydrogenation saturation reaction. The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydrotreating reaction effluent R2P is less than 35% by weight. The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydrotreating reaction effluent R2P is less than 15% by weight. The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 10% by weight.

17. The method according to any one of claims 1 to 10, characterized in that: (3) The reaction parameters of R2 in the hydrogenation purification process are as follows: In the hydrogenation purification reaction process R2, the organic oxygen in the feed hydrocarbon is hydrogenated to water with a hydrogenation conversion rate of over 90%. In the hydrogenation purification reaction process R2, the organic nitrogen in the feed hydrocarbon is hydrogenated to ammonia with a hydrogenation conversion rate of over 90%. In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 90%. The hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon content by more than 70%. In the hydrogenation purification reaction process, the hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feed hydrocarbons of R2 reduces the aromatic carbon content by more than 80%. The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon content by more than 90%. The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydrotreating reaction effluent R2P is less than 17.5% by weight. The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydrotreating reaction effluent R2P is less than 7.5% by weight. The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 5.0% by weight.

18. The method according to any one of claims 1 to 10, characterized in that: (3) The reaction parameters of R2 in the hydrogenation purification process are as follows: In the hydrogenation purification reaction process R2, the organic oxygen in the feed hydrocarbon is hydrogenated to water with a hydrogenation conversion rate of over 98%. In the hydrogenation purification reaction process R2, the organic nitrogen in the feed hydrocarbon is hydrogenated to ammonia with a hydrogenation conversion rate of over 98%. In the hydrogenation purification reaction process R2, the hydrogenation conversion rate of organic sulfur in the feed hydrocarbon to hydrogen sulfide is higher than 98%. In the hydrogenation purification reaction process, the hydrogenation saturation reaction of the total monocyclic aromatic hydrocarbons in the feed hydrocarbons of R2 reduces the aromatic carbon content by more than 80%. The hydrogenation saturation reaction of the total bicyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon content by more than 90%. The hydrogenation saturation reaction of the total polycyclic aromatic hydrocarbons in the feedstock hydrocarbons of R2 in the hydrogenation purification reaction process reduces the aromatic carbon content by more than 95%. The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydrotreating reaction effluent R2P is less than 9% by weight. The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydrotreating reaction effluent R2P is less than 6% by weight. The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 3% by weight.

19. The method according to any one of claims 1 to 10, characterized in that: (3) The purification indicators of R2 in the hydrogenation purification reaction process are as follows: The organic oxygen content in hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight; The organic nitrogen content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 5 ppm by weight; The organic sulfur content of hydrocarbons in the hydrogenation purification reaction effluent R2P is less than 2 ppm by weight.

20. The method according to claim 19, characterized in that: (3) The purification indicators of R2 in the hydrogenation purification reaction process are as follows: The weight content of hydrocarbon components with conventional boiling points above 250°C in the hydrotreating reaction effluent R2P is less than 5% by weight. The weight content of hydrocarbon components with conventional boiling points above 300°C in the hydrotreating reaction effluent R2P is less than 2% by weight. The weight content of hydrocarbon components with conventional boiling points above 350°C in the hydropurification reaction effluent R2P is less than 1 wt%.

21. The method according to any one of claims 1 to 10, characterized in that: (3) The operating conditions for the hydrogenation purification reaction R2 are: pressure 6–25 MPa, temperature 220–440 °C, and hydrogen-to-oil ratio 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

22. The method according to claim 21, characterized in that: (3) The operating conditions for the hydrogenation purification reaction R2 are: pressure 12-20 MPa, temperature 270-390℃, and hydrogen-to-oil ratio 2000-20000 Nm. 3 / t, the liquid hourly space velocity of the hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

23. The method according to any one of claims 3 to 10, characterized in that: The feedstock hydrocarbons in the hydrocarbon hydrogenation reaction process R1 are hydrocarbons containing phenols and aromatics, including hydrocarbons with conventional boiling points above 350℃; The operating conditions for hydrocarbon hydrogenation reaction R1 are: pressure 6–25 MPa, temperature 220–460 °C, and hydrogen-to-oil ratio 100–3000 Nm. 3 / t; The operating conditions for the hydrotreating and purification reaction R2 are: pressure 6–25 MPa, temperature 220–440 °C, and hydrogen-to-oil ratio 2000–20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.05–10.0 h⁻¹. -1 .

24. The method according to claim 23, characterized in that: The feedstock hydrocarbons in the hydrocarbon hydrogenation reaction process R1 are hydrocarbons containing phenols and aromatics, including hydrocarbons with conventional boiling points above 350℃; The operating conditions for hydrocarbon hydrogenation reaction R1 are: pressure 12–20 MPa, temperature 320–440 °C, and hydrogen-to-oil ratio 200–2000 Nm. 3 / t; (3) The operating conditions for the hydrogenation purification reaction R2 are: pressure 12-20 MPa, temperature 270-390℃, and hydrogen-to-oil ratio 2000-20000 Nm. 3 / t, the liquid hourly space velocity (LHSV) for hydrogenation purification catalyst is 0.2–1.0 h⁻¹. -1 .

25. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; Cold high-water fraction S7-W has a phenol content of less than 10 ppm and an aromatic hydrocarbon content of less than 200 ppm.

26. The method according to claim 25, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; Cold high-water fraction S7-W has a phenol content of less than 5 ppm and an aromatic hydrocarbon content of less than 50 ppm.

27. The method according to claim 1, characterized in that: (2) In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenol and / or aromatic hydrocarbons, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. In the first oil washing process U3, the material U2V-1VB based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil U3-AL at least once to obtain the first post-wash gas U3-PV and the first post-wash oil U3-PL. The amount of solids in the gas phase U3-V after the first wash is less than the amount of solids in the gas phase of the stream U2V-1VB.

28. The method according to claim 27, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; At least a portion of the logistics based on cold high-separation oil S7-L is recycled as washing oil U3-AL.

29. The method according to any one of claims 1 to 10, characterized in that: (3) Based on the gas-phase material R2P-VB of the hydrogenation purification reaction effluent R2P, it is mixed with the quenched material KS and cooled to a temperature below the water dew point to form a mixed-phase material R2P-VB-2 containing gas and liquid phases. The mixed-phase material R2P-VB-2 contains an aqueous phase with dissolved ammonia components.

30. The method according to claim 29, characterized in that: (3) Rapidly cooled logistics KS refers to rapidly cooled hydrogen-rich gas and / or rapidly cooled oil and / or rapidly cooled water.

31. The method according to claim 30, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; The quenched logistics KS is based on quenched hydrogen-rich gas from the high-density gas separator S7-V, and / or quenched oil from the high-density oil separator S7-L, and / or quenched water from the high-density water separator S7-W.

32. The method according to any one of claims 3 to 10, characterized in that: (3) In the hydrocarbon hydrogenation reaction process R1, the feedstock hydrocarbon R1F is the distillate obtained by the direct liquefaction reaction of coal hydrogenation. In the hydrocarbon hydrogenation reaction process R1, a partial hydrogenation saturation reaction of bicyclic aromatic hydrocarbons and / or polycyclic aromatic hydrocarbons occurs. The hydrogen supply index of hydrocarbons with a conventional boiling point above 200℃ in the reaction effluent R1P of the hydrocarbon hydrogenation reaction process R1 is higher than that of hydrocarbons with a conventional boiling point above 200℃ in the feedstock hydrocarbon R1F. Hydrogen-rich hydrocarbon oil obtained from the hydrotreating effluent R1P is used as a hydrogen-donating solvent to prepare coal oil slurry with coal powder. This slurry is then converted into coal hydrotreating direct liquefaction effluent through the coal hydrotreating direct liquefaction reaction process. The effluent from the direct liquefaction reaction of coal hydrogenation is separated to obtain distillate oil based on the oil produced by direct liquefaction of coal hydrogenation, which is used as feedstock oil R1F for the hydrocarbon hydrogenation reaction process R1. The process of separating the effluent from the direct liquefaction reaction of coal hydrogenation yields initial wastewater containing phenols and aromatics. Based on the initial phenol- and aromatic-containing wastewater, the first wastewater was obtained.

33. The method according to any one of claims 1 to 10, characterized in that: (1) Primary source of sewage The first type of wastewater, which may or may not contain solid particles, is wastewater that has undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal, free oil removal, hydrogen sulfide removal, carbon dioxide removal, ammonia removal, and phenol removal.

34. The method of any one of claims 1 to 10, wherein: (1) The first wastewater is an aqueous solution containing phenols and aromatic hydrocarbons, and also contains chloride ions and / or fluoride ions.

35. The method according to any one of claims 1 to 10, characterized in that: (2) Wastewater vaporization process U2 In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. During the cooling and condensation process U203, the first wastewater vaporized gas U2V-1 is separated into dry water gas U203-V and condensed oil U203-L.

36. The method according to claim 35, characterized in that: During the heating process, U204, the dry water gas U203-V absorbs heat and becomes the preheated gas U203-V2 after heating; After preheating, the gas U203-V2 enters the hydrogenation purification reaction process R2.

37. The method according to any one of claims 1 to 10, characterized in that: (2) Wastewater vaporization process U2 The first wastewater vaporized gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics. In the oil washing process KU52, the gas based on the first sewage vaporization gas U2V-1 comes into contact with the washing oil KU52-LF at least once to obtain the washing gas KU52-VP and the washing oil KU52-LP with lower dust content and / or lower high-boiling phenol content and / or lower high-boiling aromatic content. The washing gas then enters the hydrogenation purification reaction process R2. At least a portion of the wash oil KU52-LF comes from the condensate oil separated during the separation process before the washed gas KU52-VP enters the hydropurification reaction process R2, or from the hydrocarbon oil obtained from the separation of the hydropurification reaction effluent R2P.

38. The method according to any one of claims 1 to 10, characterized in that: (3) In the hydrogenation purification reaction process R2, two parallel operations are set up: the first branch hydrogenation purification reaction process R2B1 and the second branch hydrogenation purification reaction process R2B2. When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, most to all of the material entering the first branch hydrogenation purification reaction process R2B1 will be introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction, so as to extend the continuous operation cycle.

39. The method according to any one of claims 1 to 10, characterized in that: (3) In the hydrogenation purification reaction process R2, two parallel operations are set up: the first branch hydrogenation purification reaction process R2B1 and the second branch hydrogenation purification reaction process R2B2. When the catalyst operating conditions of the first branch hydrogenation purification reaction process R2B1 are in the final stage, all the material entering the first branch hydrogenation purification reaction process R2B1 is introduced into the second branch hydrogenation purification reaction process R2B2 for hydrogenation purification reaction. The first branch hydrogenation purification reaction process R2B1 is isolated from the feed system of the upstream material U2V-1B, but hot hydrogen-rich gas is introduced for flow to maintain the operating temperature of the first branch hydrogenation purification reaction process R2B1 within a reasonable range.

40. The method according to any one of claims 1 to 10, characterized in that: (3) In the hydrogenation purification reaction process R2, two and / or more catalyst beds operating in series are set up to form two or more sub-region hydrogenation purification reaction processes operating in series. According to the timeline, in the first stage, the logistics U2V-1B undergoes the first sub-zone hydrogenation purification reaction process R201, while ensuring that each other sub-zone has at least hot hydrogen-rich gas flowing through to maintain the operating temperature within a reasonable range. According to the timeline, in the second stage, when the catalyst operating conditions of the first sub-region hydrogenation purification reaction process R201 are in the final stage, part of the total flow U2V-1B entering the first hydrogenation purification reaction process R201 is introduced into the second sub-region hydrogenation purification reaction process R202 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the first sub-region hydrogenation purification reaction process R201 to maintain the temperature of the first hydrogenation purification reaction process R201 within a reasonable range. When the hydrogenation purification reaction process R2 is set with three or more catalyst beds operating in series, according to the time progress, in the third stage, when the catalyst operating conditions of the second sub-region hydrogenation purification reaction process R202 are in the final state, part of the total flow U2V-1B entering the second hydrogenation purification reaction process R202 is introduced into the third sub-region hydrogenation purification reaction process R203 for hydrogenation purification reaction. Then, it is ensured that at least hot hydrogen-rich gas flows through the second sub-region hydrogenation purification reaction process R202 to maintain the temperature of the second hydrogenation purification reaction process R202 within a reasonable range. This process continues until the catalyst operating conditions of the final sub-region hydrogenation purification reaction process R209 are in the final stage, at which point a complete operating cycle is completed. The hydrogenation purification reaction process R2 then enters a shutdown step or a low-load operation step that reduces the first wastewater treatment volume.

41. The method according to claim 40, characterized in that: (3) In the hydrogenation purification reaction process R2, when the processing stream U2V-1B is processed in the sub-region hydrogenation purification reaction process R20M, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged from the hydrogenation purification reaction process R2 as the hydrogenation purification reaction product R2P without passing through other sub-region hydrogenation purification reaction processes. Meanwhile, the sub-regional hydrogenation purification reaction processes of R2 other than the sub-regional hydrogenation purification reaction process R20M do not receive either the stream U2V-1B or the reaction product R20MP of the sub-regional hydrogenation purification reaction process R20M; only hot, water-poor hydrogen-rich gas flows through. In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell and the gas phase space is connected. The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

42. The method according to claim 40, characterized in that: (3) In the first stage of the hydrogenation purification reaction process R2, when the process stream U2V-1B is processed in the first sub-region hydrogenation purification reaction process R201, the reaction product R201P of the first sub-region hydrogenation purification reaction process R201 is discharged from the hydrogenation purification reaction process R2 after passing through all the other sub-region hydrogenation purification reaction processes located downstream, and is used as the hydrogenation purification reaction product R2P. When the sub-region hydrogenation purification reaction process R20M processes the stream U2V-1B, the reaction product R20MP of the sub-region hydrogenation purification reaction process R20M is discharged after passing through the downstream sub-region hydrogenation purification reaction process R2, and is used as the hydrogenation purification reaction product R2P. Meanwhile, all sub-region hydrogenation and purification reaction processes located upstream of sub-region hydrogenation and purification reaction process R20M do not receive stream U2V-1B; only hot, water-deficient, hydrogen-rich gas flows through them. Sub-region hydrogenation and purification reaction process R20M receives the effluent from the upstream sub-region hydrogenation and purification reaction process. In the reactor of the hydrogenation purification reaction process R2, two or more or all of the sub-region hydrogenation purification reaction processes are arranged in the same pressure vessel shell. The hydrogenation purification reaction process of all sub-regions of R2 is arranged in one, two or more reactors.

43. The method according to any one of claims 3 to 10, characterized in that: (3) The hydrocarbon feed for the hydrogenation reaction process R1 contains one or more of the following fractions: ① Hydrocarbons with a conventional boiling point of 200–350℃, including phenols and / or aromatics; ② Hydrocarbons with a conventional boiling point of 350–450℃, including phenols and / or aromatics; ③ Hydrocarbons with a conventional boiling point of 450–550℃, including phenols and / or aromatics; The hydrogenation reaction process R1 is either a fluidized bed hydrogenation reaction process or a suspended bed hydrogenation reaction process. The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

44. The method according to any one of claims 3 to 10, characterized in that: (3) The hydrocarbon feed for the hydrogenation reaction process R1 is a hydrocarbon stream containing phenols and aromatics obtained from the direct liquefaction reaction product of coal hydrogenation, mainly composed of hydrocarbons with conventional boiling points of 150 to 550°C. The hydrogenation reaction process R1 is either a fluidized bed hydrogenation reaction process or a suspended bed hydrogenation reaction process. The effluent R1P from the hydrogenation reaction R1 is a material containing phenols, aromatics, and water.

45. The method according to any one of claims 1 to 10, characterized in that: (2) The operating temperature of the first wastewater vaporized gas U2V-1 obtained in the wastewater vaporization process U2 is at least 30°C higher than the water dew point; (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 50°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 6.0~18.0MPa.

46. ​​The method according to any one of claims 1 to 10, characterized in that: (2) The operating temperature of the first wastewater vaporized gas U2V-1 obtained in the wastewater vaporization process U2 is at least 30°C higher than the water dew point; (3) The operating temperature of R2 in the hydrogenation purification reaction process is at least 70°C higher than the water dew point, and the hydrogen partial pressure of R2 in the hydrogenation purification reaction process is 9.0~14.0MPa.

47. The method according to any one of claims 3 to 10, characterized in that: (3) In the hot high pressure separation process R1P-S1, the reaction effluent R1P from the hydrogenation reaction process R1 is separated to obtain hot high pressure gas R1P-S1V and hot high pressure oil R1P-S1L. The hydrocarbon stream R1P-S1L-TOR2 obtained from separating the hot high-density oil R1P-S1L enters the hydropurification reaction process R2; Hydrocarbon stream R1P-S1L-TOR2 is mainly composed of hydrocarbons with conventional boiling points below 250℃ and / or hydrocarbons with boiling points between 250℃ and 320℃.

48. The method according to any one of claims 1 to 10, characterized in that: (3) The clean hydrocarbon stream KEYS containing hydrocarbon components with a conventional boiling point of 300-350℃ undergoes a hydrogenation purification reaction process R2, and at least a portion of the clean hydrocarbon stream KEYS remains in a liquid phase during the hydrogenation purification reaction process R2.

49. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX used for heat recovery and becomes the stream K-HX-HP. The weight flow rate of the liquid water component in the stream K-HX-HP is not less than 85% of the weight flow rate of the water component in the cold high-pressure water S7-W. After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

50. The method according to any one of claims 1 to 10, characterized in that: (3) Cold high pressure separation process S7 separates hydrogen-containing, water-containing, and hydrocarbon-containing streams based on hydrogenation purification reaction effluent R2P to obtain cold high pressure gas S7-V, cold high pressure water S7-W, and cold high pressure oil S7-L; The feed for the cold high-pressure separation process based on the hydrogenation purification reaction effluent R2P flows out of the last heat exchanger K-HX for heat recovery and becomes the stream K-HX-HP. The temperature of the stream K-HX-HP is not higher than 150-170℃. After being cooled down, the K-HX-HP logistics components enter the cold high-pressure separation process S7.

51. The method according to claim 27, characterized in that: (2) Washing oil U3-AL is a component of heavy diesel oil with a conventional boiling point of 250-350℃.

52. The method according to claim 37, characterized in that: (2) Washing oil KU52-LF is a component of heavy diesel oil with a conventional boiling point of 250-350℃.

53. The method according to claim 51 or 52, characterized in that: (1) Primary source of sewage The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It includes wastewater that has undergone or has not undergone wastewater pretreatment. The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process; (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

54. The method according to claim 51 or 52, characterized in that: (1) Primary source of sewage The first type of wastewater includes wastewater containing phenols, aromatics, and solid particles generated from the separation process of products from direct coal hydrogenation liquefaction reaction. It includes wastewater that has undergone or has not undergone wastewater pretreatment. The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process; (2) Washing oil KU52-LF is a heavy diesel oil component with a conventional boiling point of 250-350℃. It is a heavy diesel oil DIES100 produced by the hydrotreating reaction of "coal hydrogenated direct liquefaction oil and / or hydrotreated oil modified by coal hydrogenated direct liquefaction oil", or a rich absorbent oil formed by the absorption process of heavy diesel oil DIES100 through the recovery of liquefied gas and gasoline containing liquefied gas and light gasoline components. In this way, heavy diesel oil DIES100 is used in series twice.

55. The method according to any one of claims 1 to 10, characterized in that: (1) Primary source of sewage The first type of wastewater, which may or may not contain solid particles, is the initial wastewater that has undergone or has not undergone a wastewater pretreatment process; The wastewater pretreatment process includes one or more of the following functions: solids removal process before hydrogen sulfide and ammonia removal, free oil removal process, hydrogen sulfide and carbon dioxide removal process, ammonia removal process, and phenol removal process; (2) Wastewater vaporization process U2 In the first wastewater light oil desolidification process, the first wastewater is mixed and contacted with the first desolidified hydrocarbon oil feedstock, and then separated into the first desolidified rich oil and the first desolidified wastewater. The solid content in the first desolidified rich oil is higher than the solid content in the first desolidified hydrocarbon oil feedstock; The solid content in the first wastewater with reduced solids is lower than the solid content in the first wastewater. In the wastewater vaporization process U2, at least a portion of the vaporizable pollutant component KCM in the first solids-degrading wastewater, which contains water, phenols and / or aromatics, is vaporized into vaporized gas KCM-V, and the first wastewater vaporized gas U2V-1 is obtained based on the vaporized gas KCM-V. The first wastewater vaporized gas, U2V-1, is either a wet gas or a dry gas. The first wastewater vaporized gas, U2V-1, may or may not contain liquid hydrocarbon oil.

56. The method according to claim 55, characterized in that: (2) In the first wastewater light oil desolidification process, the first desolidified hydrocarbon oil feedstock is hydrocarbon oil based on the condensed oil of the wastewater vaporization process U2, and / or is hydrocarbon oil obtained by separating the hydrogenation purification reaction effluent R2P; The first step is to remove solids from the oil, which is then removed from the oil through a solids removal process before the hydrogen sulfide and ammonia removal processes. In the pre-solids removal process before the desulfurization and deammoniation process, the oil-rich stream based on the first solids removal process is mixed and contacted with the pre-sewage stream based on the initial wastewater, and then separated into pre-solids-rich oil-rich stream and pre-solids-reducing wastewater. The solid content in the pre-desolidation rich oil is higher than that in the first desolidation rich oil; The solid content in the pre-treatment solids-reducing wastewater is lower than the solid content in the pre-treatment wastewater stream; Based on the logistics of pre-treated solid wastewater, it undergoes the first wastewater light oil desolidification process.

57. The method according to claim 56, characterized in that: (3) The effluent R1P from the hydrocarbon hydrogenation process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1V; the hot high-pressure oil R1P-S1L contains solid particles. The material based on the hot high-density gas R1P-S1V is mixed and contacted with the material based on the first wastewater to form the first wastewater vaporized gas U2V-1 in a dry or wet state. During the separation and fractionation process of FRAC80, the hot high-separation oil R1P-S1L is separated into gas, narrow-separation oil, and separation bottom oil FRAC80-DV containing solid particles; Based on the pre-solidification rich oil stream, it enters the separation and fractionation process FRAC80 and is mixed and separated with the hot high-separation oil stream R1P-S1L to form narrow-separation oil products. The solid particles contained in the pre-solidification rich oil stream enter the separation bottom oil FRAC80-DV.

58. The method according to any one of claims 1 to 10, characterized in that: (3) In the hydrogenation purification reaction process R2, hydrocarbons containing phenols and / or aromatics with conventional boiling points below 350℃ are processed together (P600). Hydrocarbons P600, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

59. The method according to any one of claims 1 to 10, characterized in that: (3) In the hydrogenation purification reaction process R2, hydrocarbons containing phenols and / or aromatics with conventional boiling points below 250℃ are processed together with P700. Hydrocarbons P700, including or excluding hydrocarbon streams obtained from the direct liquefaction of separated coal to produce oil.

60. The method according to any one of claims 3 to 10, characterized in that: (3) The effluent R1P from the hydrocarbon hydrogenation process R1 is separated into hot high-pressure gas R1P-S1V and hot high-pressure oil R1P-S1L in the hot high-pressure separation process R1P-S1. The hydrocarbons containing phenols and / or aromatics with conventional boiling points below 250℃ obtained from the separation of hot high-temperature oil R1P-S1L are then processed in the hydrogenation purification reaction process R2.

61. The method according to any one of claims 1 to 10, characterized in that: (1) The primary source of wastewater is wastewater with low chloride ion content, selected from the top water of the fractionation tower and vacuum tower of the coal hydrogenation direct liquefaction to produce oil, the top water of the fractionation tower of the coal hydrogenation direct liquefaction to produce oil through hydrogenation modification, and acidic water from gas fractionation.

62. The method according to any one of claims 3 to 10, characterized in that: (3) Hydrocarbon hydrogenation reaction process R1 is the hydrogenation and upgrading reaction process of direct coal liquefaction oil or hydrogenated modified oil of direct coal liquefaction oil.

63. The method according to any one of claims 1 to 10, characterized in that: (2) Wastewater vaporization process U2 The first wastewater vaporization gas U2V-1 is a material containing dust and / or high-boiling-point phenols and / or high-boiling-point aromatics. Based on the gas of the first wastewater vaporization gas U2V-1, after cooling, condensation, separation and deliquescence process KU51 and / or oil washing and deliquescence process KU52, a gas with lower dust content and / or lower high-boiling-point phenol content and / or lower high-boiling-point aromatic content is obtained and enters the hydrogenation purification reaction process R2.