Process method and reaction system for residual oil conversion

Abstract

A residual oil conversion process method and a reaction system belong to the field of oil refining processing, and the process method comprises the following steps: mixing a heavy inferior residual oil raw material with a dispersed molybdenum-containing catalyst and a partially circulated heavy fraction cracking product; after heat exchange and temperature rise, pretreatment is conducted through a 10-30 KHz ultrasonic device; after preheating, entering a slurry bed hydrogenation reactor, and carrying out a hydro-conversion reaction in a hydrogen atmosphere under the conditions of 380-500 DEG C and 5-18 MPa; after subsequent processes and equipment separation, the heavy liquid hydrocarbon part enters a catalytic cracking device and is subjected to a contact reaction with a residual oil cracking catalyst containing aluminum extraction and silicon supplement Y zeolite under the conditions that the temperature is 500-540 DEG C and the catalyst-oil ratio is 5-15; fractionating the product in a fractionating tower; the reaction system comprises an ultrasonic pretreatment device, a slurry bed reactor, a catalytic cracking device, a product fractionating tower and heat exchange, separation and circulation equipment. According to the method, the conversion efficiency and process stability of the heavy inferior residual oil raw material are improved, the yield of light fraction gasoline is increased, the energy consumption is reduced, and the method has good economical efficiency and practicability.

Description

Technical Field

[0001] The present invention relates to a process method and a reaction system for residual oil conversion, and specifically to a conversion method and a reaction system for inferior heavy oil / residue oil by a slurry bed hydrogenation and heavy oil catalytic cracking process combination, belonging to the technical field of oil refining processing. Background Art

[0002] With the extensive use of oil resources, there has been a trend of heavy and inferior oils. Deep processing and refining of heavy and inferior oils, especially residual oils, such as residual oil hydrogenation, is the core content of improving the utilization rate of oil resources and increasing the economic benefits of refineries. Decarbonization or hydrogenation of inferior heavy oil / residue plays an increasingly important role in further improving the yield of light oil products, and has been highly valued by various oil refining companies.

[0003] The slurry bed hydrogenation process can process heavy low-quality crude oil with high metal content (nickel and vanadium mass content above 100 μg / g), high residual carbon (mass content of residual carbon greater than 15%) and high sulfur (mass content of sulfur greater than 2%), and has a high light oil yield and good product quality. As described in technical documents such as U.S. Patents USP4066530, USP4125455, and USP4134825, it overcomes some problems existing in other industrial technologies such as coking, thermal cracking, and residual oil catalytic cracking, and improves the lightweighting capability in heavy raw material processing.

[0004] Typical foreign slurry bed hydrogenation technologies include VCC technology, EST technology, UniflexSHC technology, HDH-PLUS technology, etc. All four slurry bed hydrogenation technologies have successfully achieved the lightweight treatment of heavy and inferior oil products. However, for inferior heavy oil / residue oil raw materials, the single slurry bed hydrogenation process still has the disadvantages of not being ideal in conversion process and effect, and it is difficult to fully meet the requirements, and the tail oil is not easy to handle and utilize.

[0005] Chinese patent CN1107705C discloses that a fixed bed pretreatment hydrogenation reactor is placed in front of a slurry bed hydrogenation reactor to further improve the conversion effect; CN104017601B adopts a slurry bed hydrocracking and a fixed bed hydrocracking process combination; in a series of Chinese patents CN106147845B, CN106147846B, CN106147847B and CN106544055B, CN106544056B, a slurry bed hydrogenation reactor is followed by a fixed bed hydrogenation reactor as the second hydrogenation reactor; and in a series of Chinese patents CN103540348B, CN103540349B, CN103540350B, more fixed bed reactors are connected in series to further improve the hydrogenation conversion effect, and to take into account various needs and meet the diverse refining and processing purposes.

[0006] In addition to the combination of a slurry bed hydrogenation reactor and a fixed bed hydrogenation reactor, Chinese patents such as CN112175668B, CN1107706C and CN104560159B also use two slurry bed reactors in series to carry out residue oil hydrogenation conversion in order to extend the conversion life, inhibit coking and improve the conversion rate.

[0007] In addition to combining hydrogenation processes with different reactor forms, conversion methods combining slurry bed hydrogenation with other processing technologies have also emerged. For example, CN103242894A combines slurry bed hydrogenation with tailings gasification hydrogen production technology, thus eliminating the need for an external hydrogen source. As the core process for lightening heavy raw materials, catalytic cracking and slurry bed hydrogenation are naturally given special attention.

[0008] For example, Chinese patent CN114045179B discloses a combined process and reaction system for multiphase flow residue oil hydro-modification and catalytic cracking, wherein the residue oil is hydro-modified by a suspended bed hydrogenation process, and the metal elements and carbon residue in the raw material are removed to the maximum extent by shallow hydro-modification under mild reaction conditions in the presence of hydrogen. The reaction products are initially separated by gas and liquid to obtain heavy distillate oil, light distillate oil and medium distillate oil; the medium distillate oil is the first-stage raw material for catalytic cracking, and the heavy distillate oil and the catalytic cracking reaction products enter the catalytic cracking fractionation tower together to complete the removal of catalyst or solid impurities and product separation. The products include gas products, gasoline fractions, diesel fractions, recycled oil and oil slurry, wherein the recycled oil is returned as the second-stage raw material for catalytic cracking, a small part of the oil slurry is discharged as fuel oil, and the rest of the oil slurry is returned to the suspended bed for secondary hydrogenation reaction, and the reaction system realizes energy mutual supply and resource mutual use, and maximizes the improvement of the residue oil conversion rate and the clean oil yield.

[0009] Chinese patent CN101724463B also discloses a combined process of suspended bed residue oil hydrocracking and catalytic cracking, which includes: the residue oil feedstock is heat-exchanged with a high-temperature regenerated catalyst from a catalytic cracking regenerator and then enters a suspended bed residue oil hydrogenation unit for a hydrocracking reaction; all or part of the suspended bed hydrocracking tail oil enters a catalytic cracking unit for a cracking reaction to obtain a gasoline fraction and a diesel fraction; after the catalytic cracking catalyst is regenerated, part of the regenerated catalyst is circulated back to the catalytic cracking unit, and part of the regenerated catalyst is used to preheat the suspended bed residue oil feed to the reaction temperature, thereby saving energy and reducing the heat load of the heating furnace.

[0010] In a suspended bed residue oil hydrogenation and catalytic cracking combined process disclosed in Chinese patent CN101434867 B, the residue oil and catalytic cracking clarified oil are fed into a suspended bed hydrogenation reaction unit together, and a hydrogenation reaction is carried out in the presence of hydrogen and a catalyst; the vacuum distillate oil obtained by the hydrogenation reaction enters the catalytic cracking unit, and the vacuum residue oil is circulated back to the suspended bed hydrogenation unit. The catalytic cracking clarified oil and the heavy cycle oil can enter the suspended bed hydrogenation unit in whole or in part, and the suspended bed hydrogenation unit adopts relatively mild operating conditions. The invention improves the impurity removal capacity, the quality of the raw materials of the catalytic cracking unit, the yield of light oil products, and the stability of the operation of the unit.

[0011] In addition, Chinese patent CN100497546C also discloses the organic combination of more processes, including fixed bed hydrogenation, suspended bed hydrogenation, solvent deasphalting and catalytic cracking processes, to maximize the conversion effect and produce more light products. Chinese patent CN100569924C also includes the combination of multiple processes such as fixed bed hydrogenation, suspended bed hydrogenation and catalytic cracking processes, which improves the processing capacity and processing flexibility of the device, as well as the total liquid yield and distillate oil liquid yield of the conversion process.

[0012] Although the slurry bed hydrogenation process and the improved method process, including the combined process technology combined with the catalytic cracking process, have been widely reported in the public prior art patent literature, and positive technological progress has been achieved, the processing and conversion of inferior heavy oil / residue oil is still the core element and technical difficulty in crude oil refining, and is related to the economic benefits of oil refining enterprises. There are still many shortcomings, such as the conversion ratio of coke, circulating slurry oil, and external slurry oil has remained high, and the conversion rate of inferior heavy oil / residue oil is difficult to continue to break through.

[0013] Therefore, technical research in this field still needs to continuously improve and enhance the conversion methods and reaction systems such as the process and catalyst for slurry bed residue oil hydrogenation, as well as the combined process combined with heavy oil catalytic cracking technology, so as to continuously improve the lightweight conversion efficiency, process stability and technical economy of raw materials such as inferior heavy oil and residue oil in the refining and processing process, so as to meet the actual needs of oil refining enterprises in production. Summary of the invention

[0014] Residue oil slurry bed hydrogenation is a process of thermal conversion of inferior heavy oil under high temperature and high hydrogen pressure. A small amount of catalyst is fully in contact with the raw material residual oil and hydrogen in the reactor, and is in a fully back-mixed state. The dispersed catalysts used are divided into those with water as a dispersant and those with oil as a dispersant. The role of the dispersed catalyst is mainly to inhibit the coking of inferior heavy oil with high residual carbon value and high viscosity during the conversion process, to treat high content of metal nickel, vanadium, calcium, etc., and to achieve a high conversion rate of hydrogenation conversion process.

[0015] The coke suppression effect of hydrogenation of catalysts with oil as dispersant is often better than that of catalysts with water as dispersant. Generally speaking, the hydrogenation activity of molybdenum is higher than that of other transition metals, such as nickel, cobalt, iron, etc. Therefore, in recent years, the slurry bed hydrogenation process has mostly adopted homogeneous molybdenum catalysts, which have the advantages of small dosage, high activity, low cost, easy dispersion, etc., and can further improve the conversion effect, operation flexibility and economy.

[0016] In the residue oil slurry bed hydroconversion, the raw materials and catalysts are fully dispersed to form a cavitation effect to promote component changes and produce effective high-activity phase hydrogenation components. This overcomes the defects of the existing technology such as reduced catalytic activity and high coke yield. How to deal with impure metal elements and high sulfur and residual carbon content are all key points for efficient conversion.

[0017] The catalytic cracking process has high processing flexibility. There are many types of catalysts and cracking active components therein, such as Y zeolite, with great differences in performance. They are greatly affected by the properties of the feed. There are difficulties in processing and converting inferior heavy oil, especially residual oil raw materials. How to reasonably and effectively combine it with the slurry bed hydrogenation process to form an enhanced residual oil conversion capacity are some of the key influencing factors for obtaining efficient conversion effects. In addition, it is difficult to obtain technical progress effects simply through experimental exploration based on the existing technology.

[0018] The purpose of the present invention is to meet the needs of the above-mentioned actual conversion process, overcome the shortcomings of the prior art, further reduce the use of expensive molybdenum elements in the processing process, and improve the conversion efficiency of the combined process of slurry bed residue oil hydrogenation and heavy oil catalytic cracking process, obtain more light fraction products such as gasoline, and reduce energy consumption and costs. An improved conversion method and reaction system for inferior heavy oil / residue feed by slurry bed hydrogenation conversion and residue oil catalytic cracking process is provided.

[0019] The present invention provides a process for residual oil conversion, characterized in that the method comprises:

[0020] After the inferior heavy oil / residue oil raw material is heated to 70-150° C., it is mixed with the heavy distillation cracking product (5%-90%) of part of the recycling after separation in the product fractionation tower and a dispersed catalyst containing molybdenum and iron, phosphorus, sulfur and aluminum elements, with Mo / feed oil 200-350ppm in an ultrasonic pretreatment device; and the mixture is heated to 10-30KHz and the average contact surface power is 1-10W / cm 2 Ultrasonic treatment for 5 to 120 minutes; mixed with hydrogen and further heated to 150 to 350°C, then entering the slurry bed reactor at 380 to 500°C, 5 to 18 MPa, hydrogen-to-oil volume ratio of 100 to 3000, and liquid space velocity of 0.1 to 2.5 h -1Under the conditions of , hydrogenation conversion is carried out; after the product is separated, the heavy liquid hydrocarbon part enters the riser heavy oil catalytic cracking unit, and contacts and reacts with the residual oil cracking catalyst containing 20wt% to 60wt% of aluminum-extracted silicon-supplemented Y zeolite under the conditions of 500-540°C, catalyst-oil weight ratio of 5-15, and reaction time of 0.1 to 10 seconds, and the cracking products enter the product fractionation tower for separation.

[0021] The "partially recycled heavy distillation cracking products (5% to 90%) after separation in the product distillation tower" refers to the heavy distillate oil from the side line of the product distillation tower (such as the distillation section >350°C), the bottom clarified oil and the externally-thrown oil slurry used for circulation, which account for 5 to 90% of this part of the heavy distillation cracking products after separation; preferably, the proportion is 30 to 85%.

[0022] In the process for converting residual oil provided by the present invention, preferably, the raw material is heated to 100-120°C, and subjected to 12-25KHz and an average contact surface power of 3-6W / cm 2 Ultrasonic device pretreatment for 10 to 60 minutes; further heated to 200 to 300 ° C, and then into the slurry bed reactor at 400 to 460 ° C, 8 to 15 MPa, hydrogen to oil volume ratio of 500 to 2000, liquid space velocity of 0.2 to 2.0 h -1 under the conditions of 510-530°C, catalyst-oil weight ratio of 6-10, reaction time of 0.5-5 seconds, and a residual oil cracking catalyst containing 35wt%-55wt% of aluminum-extracted silicon-supplemented Y zeolite to react in contact.

[0023] In a process for the conversion of residual oil provided by the present invention, it is characterized in that the inferior heavy oil / residue oil raw material is one of inferior crude oil, atmospheric residual oil, vacuum residual oil, deoiled asphalt, oil sand asphalt, coal liquefaction heavy oil, coal tar, steam cracking tar, coking tail oil, catalytic oil slurry or a mixture thereof. Preferably, the raw material has high metal, high residual carbon and high sulfur content, and the mass content of nickel and vanadium can reach more than 100 micrograms / gram, the mass content of residual carbon is greater than 15wt%, and the mass content of sulfur is greater than 2wt%.

[0024] The process method for residual oil conversion provided by the present invention is characterized in that the dispersed catalyst uses oil or water as a dispersant; Mo / feed oil is 280-320 ppm; Fe / (Mo+Fe) is 0.1-0.3, P / (Mo+P) is 0.1-0.25, S / (Mo+S) is 0.75-0.85, and Al / (Mo+Al) is 0.7-0.9; preferably, oil is used as a dispersant.

[0025] The process method for residual oil conversion provided by the present invention is characterized in that the molybdenum component introduced into the dispersed hydrogenation catalyst during the preparation process is provided by one or more of molybdenite, molybdenum chalcopyrite, molybdenum antimony copper ore or molybdenum salt particles; the introduced iron component is provided by one or more of bauxite, red mud, iron sulfate, limonite, laterite or iron salt particles; the introduced aluminum component is provided by one or more of bauxite, aluminum hydroxide, aluminum oxide, diaspore, aluminum sol or aluminum salt particles; the introduced phosphorus component is provided by phosphorus salts and phosphorus-containing compounds; and the introduced sulfur component is provided by sulfide.

[0026] In the process method for residual oil conversion provided by the present invention, preferably, the molybdenum component introduced in the process of preparing the dispersed catalyst is a molybdenum-containing salt selected from one or more of ammonium molybdate, molybdenum chloride, molybdenum sulfate, molybdenum nitrate, sodium molybdate, and molybdenum trioxide; the iron component introduced is an iron-containing salt selected from one or more of ferric chloride, ferric sulfate, ferric nitrate, ferrous chloride, ferrous sulfate, ferrous nitrate, ferric oxide, ferric tetroxide, ferrous oxide, and ferric hydroxide; the phosphate salt and phosphorus-containing compound of the introduced phosphorus component are selected from one or more of phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate; the introduced aluminum component is selected from one or more of aluminum hydroxide, aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, potassium aluminate, aluminum oxide, boehmite, pseudo-boehmite, and aluminum sol; the sulfide of the introduced sulfur component is selected from one or more of carbon disulfide, sodium sulfide, ammonium sulfide, and potassium sulfide; these chemicals can be easily obtained through commercial purchase.

[0027] The process method for residual oil conversion provided by the present invention is characterized in that the residual oil cracking catalyst contains 40wt% to 50wt% of aluminum-extracted silicon-supplemented Y zeolite, which is an artificially synthesized Y zeolite with a silicon-aluminum molar ratio of 2.3 to 2.7, and is processed into a high-silicon Y zeolite with a silicon-aluminum molar ratio of 4 to 10 by extracting aluminum and silicon with silicon tetrachloride in the gas phase and / or extracting aluminum and silicon with ammonium fluorosilicate in the liquid phase, and serves as the cracking active component of the residual oil cracking catalyst.

[0028] The process method for residual oil conversion provided by the present invention is characterized in that the residual oil cracking catalyst is circulated from the riser reactor to the fluidized bed regenerator after being deactivated by carbon deposition in the heavy oil catalytic cracking unit, and is regenerated and reactivated by burning with air at 680-820°C, preferably using two-stage regeneration.

[0029] The present invention also provides a process system for residual oil conversion, characterized in that the system comprises: heavy low-quality raw oil, dispersed hydrogenation catalyst, ultrasonic pretreatment device, slurry bed reactor, gas-liquid separation equipment, catalytic cracking device, residual oil cracking catalyst, product fractionation tower, hydrogen circulation compressor, heat exchanger / heater and circulation pump; after the heavy low-quality raw oil (1) is heated, it is mixed with part of the circulating heavy distillation cracking product and the dispersed hydrogenation catalyst (3) in the ultrasonic pretreatment device (4); after ultrasonic pretreatment; after being mixed with hydrogen (2) and further preheated and heated, it enters the slurry bed reactor (5) for hydrogenation conversion; after the product is separated by the gas-liquid separation equipment (6, 7), the heavy liquid hydrocarbon part enters the riser heavy oil catalytic cracking device (8) to contact and react with the residual oil cracking catalyst, and the product enters the product fractionation tower (9) for separation to obtain products of different fractions (11-15); preferably, gasoline, diesel and liquefied gas. Generally, the clarified and impurity-free slurry is used for circulation, and the part containing solid impurities is used as external slurry.

[0030] The present invention provides a reaction system for residual oil conversion, characterized in that the slurry bed hydrogenation reactor is a mechanically stirred kettle, a bubbling tower, a three-phase fluidized bed, a straight barrel or an annular slurry bed reactor, and other types of slurry bed reactors.

[0031] The present invention provides a process system for residual oil conversion, characterized in that the heat exchange process in the reaction system uses the high-temperature regenerated catalyst of the catalytic cracking unit regenerator as a heat source, and provides heat for the heating and preheating of the feed of the pretreatment device, reactor and distillation tower through the heat exchanger and / or heat exchange medium; at the same time, the heat absorption / exothermicity in the catalytic cracking unit and the entire reaction system is also better balanced.

[0032] The chemical operations involved in the present invention are conventional operations well known to those skilled in the art and used daily.

[0033] The beneficial effects of the present invention are as follows: the provided conversion method and reaction system, when used for low-quality heavy oil / residue oil feed with high metal, high residual carbon and high sulfur content, after ultrasonic pretreatment and cavitation, the dispersed molybdenum catalyst, including the catalyst fine powder in the circulating oil, can be highly dispersed and acted on the heavy low-quality raw materials with changed components, the slurry bed hydrogenation conversion and the cracking process of the aluminum-extracted silicon-supplemented Y zeolite with high residue oil cracking activity, realize the reasonable coordination and enhanced complementarity in conversion performance, improve the efficiency of converting heavy low-quality raw materials into light fractions, have better catalytic activity, reaction stability and light fraction (such as liquefied gas, gasoline and diesel) yield, reduce the heavy fraction products, molybdenum dosage, energy consumption and process operation cost, and improve the economy and practicality of the conversion process. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The present invention is a schematic flow diagram of a process for converting residual oil.

[0035] Figure 1 In: 1-heavy low-quality crude oil; 2-hydrogen; 3-dispersed hydrogenation catalyst; 4-ultrasonic pretreatment device; 5-slurry bed reactor; 6-gas-liquid separation equipment I; 7-gas-liquid separation equipment II; 8-riser heavy oil catalytic cracking unit; 9-product fractionation tower; 10-circulating hydrogen compressor; 11-dry gas; 12-liquefied gas; 13-gasoline; 14-diesel; 15-oil slurry.

[0036] It should be noted that, for the purpose of simplicity, clarity and ease of description, the flow chart used to illustrate the present invention only shows the core units and contents related to the present invention; and does not list in detail some pumps, heat exchangers, coolers, fans and towers that are also needed in the present invention. DETAILED DESCRIPTION

[0037] The following specific implementation modes and examples are used to further describe the content and use effects of the present invention. The examples are used as illustrative explanations of the implementation modes of the present invention, but the present invention is not limited thereto.

[0038] like Figure 1 As shown, after the heavy low-quality feedstock oil (1) is heated, it is mixed with part of the recycled heavy distillation cracking products and a dispersed hydrogenation catalyst (3) in an ultrasonic pretreatment device (4); after ultrasonic pretreatment; after being mixed with hydrogen (2) and preheated to a high temperature, it enters a slurry bed reactor (5) for hydrogenation conversion; after the products are separated by gas-liquid separation equipment I (6) and II (7), the heavy liquid hydrocarbons enter the riser heavy oil catalytic cracking device (8) and contact and react with the residual oil cracking catalyst, and the products enter the product fractionation tower (9) for separation to obtain product gasoline (13) and diesel (14), and liquefied gas (12); as well as dry gas (11) and oil slurry (15).

[0039] In the examples, the composition analysis of the raw materials and the reaction products was performed by gas chromatography. The content of the elements was determined by atomic emission spectroscopy and X-ray fluorescence. For other analysis and detection, reference may be made to the relevant analysis methods in (National Standard for Test Methods for Petroleum and Petroleum Products, published by China Standards Press in 1989) and (Petrochemical Analysis Methods (RIPP Test Methods), published by Science Press in 1990).

[0040] Example 1

[0041] This example is used to illustrate the preparation of a dispersed hydrogenation catalyst required for the conversion process of the present invention.

[0042] Referring to the invention content and implementation steps in Example 2 of the patent CN115722269B authorized by the inventor, in a small enamel autoclave in the laboratory, after replacing with nitrogen and isolating the air, under high shear stirring and dispersion, industrial light diesel and biodiesel are used as dispersants, and chemical reagents ammonium molybdate, ferric nitrate, ammonium dihydrogen phosphate and boehmite powder are used as raw materials, and the materials are added according to the calculated amount ratio to prepare the oil-dispersed slurry bed hydrogenation conversion catalyst of Example 1 of the present invention. When the catalyst is used, it should be reduced and sulfurized according to the operating steps of the general hydrogenation catalyst.

[0043] The specific preparation method of the catalyst is as follows:

[0044] In a small laboratory enamel autoclave, the air was replaced with inert gas argon and isolated. 19 g of ammonium molybdate tetrahydrate powder (95 wt%) and 7.5 g of ferric nitrate (95 wt%) were added to 500 ml of water. Under high shear stirring and dispersion, 100 g of pseudo-boehmite powder (Al2O3 65 wt%) and 3 g of ammonium dihydrogen phosphate (95 wt%) were added. Then 100 g of catalytic cracking light cycle oil (total aromatic content 65 v%) was added. The mixture was acidified with 20 wt% dilute nitric acid to a pH <1, reacted for 20 minutes, cooled to room temperature, and slowly neutralized to a pH of 10.5 by adding ammonia water within 35 minutes. 9.0, and add 7.5 grams of ammonium sulfide (95wt%) and 3 grams of carbon disulfide (same as above), react for 30 minutes, heat to 110°C and continue to react for 4 hours. After the reaction, the product is cooled and dehydrated, and then 12 grams of didecyldimethylammonium chloride solution (10wt%) and 20 grams of biodiesel (FAME content 97.5wt%) are added, and high shear stirring and dispersion at 85°C for 40 minutes to obtain an oil-soluble dispersed composition.

[0045] Example 2

[0046] This example illustrates the preparation of a catalyst suitable for catalytic cracking of residual oil required for the conversion process of the present invention.

[0047] Referring to the invention content and implementation steps in Example 3 of the inventor's authorized patent CN106517238B, and using the experimental equipment of the invention, and using chemical reagent silicon tetrachloride and superior industrial product NaY zeolite (crystallinity 95%, Si / Al molar ratio 2.5, Sichuan Runhe Catalyst Company) as raw materials, low sodium high silicon Y zeolite (crystallinity 80%, Si / Al molar ratio 5.1) was prepared; and it was used as the cracking active component in the residual oil cracking catalyst, and 40wt% industrial grade kaolin (Suzhou Kaolin Company) and 10wt% of the binder aluminum sol (Al2O3 20wt%, Sichuan Runhe Catalyst Company) were added on a dry basis of the catalyst, the content of the aluminum-supplemented Y zeolite was 50wt%, and it was formed on a small spray drying tower in the laboratory, and after ammonium washing, drying and roasting, the microsphere type residual oil cracking catalyst of Example 2 of the present invention was prepared, and the average diameter of the microspheres was 67 microns, and the content of sodium oxide was <0.1wt%.

[0048] Before use, the catalyst was aged at 760°C for 6 hours in a fluidized bed steam aging device.

[0049] Comparative Example 1

[0050] This comparative example is used to illustrate a dispersed hydrogenation catalyst in the prior art that is suitable for comparison with the present invention.

[0051] Referring to the contents and steps in the examples of U.S. Patent USP4125455, and referring to the preparation technology of the bimetallic catalyst disclosed in the prior art, and the composition ratio of the Mo and Fe elements being approximately the same as those in Example 1, a preparation method dispersed in oil is adopted to obtain a molybdenum-iron bimetallic catalyst dispersed in oil as a solvent, which is used as a slurry bed residue oil hydroconversion catalyst to be used in a comparative example representing the prior art.

[0052] When the catalyst is in use, it must be reduced and sulfided according to the operating procedures of general hydrogenation catalysts.

[0053] Comparative Example 2

[0054] This comparative example is used to illustrate a prior art heavy oil catalytic cracking catalyst suitable for comparison with the present invention.

[0055] A commercially available heavy oil catalytic cracking catalyst was used for evaluation in the comparative example. Its active component was Y zeolite after hydrothermal calcination. The contents of kaolin, binder alumina and Y zeolite on a catalyst dry basis were similar to those in Example 2 of the present invention. The average diameter of the microspheres of the catalyst was 67 microns and the sodium oxide content was <0.1 wt%. The catalyst was also aged at 760° C. for 6 hours in a fluidized bed steam aging device before use.

[0056] Example 3

[0057] This example is used to illustrate the implementation effect of the residual oil conversion process and reaction system of the present invention.

[0058] A joint simulation experiment was conducted in the laboratory using a commercial small adjustable constant temperature ultrasonic instrument (maximum amplitude 15 microns), a laboratory small kettle slurry bed hydrogenation evaluation device, a small riser catalytic cracking evaluation device, and laboratory distillation equipment.

[0059] Using Examples 1 to 2 as slurry bed residue oil hydrogenation catalyst and residue oil catalytic cracking catalyst, according to Figure 1 The process flow and implementation conditions of the present invention are shown in Table 1. After the reaction is operated to a balanced state, stable test data are obtained to evaluate the implementation effect of the present invention. The test raw material is an industrial low-quality residual oil, and some properties of the raw material are shown in Table 1.

[0060] Table 1. Some properties of crude oil

[0061]

[0062] The pretreatment conditions of the ultrasonic instrument are: frequency 15KHz, average contact surface power 5W / cm 2 , treatment time 30min; the reaction conditions of slurry bed hydrogenation conversion are: reaction temperature 410℃, reaction pressure 10MPa, hydrogen-to-oil ratio 500, space velocity 1.0h -1 , Molybdenum addition amount based on raw material weight 270 / μg·g -1 The reaction conditions of the catalytic cracking unit are: 520°C, catalyst-oil ratio 8; the regeneration conditions are: burning carbon deposits with air at 680°C.

[0063] Comparative Example 3

[0064] This comparative example is used to illustrate the effect of implementing the representative prior art residual oil conversion technology of the present invention.

[0065] The same experimental equipment and raw oil as in Example 3 were used, and Comparative Examples 1 to 2 were used as slurry bed residue oil hydrogenation catalysts and heavy oil catalytic cracking catalysts. According to the representative process flow, technical scheme and implementation conditions in the prior art, after the reaction was operated to a equilibrium state, stable test data were obtained as a comparative implementation effect for evaluating the present invention.

[0066] Example 4

[0067] This embodiment is used to help illustrate the role and influence of the main steps in the process implementation of the present invention.

[0068] The same as Example 3, but the ultrasonic pretreatment step is deliberately removed, and by comparison with Example 3, the three main processes of ultrasonic pretreatment, slurry bed hydroconversion and residue catalytic cracking are examined. The synergistic effect of the conversion of inferior / heavy residue oil in the present invention is revealed, and the special effect of the ultrasonic process in the present invention is revealed; and in the data comparison with Comparative Example 3, the combination of the slurry bed hydroconversion and residue catalytic cracking processes in the present invention is significantly different from the prior art in terms of technical effect.

[0069] Comparative Example 4

[0070] This embodiment is to help illustrate the limited effect and impact that can be achieved on the existing technology even after the ultrasonic pretreatment step is specially added.

[0071] The same as in Comparative Example 3, but according to the same method and implementation conditions as in Example 3, an ultrasonic pretreatment step is particularly added. It should be particularly emphasized that in the prior art, there is no such technical combination to examine the role and influence of the prior art combination compared with the present invention, even if the ultrasonic pretreatment step is deliberately added, on the conversion of inferior / heavy residue oil in the conventional slurry bed hydroconversion and heavy oil catalytic cracking combined process, especially whether the same technical effects and synergistic effects in the present invention can be obtained.

[0072] Example 5

[0073] This example is used to illustrate the present invention and the prior art, and the conversion effect comparison in implementation is shown in Table 2.

[0074] Table 2. Reaction results of low-quality residual oil conversion in Examples and Comparative Examples

[0075] Test No. Example 3 Example 4 Comparative Example 3 Comparative Example 4 Dry gas / wt% 1.8 1.6 2.4 2.3 Liquefied gas / wt% 6.9 6.5 9.1 9.4 Gasoline / wt% 52.9 52.1 43.5 43.2 Diesel / wt% 32.8 31.6 32.4 32.6 Clarified oil + external oil slurry / wt% 1.7 4.5 5.2 5.1 Coke / wt% 3.9 3.7 7.4 7.4

[0076] By comparing the data in Table 2, it can be seen that the process method and reaction system for residue oil conversion of the present invention, compared with the typical process method and reaction system disclosed in the prior art, under the same molybdenum content and similar process conditions, reflects a better conversion of inferior / heavy residue oil. Through ultrasonic pretreatment, slurry hydrogenation conversion, residue oil catalytic cracking, and the dispersed hydrogenation catalyst and residue oil catalytic cracking catalyst matched therewith, a good synergistic conversion effect is reflected, with good characteristics of converting heavy components, reducing coke and increasing light distillate oil products, and the total desulfurization rate is close to 90%, the total denitrification rate is close to 60% and the good technical effects of nearly complete demetallization are all not available in the prior art, and it is impossible to achieve the same technical effect by simply arranging and combining the prior art. Even if an ultrasonic pretreatment step is deliberately added as in the present invention, the effect that can be played is extremely limited, and the same technical effect as the present invention cannot be obtained.

[0077] It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A process for residual oil conversion, comprising: After the inferior heavy oil / residue oil raw material is heated to 70-150° C., it is mixed with the heavy distillation cracking product (5%-90%) of part of the recycling after separation in the product fractionation tower and a dispersed catalyst containing molybdenum and iron, phosphorus, sulfur and aluminum elements, with Mo / feed oil 200-350ppm in an ultrasonic pretreatment device; and the mixture is heated to 10-30KHz and the average contact surface power is 1-10W / cm 2 Ultrasonic treatment for 5 to 120 minutes; mixed with hydrogen and further heated to 150 to 350°C, then entering the slurry bed reactor at 380 to 500°C, 5 to 18 MPa, hydrogen-to-oil volume ratio of 100 to 3000, and liquid space velocity of 0.1 to 2.5 h -1 Under the conditions of , hydrogenation conversion is carried out; after the product is separated, the heavy liquid hydrocarbon part enters the riser heavy oil catalytic cracking unit, and contacts and reacts with the residual oil cracking catalyst containing 20wt% to 60wt% of aluminum-extracted silicon-supplemented Y zeolite under the conditions of 500-540°C, catalyst-oil weight ratio of 5-15, and reaction time of 0.1 to 10 seconds, and the cracking products enter the product fractionation tower for separation.

2. The process for residual oil conversion according to claim 1, characterized in that: The raw material is heated to 100-120°C and subjected to 12-25KHz and an average contact surface power of 3-6W / cm 2 Ultrasonic device pretreatment for 10 to 60 minutes; further heated to 200 to 300 ° C, and then into the slurry bed reactor at 400 to 460 ° C, 8 to 15 MPa, hydrogen to oil volume ratio of 500 to 2000, liquid space velocity of 0.2 to 2.0 h -1 under the conditions of 510-530°C, catalyst-oil weight ratio of 6-10, reaction time of 0.5-5 seconds, and a residual oil cracking catalyst containing 35wt%-55wt% of aluminum-extracted silicon-supplemented Y zeolite to react in contact.

3. The process for residual oil conversion according to claim 1, characterized in that: The inferior heavy oil / residue oil raw material is one of inferior crude oil, atmospheric residue oil, vacuum residue oil, deoiled asphalt, oil sand asphalt, coal liquefaction heavy oil, coal tar, steam cracking tar, coking tail oil, catalytic oil slurry or a mixture of several of them.

4. The process for residual oil conversion according to claim 1, characterized in that: The dispersed catalyst uses oil or water as dispersant; Mo / feed oil 280-320ppm; Fe / (Mo+Fe) 0.1-0.3, P / (Mo+P) 0.1-0.25, S / (Mo+S) 0.75-0.85, Al / (Mo+Al) 0.7-0.

9.

5. A process for residual oil conversion according to claim 4, characterized in that: The molybdenum component introduced in the preparation process of the dispersed hydrogenation catalyst is provided by one or more of molybdenite, molybdenum chalcopyrite, molybdenum antimony copper ore or molybdenum salt particles; the iron component introduced is provided by one or more of bauxite, red mud, iron sulfate, limonite, laterite or iron salt particles; the aluminum component introduced is provided by one or more of bauxite, aluminum hydroxide, aluminum oxide, diaspore, aluminum sol or aluminum salt particles; the phosphorus component introduced is provided by phosphorus salt phosphorus compounds; the sulfur component introduced is provided by sulfide.

6. The process for residual oil conversion according to claim 1, characterized in that: The residue oil cracking catalyst contains 40wt% to 50wt% of aluminum-extracted silicon-supplemented Y zeolite, which is artificially synthesized Y zeolite with a silicon-aluminum molar ratio of 2.3 to 2.7, and is processed into a high-silicon Y zeolite with a silicon-aluminum molar ratio of 4 to 10 by silicon tetrachloride vapor phase extraction of aluminum and / or ammonium fluorosilicate liquid phase extraction of aluminum and silicon, and serves as the cracking active component of the residue oil cracking catalyst.

7. The process for residual oil conversion according to claim 1, characterized in that: The residual oil cracking catalyst is deactivated by carbon deposition in a heavy oil catalytic cracking unit and then circulated from a riser reactor to a fluidized bed regenerator, where air is introduced at 680-820°C to burn and regenerate the catalyst to restore its cracking activity.

8. The process for residual oil conversion according to claim 1, characterized in that: The process for the conversion of residual oil comprises a reaction system comprising: heavy low-quality raw oil, a dispersed hydrogenation catalyst, an ultrasonic pretreatment device, a slurry bed reactor, a gas-liquid separation device, a catalytic cracking device, a residual oil cracking catalyst, a product fractionation tower, a hydrogen circulation compressor, a heat exchanger / heater and a circulation pump; after the heavy low-quality raw oil (1) is heated, it is mixed with a part of the circulating heavy distillation cracking product and a dispersed hydrogenation catalyst (3) in an ultrasonic pretreatment device (4); after ultrasonic pretreatment; after being mixed with hydrogen (2) and further preheated and heated, it enters a slurry bed reactor (5) for hydrogenation conversion; after the product is separated by the gas-liquid separation device (6, 7), the heavy liquid hydrocarbon part enters the riser heavy oil catalytic cracking device (8) to contact and react with the residual oil cracking catalyst, and the product enters the product fractionation tower (9) for separation to obtain products of different fractions (11-15).

9. The process for residual oil conversion according to claim 8, characterized in that: In the reaction system, the slurry bed hydrogenation reactor is a mechanical stirring kettle, a bubbling tower, a three-phase fluidized bed, a straight barrel or a loop flow slurry bed reactor.

10. The process for residual oil conversion according to claim 8, characterized in that: The heat exchange process in the reaction system uses the high-temperature regenerated catalyst in the catalytic cracking unit regenerator as a heat source to provide heat for heating and preheating the feed of the pretreatment unit, reactor and distillation tower through a heat exchanger and / or heat exchange medium.

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