Method for oxidative desulfurization of oil and liquid hidrocarbon fuel and reduction of harmful emissions of sulfur and carbon oxides

Abstract

The invention relates to the field of oxidative desulfurization of oil and sulfur-containing liquid hydrocarbon fuels (including diesel fuel) and can be used to reduce harmful emissions and exhausts (in the form of sulphur oxide and carbon monoxide - SO2 and CO) of oil refineries, as well as various industrial enterprises (including energy), facilities and engines using hydrocarbon fuels. Method of oxidative desulfurization of oil and liquid hydrocarbon fuel and reducing harmful emissions of sulfur oxides and carbon provides a process of oxidation in tanks or pipelines by ozone (O3) or ozone-containing gases, in which sulfur oxides (SO2 and SO), without releasing them into the atmosphere, mix in a closed vessel or pipeline with carbon monoxide (CO) and by means of chemical reactions of sulfur monoxide decomposition (2SO↑ → SO2↑+S↓) and sulfur recovery (SO2↑ + 2CO↑ → S↓ + 2CO2↑) elemental sulfur (S) is extracted from oil or liquid hydrocarbon fuel and carbon monoxide (CO) is converted into its dioxide (CO2). The oxidation, also decomposition and recovery reactions are carried out one-step or sequentially, in the presence of oxidation-recovery group catalysts corresponding to these reactions, such as tert-Butyl hydroperoxide (C₄H₁₀O₂). Ozonized atmospheric air is used as ozone-containing gas.

Description

[0001] METHOD FOR OXIDATIVE DESULFURIZATION OF OIL

[0002] AND LIQUID HIDROCARBON FUEL AND REDUCTION OF HARMFUL EMISSIONS

[0003] OF SULFUR AND CARBON OXIDES

[0004] Field of technology

[0005] The invention relates to the field of oxidative desulfurization of oil and sulfur- containing liquid hydrocarbon fuels (including diesel fuel) and can be used to reduce harmful emissions and exhausts (in the form of sulfur oxide and carbon monoxide) of oil refineries, as well as various industrial enterprises (including power generation), vehicles and engines using hydrocarbon fuels.

[0006] State of the art

[0007] It is generally known from extensive information / scientific sources that oil contains a significant proportion of sulfur (0.1-7%) in the form of various compounds such as hydrogen sulfide, mercaptans, elemental sulfur, also sulfides, disulfides, thiophene and thiophene homologues. Oil grades and petroleum products (e.g. diesel fuel) with higher sulfur content have lower value on the world market. Modern technologies make it possible to increase their value through desulfurization.

[0008] Desulfurization technologies are complex and capital-intensive, but standards are becoming stricter every year due to environmental necessity. If for EURO-3 the maximum limit of sulfur compounds was 350 mg / kg, then for EURO-5 the indicator was reduced to 10 mg / kg, i.e. the sulfur content in diesel fuel was reduced to 0.001%, based on the fact that sulfur in oil affects the performance properties of petroleum products. Active sulfur-containing compounds cause corrosion, which leads to equipment damage and soot formation. It is necessary to choose fuel with optimal sulfur content. During distillation of raw materials sulfur and sulfur gases are obtained. The sulfur content in oil affects atmospheric pollution, as combustion of sulfur impurities of oil products generates toxic sulfur oxide (causing, in the environment of other harm, and acid rain) and even sulfur dioxide. It is impossible and not necessary to completely exclude sulfur from the composition of diesel fuel. The substance has lubricating properties and prevents the formation of nicks on the metal parts of the engine. The most important purpose of sulfur removal is to reduce emissions of sulfur oxides into the atmosphere, which are formed during combustion of sulfur compounds. To date, one of the most mastered technologies for desulfurization of oil fractions is hydrotreating, but the prospect of further development of this method is in doubt, as it has a number of disadvantages. However, hydrotreating processes have practically reached the limit of their efficiency and to bring the sulfur content in petroleum products to 50 ppm and below by means of hydro treating requires economic costs. Sulfuric acid method of fuel purification is also used. A 90% concentration of sulfuric acid is added to the fuel. It binds tars and carcinogens, turning them into tar. After the end of the reagents' action, the liquid is poured into a special tank, the resulting residue can be used for further processing.

[0009] This problem gave impetus to the development of alternative directions of desulfurization, among which oxidation (molecular oxygen, ozone), extraction, precipitation, alkylation and adsorption stand out. This of the methods of selective recovery (extraction) of sulfur organics is oxidative desulfurization, i.e. removal of sulfur-containing compounds.

[0010] Today one of the most mastered technologies for desulfurization of oil fractions is hydrotreating, but the prospect of further development of this method is in doubt, as it has a number of drawbacks. However, hydrotreating processes have practically reached the limit of their efficiency and to bring the sulfur content in petroleum products to 50 ppm and below by means of hydrotreating requires economic costs. Sulfuric acid method of fuel purification is also used. A 90% concentration of sulfuric acid is added to the fuel. It binds tars and carcinogens, turning them into tar. After the end of the reagents' action, the liquid is poured into a special tank, the resulting residue can be used for further processing.

[0011] This problem gave impetus to the development of alternative directions of desulfurization, among which oxidation (molecular oxygen, ozone), extraction, precipitation, alkylation and adsorption stand out. One of the methods of selective recovery (extraction) of sulfur organics is oxidative desulfurization, i.e. removal of sulfur-containing compounds. Technologies of desulfurization / demercaptanization of hydrocarbon feedstock by direct oxidation of hydrogen sulfide and mercaptans directly in gas streams during distillation are being developed. The desulfurization process is carried out by passing sulfur-containing hydrocarbon aerosol through catalyst blocks at different temperatures. The technology consists in oxidation of low-molecular mercaptans and hydrogen sulfide contained in oils by air oxygen in the presence of a catalyst with subsequent separation in an alkaline environment.

[0012] The most reliable and available methods for the separation of organosulfur compounds are oxidation with various oxidizing agents. Among other methods of oxidative effect on various types of hydrocarbon raw materials it should be noted desulfurization of heavy oil fractions by ozonation and radiolysis, ultrasonic treatment of diesel fractions in the presence of an aqueous solution of hydrogen peroxide and quaternary ammonium salt as an interfacial catalyst.

[0013] Let us give some examples of many known methods of oxidative desulfurization of crude oil and petroleum products using ozone:

[0014] JP2003193066A - METHOD FOR OXIDATIVE DESULFURIZATION OF LIQUID PETROLEUM PRODUCT AND OXIDATIVE DESULFURIZATION PLANT;

[0015] JP2005015533A - METHOD AND APPARATUS FOR OXIDATIVE

[0016] DESULFURIZATION OF LIQUID PETROLEUM PRODUCTS;

[0017] JP2004155844A - DEVICE AND METHOD FOR REMOVING CONTAMINANT FROM LIQUID FUEL;

[0018] EA003072B1 - DESULFURIZATION PROCESS;

[0019] RU2008113311A - DEVICE FOR MODIFICATION OF EXISTING DIESEL FUELS;

[0020] RU97110304A - METHOD OF OBTAINING AN ADDITIVE FOR ACTIVATION OF SECONDARY OIL REFINING PROCESSES;

[0021] JPS62290793A - METHOD OF DESULFURIZING HYDROCARBON OIL;

[0022] RU2123026C1 - METHOD OF PROCESSING HEAVY OIL FRACTIONS. All of the above mentioned methods and devices remove sulfur - reduce its content - with varying degrees of efficiency. At the same time, these sources do not pay special attention to the by-product of these processes, the sulfur oxide (SO2) gas emitted into the atmosphere.

[0023] More closely related to the present invention are:

[0024] - “Method of pretreatment of petroleum product in ozone-air mixture to reduce sulfur content”, according to Russian patent RU2786974C1. It provides for saturation of the petroleum product with ozone-air mixture by means of arrangement of nozzles for supply of ozone-air mixture and nozzles for supply of petroleum product in tanks. By means of nozzles the oil product is subjected to fine atomization with simultaneous exposure to ozone-air mixture at the temperature of 20-25°C. For the efficiency of the saturation process, electromagnetic field is applied. Oxidation of sulfur compounds by ozone with subsequent extraction of oxidized compounds and reduction of costs for the use of expensive catalysts takes place;

[0025] - US2015232765A1 - COLD PROCESS FOR REMOVAL OF SULFUR IN STRAIGHT RUN DIESEL BY OZONE AND TERT-BUTYL HYDROPEROXIDE. This is the process of removing sulfur compounds from a real fuel product by the action of ozone and tert-Butyl hydroperoxide (t-BUOOH) barbotation under normal laboratory conditions. A slight desulfurization occurs after the ozone barbotation process, which can be attributed to the removal of sulfur compounds in gaseous form (SOx). Most of the organically bound sulfur and / or elemental sulfur and hydrogen sulfide are still present in the ozonized samples. Sulfur removal from diesel SRD samples was achieved by combining ozone bubbling with extraction using various solvents to remove the oxidized sulfur compound (polar) from the ozonated samples. This method provides a significant level of total sulfur reduction, with sulfur reductions as high as 93%.

[0026] At the same time, these sources do not pay special attention to the complexity of extraction of oxidized compounds (including SO2), which is undoubtedly possible, but requires separate considerable costs. In addition, it is not clear what is to be done with the extracted harmful sulfur oxide (SO2). The closest to the present invention in its essential features is selected as a prototype “Split-phase desulfurization method and device based on ozone oxidation”, according of Chinese patent application CN113234479A. A split-phase desulfurization method and device based on ozone oxidation is disclosed herein. The method includes the following several steps: extraction, mixing an oil product to be desulfurized with an extractant, mixing uniformly to obtain a first oil phase and a first extraction phase, and collecting the first oil phase; performing oxidative desulfurization: introducing ozone into the first extraction phase for the first oxidative desulfurization and introducing air after the oxidation is completed to remove the ozone dissolved in the first extraction phase to obtain a primary desulfurization product; and circulating: uniformly mixing the primary desulfurization product with the first oil phase, repeating the extraction and oxidative desulfurization steps, and finally collecting the obtained oil phase, namely the desulfurized oil product. The sulfur-containing compound in the oil phase is extracted into the extraction phase by extraction, and then the extraction phase is desulfurized by ozone oxidation after phase separation, so that the sulfur content of the oil product is less than 10 parts per million, and the desulfurization degree reaches 98.68%.

[0027] However, this method, as well as all the previous ones, does not solve in any simple way the ecological issue of utilization of extracted sulfur oxide in order not to emit it into the atmosphere in such a form or to convert it by expensive methods into something else, for example, by mixing it with water, into sulfuric (H2SO4) or sulfurous (H2SO3) acid, which is unnecessary in large quantities and difficult for safe storage.

[0028] Purpose of the Invention

[0029] The invention is aimed at reducing harmful emissions in the form of sulfur oxide (SO2), which is a by-product of oil and oil products desulfurization processes, as well as exhausts in the form of carbon monoxide (CO), which is a product of incomplete combustion of hydrocarbon fuel in various installations and technological processes.

[0030] Disclosure of the invention

[0031] The essence of the invention lies in the possibility of combining the said harmful gases and as a result transforming them into harmless substances. Namely, the purpose of the invention is achieved, the problem is solved and the mentioned effect is achieved by the fact that the method of oxidative desulphurization of oil and liquid hydrocarbon fuel and reduction of harmful emissions of sulfur and carbon oxides, which at a temperature not exceeding the boiling point of oil or fuel provides a process, at least one-stage, their oxidation in tanks or pipelines by ozone (O3) or ozonecontaining gases, with possible additional use of ultrasonic, electromagnetic or radiant actions to enhance the effect, with the side effect of release, possibly along with other gases, including sulfur dioxides (SO2) and intermediate / unstable sulfur monoxide (SO), according to the present invention, has the following essential distinguishing features:

[0032] - sulfur oxides (SO2and SO), possibly along with other gases, without full or partial release into the atmosphere, are combined / mixed in a closed tank or pipeline with waste / process and / or exhaust gases of industrial enterprises, vehicle engines or power plants, containing, possibly along with other gases, the products of incomplete combustion of hydrocarbon fuels, and carbon monoxide (CO, and the way of realization of the following well-known chemical reactions occurring by themselves, at the mentioned combination / mixing:

[0033] - decomposition of sulfur monoxide: ;

[0034] - and recovery of sulfur: , extract elemental sulfur (S) from oil or liquid hydrocarbon fuel, mainly in powdered form, and convert carbon monoxide (CO) into its dioxide (CO2), with the possibility of subsequent release of the latter into the atmosphere;

[0035] - said chemical reactions of decomposition and recovery are carried out sequentially, with heating during recovery, in one tank or pipeline and cooling during decomposition, in another, or vice versa.; - oxidation with ozone or ozone-containing gases and / or said chemical reaction of recovery of sulfur is carried out in the presence of oxidation-recovery group catalysts corresponding to these reactions;

[0036] - oxidation by ozone or ozone-containing gases and / or said chemical reaction of recovery of sulfur is carried out in the presence of / using tert-Butyl hydroperoxide (C4H10O2);

[0037] - ozonized atmospheric air is used as the ozone-containing gas.

[0038] There is a cause-and-effect relationship between the distinctive features of the invention and the achieved result.

[0039] On the one hand, it is generally known (at least from the above-mentioned information sources of the state of the art) that oil or petroleum product refineries, in order to desulphurize them by oxidizing them with ozone, emit harmful gas in the form of sulfur oxides (SO2, accompanied by unstable SO) into the atmosphere.

[0040] On the other hand, it is well known that completely different enterprises, installations or internal combustion engines, located perhaps in completely different places, i.e. far from oil refineries, consuming the same hydrocarbon fuel, emit into the atmosphere harmful technological (or as a product of non-combustion) gas in the form of carbon monoxide (CO).

[0041] These enterprises are usually located in different places by themselves and are not necessarily located close to each other for any special purpose.

[0042] On the third hand, from special / scientific, encyclopedic or even educational literature, the chemical reactions of “Decomposition” of monoxide are generally known sulfur and “Recovery” of sulfur , with the help of carbon monoxide, with the production of elementary sulfur and carbon dioxide.

[0043] As a result of the juxtaposition of the mentioned three well-known facts, an inventive concept is manifested, which is unknown from the art and for the skilled person does not clearly follow from it (and therefore the present invention satisfies the criteria of “Novelty” and “Inventive step”), a convergence / connection is called for, before release into the atmosphere, of these two harmful gases (SO2and CO) in a closed vessel or pipeline and thus, without much effort, to convert / transform them and obtain elementary sulfur (S) and comparatively much more harmless (than carbon monoxide CO) carbon dioxide (CO2), with the possibility of subsequent release of the latter into the atmosphere.

[0044] By said proximity may be understood the proximity / location of an oil or fuel refinery, for example in proximity to a thermal power plant or to a metallurgical plant, but this proximity (which is desirable for the effective implementation of the invention) is not the subject of the present invention - it is a matter of organization / hosting.

[0045] Example of an embodiment of the invention (Industrial applicability)

[0046] An oil or fuel refinery for desulfurization of, for example, heavy oil or, for example, diesel fuel by ozone oxidation is located (or is already located) in reasonable proximity to, for example, a thermal power plant consuming, for example, natural gas.

[0047] The desulphurization of the oil or petroleum product is carried out by oxidation with ozone or ozone-containing gas (e.g. artificially ozonized atmospheric air) by any of the methods (e.g. those mentioned above) known from the prior art. The sulfur oxide (SO2, possibly accompanied with SO) and carbon monoxide (CO, so-called “carbon monoxide”) emitted by an oil or fuel refinery, without releasing them into the atmosphere, are piped and combined into a common tank (or several tanks) or pipeline.

[0048] In these tanks or common pipelines the mentioned chemical reactions of “Decomposition” of sulfur monoxide ) and “Recovery” of sulfur take place by themselves, one-stage, or carry out sequentially, in several communicating tanks, possibly with heating during recovery, in one tank or pipeline and with cooling during decomposition - in another, or in subsequent ones, or vice versa. In this way, elemental sulfur (S) is extracted from oil or liquid hydrocarbon fuel, mainly in powdered form, and carbon monoxide (CO) is converted into its dioxide (CO2), which is subsequently released into the atmosphere from said vessels or common piping.

[0049] To accelerate the processes, the oxidation with ozone or ozone-containing gases and / or the said chemical reaction of sulfur reduction are carried out in the presence of catalysts from the oxidation-reduction group corresponding to these reactions, for example in the presence of / using tert-butyl hydroperoxide (C4H10O2).

[0050] In carrying out the mentioned chemical reactions of “Decomposition” of sulfur monoxide and “Recovery” of sulfur , the mixing flows of the mentioned harmful gases from the oil or fuel refinery and from the power plant are controlled by the known technical means, controlling the final release of the minimum amount of harmful gases into the atmosphere.

Claims

CLAIMS1. Method for oxidative desulfurization of oil and liquid hydrocarbon fuel and reduction of harmful emissions of sulfur and carbon oxides, which at a temperature not exceeding the boiling point of oil or fuel provides a process, at least one-stage, their oxidation in tanks or pipelines by ozone (O3) or ozone-containing gases, with possible additional use of ultrasonic, electromagnetic or radiant actions to enhance the effect, with the side effect of release, possibly along with other gases, including sulfur dioxides (SO2) and intermediate / unstable sulfur monoxide (SO), characterized by, that the sulfur oxides (SO2and SO), possibly along with other gases, without full or partial release into the atmosphere, are combined / mixed in a closed tank or pipeline with waste / process and / or exhaust gases of industrial enterprises, vehicle engines or power plants, containing, possibly along with other gases, the products of incomplete combustion of hydrocarbon fuels, and carbon monoxide (CO, and the way of realization of the following well-known chemical reactions occurring by themselves, at the mentioned combination / mixing:- decomposition of sulfur monoxide:;- and recovery of sulfur: ,extract elemental sulfur (S) from oil or liquid hydrocarbon fuel, mainly in powdered form, and convert carbon monoxide (CO) into its dioxide (CO2), with the possibility of subsequent release of the latter into the atmosphere.

2. Method according to claim 1, characterized by, that said chemical reactions of decomposition and recovery are carried out sequentially, with heating during recovery, in one tank or pipeline and cooling during decomposition, in another, or vice versa.

3. Method according to any one of claims 1-2, characterized by, that the oxidation with ozone or ozone-containing gases and / or said chemical reaction of recovery of sulfuris carried out in the presence of oxidation-recovery group catalysts corresponding to these reactions.

4. The method according to any one of claims 1-3, characterized by, that the oxidation by ozone or ozone-containing gases and / or said chemical reaction of recovery of sulfur is carried out in the presence of / using tert-Butyl hydroperoxide (C4H10O2).

5. The method according to any one of claims 1-4, characterized by, that ozonized atmospheric air is used as the ozone-containing gas.

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