CN109513459B - Molybdenum-tungsten composite oil-soluble residual oil suspension bed hydrogenation catalyst and preparation method thereof - Google Patents
Molybdenum-tungsten composite oil-soluble residual oil suspension bed hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum-tungsten composite oil-soluble residual oil suspension bed hydrogenation catalyst and a preparation method thereof. The preparation method comprises the following steps: (1) under the protection of nitrogen, heating phenols to a molten state, adding the phenols into phosphorus pentasulfide in batches for reaction, controlling the molar ratio of the phenols to the phosphorus pentasulfide to be 3.5:1-4.5:1, the reaction temperature to be 90-130 ℃, and the reaction time to be 2-4h to obtain aryl thiophosphoric acid; (2) sequentially adding water, sodium molybdate, sodium tungstate and sulfuric acid into a reactor, adding a solvent, an acidic cation exchange catalyst and aryl thiophosphoric acid for reaction after the reaction is completed, wherein the reaction temperature is 70-120 ℃, and the reaction time is 2-4 hours; (3) and after the reaction is finished, cooling to room temperature, washing, dehydrating and drying the crude product, and removing the solvent to obtain the final Mo-W composite oil-soluble catalyst. The catalyst of the invention is an excellent residual oil suspension bed catalyst, and has the advantages of easy dispersion, no need of adding a vulcanizing agent, good synergistic effect and high coke inhibition activity.
Description
Technical Field
The invention belongs to the technical field of hydrocracking agents in petrochemical industry, relates to a molybdenum-tungsten type composite oil-soluble catalyst, and particularly relates to a hydrogenation catalyst suitable for a residual oil suspension bed and a preparation method thereof.
Background
With the continuous development of suspension bed hydrogenation, the heavy oil suspension bed catalyst is more and more widely concerned. In general, the suspension bed hydrogenation catalyst mainly goes through two development stages, namely, a non-uniform solid powder catalyst and a uniformly dispersed catalyst, and the uniformly dispersed catalyst can be divided into a water-soluble dispersed catalyst and an oil-soluble dispersed catalyst. Both catalysts are present in the form of metal particles and their sulphides during the reaction. The catalytically active metal may be a transition metal of groups IVB, VB, VIB, VIIB and VIII, typically Fe, Ni and Mo. It can be said that the success or failure of the suspension bed hydrogenation process is directly influenced by the performance of the catalyst.
The solid powder catalyst has the defects of low dispersity, short service life and easy coking. The water-soluble catalyst is difficult to industrialize due to the problems of complex dispersion process, low hydrogenation activity and the like; compared with water-soluble catalysts, the oil-soluble catalyst has the advantages of simple dispersion process, high hydrogenation activity, obvious coke inhibition effect and easy industrialization. Therefore, the development of new and highly efficient oil-soluble catalysts is receiving more and more extensive attention.
CN201410208927.4 discloses an oil-soluble molybdenum-based catalyst precursor, a preparation method and application thereof, relating to the technical field of heavy oil hydrocracking catalysts and solving the problems of low catalytic hydrogenation activity and high cost of the existing catalyst; the preparation method of the precursor comprises the following steps: 1) mixing a molybdenum source with water, reacting for 30-240 min at 70-90 ℃, and adding an inorganic acid; 2) addition of a higher alcohol to P2S5After the addition is finished at 50-80 ℃ within 5-15 min, reacting at 70-100 ℃ for 1-3 h; 3) adding the product obtained in the step 2) into the product obtained in the step 1), adding resin, and reacting for 4-8 hours at 70-110 ℃; 4) separating an oil phase from the product of the step 3) to obtain a target product; the invention can form MoS by self-vulcanization in-situ decomposition2The active component is used in hydrocracking process of inferior heavy oil slurry bed containing high metal, high carbon residue and high sulfur, and can lower coke yield and maintain the long period operation of the apparatus. But the catalyst is a single metalThe catalyst is added in a large proportion of 50-2000ppm and can reach 2000ppm at most.
CN201510275523.1 discloses an oil-soluble Mo-Ni bimetallic catalyst suitable for poor-quality residual oil suspension bed hydrocracking, a preparation method and application thereof, comprising the following steps: (1) dissolving nickel nitrate and ammonium molybdate in distilled water of which the mass is 15-25 times that of the nickel nitrate and the ammonium molybdate, and adding a small amount of ethylene glycol; (2) adding ammonia water into the solution to adjust the pH value to be alkaline; (3) under the stirring action, heating the solution to react for 3-5 h at 130-160 ℃, and filtering the product to obtain a solid intermediate product; (4) and drying the solid intermediate product at 100 ℃ under normal pressure, mixing the dried solid intermediate product with oleic acid, and reacting for 2-4 hours at 230-260 ℃ to obtain the oil-soluble Mo-Ni bimetallic catalyst. The catalyst has the advantages of flexible and adjustable bimetallic mass ratio, high hydrogenation activity and good coke inhibiting effect. The catalyst preparation process requires high reaction temperature, needs to be carried out at the temperature of more than 130 ℃ and 230 ℃, and needs to add a vulcanizing agent.
CN201610804914.2 discloses an oil-soluble catalyst and a preparation method thereof. The oil-soluble catalyst comprises VIB group metal Mo and/or W and at least one of VIII group metal Fe, Co or Ni, the total content of the VIB group metal and the VIII group metal is 10-30 wt%, and the molar ratio of the VIB group metal to the VIII group metal is 1: 10-10: 1. In the preparation process, the oil-soluble catalyst with high active metal content can be prepared at a lower reaction temperature without organic solvent. The catalyst has higher hydrogenation activity and excellent catalytic performance, and can be applied to the inferior heavy oil slurry bed hydrocracking process, so that the coke yield can be obviously reduced, and the conversion rate of inferior heavy oil and the yield of light oil can be improved. However, the catalyst needs to be prepared at a temperature higher than 120 ℃, the metal content in the catalyst is low and is only 2-6%, and a vulcanizing agent needs to be added.
Therefore, further research is needed on how to prepare the catalyst which has high metal content, does not need to add a vulcanizing agent, has mild reaction conditions in the preparation process and is easy to disperse and uniform.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of an oil-soluble molybdenum-tungsten composite catalyst, and the catalyst is an aryl substituent, so that the catalyst is better in intersolubility with aromatic hydrocarbon molecules in heavy oil; compared with a single metal catalyst, the activity is obviously improved; the catalyst has an in-situ activation function, and has obvious coking inhibition effect while ensuring high conversion rate when treating inferior heavy oil, particularly vacuum residue.
The technical scheme adopted by the invention is realized by solving the technical problems that:
the preparation method of the molybdenum-tungsten composite oil-soluble residual oil suspended bed hydrogenation catalyst is characterized by comprising the following steps of:
1) under the protection of nitrogen, heating phenols to a molten state, adding the phenols into phosphorus pentasulfide in batches for reaction, controlling the molar ratio of the phenols to the phosphorus pentasulfide to be 3.5:1-4.5:1, the reaction temperature to be 90-130 ℃, and the reaction time to be 2-4h to obtain aryl thiophosphoric acid;
2) sequentially adding water, sodium molybdate, sodium tungstate and sulfuric acid into a reactor, adding a solvent, an acidic cation exchange catalyst and aryl thiophosphoric acid for reaction after the reaction is completed, wherein the reaction temperature is 70-120 ℃, and the reaction time is 2-4 hours;
3) after the reaction is finished, cooling to room temperature, washing, dehydrating and drying the crude product, and then removing the solvent to obtain the final Mo-W composite oil-soluble catalyst;
the solvent is one of petroleum ether, benzene and toluene;
the catalyst comprises, by weight, 1-10% of molybdenum, 1-15% of tungsten, 15-20% of sulfur, 6-10% of oxygen and 4-6% of phosphorus.
In the above production method, the phenol is phenol, alkyl-substituted phenol, naphthol, or the like, and phenol and alkyl-substituted phenol are preferable.
In the preparation method, the molar ratio of the active metal precursor sodium molybdate to the sodium tungstate is 1:5-5: 1.
In the preparation method, the molar ratio of the total molar amount of the active metal precursors sodium molybdate and sodium tungstate to the molar amount of water and sulfuric acid is 1:5:1.5-1:2: 1.
In the preparation method, the molar ratio of the total molar amount of the active metal precursors sodium molybdate and sodium tungstate to the solvent and the aryl thiophosphoric acid is 1:1:5-1:0.5:2.5
In the preparation method, the acidic cation exchange catalyst is a hydrogen resin catalyst, and the addition amount of the acidic cation exchange catalyst is 8-12% of the total mass of the molybdenum and tungsten atoms of the active metal precursor.
On the other hand, the invention also provides the molybdenum-tungsten composite oil-soluble residual oil suspended bed hydrogenation catalyst obtained by the preparation method.
Further, the invention provides application of the catalyst in inferior heavy oil.
Specifically, the inferior heavy oil provided by the invention is inferior crude oil, coal tar, atmospheric residue oil, vacuum residue oil and other inferior heavy oils and mixed raw materials thereof.
Further, the proportion of the molybdenum-tungsten oil-soluble catalyst added into the inferior heavy oil is 100-300 ug/g.
The invention has the advantages that:
the catalyst prepared by the method has mild technological conditions, and the prepared catalyst has stable properties and is convenient to transport and store. The catalyst is an aryl substituted molybdenum tungsten phosphate type catalyst, can realize homogeneous dissolution in heavy oil, and can be better mutually dissolved with aromatic hydrocarbon molecules in oil microscopically. The catalyst is a bimetallic catalyst, can flexibly adjust the metal proportion, can prepare catalysts with different metal contents and different metal proportions, and can better play the synergistic effect of the catalyst on different raw materials. The catalyst is a self-vulcanization type catalyst, no additional vulcanizing agent is needed to be added, the active phase of molybdenum disulfide and tungsten disulfide can be generated through in-situ decomposition, the vulcanization process is greatly simplified, and the active phase molybdenum disulfide and tungsten disulfide formed through in-situ vulcanization have small particle size, high dispersion and high hydrogenation activity. The active phase formed by vulcanization is closer to aromatic hydrocarbon molecules in the heavy oil, so that aromatic hydrocarbons in the heavy oil, especially polycyclic aromatic hydrocarbon macromolecules, are easier to be hydrocracked, the polycondensation reaction of the polycyclic aromatic hydrocarbon macromolecules is inhibited, and further coking is inhibited, and the catalyst is an excellent heavy oil suspension bed catalyst.
Detailed Description
In order to make the technical features, objects and applications of the catalyst of the present invention more clearly understandable, the following examples are further detailed, but are not to be construed as limiting the practicable scope of the present invention.
Example 1
Under the protection of nitrogen, 0.6mol of phenol is taken to be heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely diphenyl thiophosphoric acid, is generated;
adding 5mol of water, 0.05mol of sodium molybdate, 0.05mol of sodium tungstate and 0.1mol of concentrated sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.4g of acidic cation exchange resin and the diphenyl sulfuric acid after the reaction is completely acidified, reacting at the reaction temperature of 90 ℃ for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-1 and contained 4.8%, 7.2% and 17.8% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Example 2
Under the protection of nitrogen, 0.6mol of phenol is taken to be heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely diphenyl thiophosphoric acid, is generated;
adding 5mol of water, 0.08mol of sodium molybdate, 0.02mol of sodium tungstate and 0.1mol of dilute sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.0g of acidic cation exchange resin and the diphenylphosphoric acid after the reaction is completely acidified, reacting at the reaction temperature of 90 ℃ for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-2 and contained 8.6%, 2.5% and 17.1% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Example 3
Under the protection of nitrogen, 1.2mol of phenol is taken to be heated until the solid is molten, slowly added into 0.3mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely diphenyl thiophosphoric acid, is generated;
sequentially adding 10mol of water, 0.12mol of sodium molybdate, 0.08mol of sodium tungstate and 0.2mol of dilute sulfuric acid into a three-neck flask, adding 2mol of toluene, 2.6g of acidic cation exchange resin and the diphenylphosphoric acid after the reaction is completely acidified, and reacting at the reaction temperature of 90 ℃ for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-3 and contained 6.3, 5.6 and 16.6% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Example 4
Under the protection of nitrogen, 1.2mol of phenol is taken to be heated until the solid is molten, slowly added into 0.3mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely diphenyl thiophosphoric acid, is generated;
sequentially adding 10mol of water, 0.04mol of sodium molybdate, 0.16mol of sodium tungstate and 0.2mol of dilute sulfuric acid into a three-neck flask, adding 2mol of toluene, 3.5g of acidic cation exchange resin and the diphenylphosphoric acid after the reaction is completely acidified, and reacting at the reaction temperature of 90 ℃ for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-4 and contained 1.8%, 12.3% and 16.6% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Example 5
Under the protection of nitrogen, 0.6mol of p-cresol is taken and heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 110 ℃, reacted for 3.5 hours until the solid disappears, and oily liquid is generated, namely benzhydryl thiophosphoric acid;
adding 5mol of water, 0.05mol of sodium molybdate, 0.05mol of sodium tungstate and 0.1mol of concentrated sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.4g of acidic cation exchange resin and the benzhydryl thiophosphoric acid after the reaction is completely acidified, reacting, controlling the reaction temperature to be 100 ℃, and reacting for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-5 and contained 4.7%, 7.4% and 16.2% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Example 6
Under the protection of nitrogen, 0.6mol of naphthol is taken to be heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 130 ℃, reacted for 4 hours until the solid disappears, and oily liquid, namely dinaphthyl thiophosphoric acid, is generated;
adding 5mol of water, 0.05mol of sodium molybdate, 0.05mol of sodium tungstate and 0.1mol of dilute sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.4g of acidic cation exchange resin and the dinaphthyl sulfuric phosphoric acid after the reaction is completely acidified, reacting at the reaction temperature of 105 ℃ for 5 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final Mo-W composite oil-soluble catalyst. The catalyst was designated HC-6 and contained 3.2%, 5.4% and 14.2% by mass of molybdenum, tungsten and sulfur, respectively, as measured by atomic emission spectroscopy and a sulfur determinator.
Comparative example 1
Under the protection of nitrogen, 0.6mol of phenol is taken to be heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely the aryl thiophosphoric acid, is generated;
adding 5mol of water, 0.1mol of sodium molybdate and 0.1mol of dilute sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.0g of acidic cation exchange resin and the diphenyl sulfuric acid after the reaction is completely acidified, reacting, controlling the reaction temperature to be 90 ℃, and reacting for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final oil-soluble molybdenum catalyst. The catalyst is marked C-1, and the mass percentages of molybdenum and sulfur in the catalyst, measured by atomic emission spectroscopy and a sulfur determinator, are 10.5% and 17.2%, respectively.
Comparative example 2
Under the protection of nitrogen, 0.6mol of phenol is taken to be heated until the solid is molten, slowly added into 0.15mol of phosphorus pentasulfide in batches, heated to 100 ℃, reacted for 3 hours until the solid disappears, and oily liquid, namely the aryl thiophosphoric acid, is generated;
adding 5mol of water, 0.1mol of sodium tungstate and 0.1mol of dilute sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.8g of acidic cation exchange resin and the diphenyl sulfuric acid after the reaction is completely acidified, reacting, controlling the reaction temperature to be 90 ℃, and reacting for 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final oil-soluble tungsten catalyst. The catalyst was designated C-2 and the mass percentages of tungsten and sulfur in the catalyst were 14.6% and 16.8%, respectively, as determined by atomic emission spectroscopy and a sulfur determinator.
Comparative example 3
Under the protection of nitrogen, slowly adding 0.6mol of isooctanol into 0.15mol of phosphorus pentasulfide in batches, heating to 90 ℃, reacting for 3 hours until the solid disappears, and generating oily liquid, namely alkyl thiophosphoric acid;
adding 5mol of water, 0.1mol of sodium molybdate and 0.1mol of dilute sulfuric acid into a three-neck flask in sequence, adding 1mol of toluene, 1.0g of acidic cation exchange resin and the alkyl sulfuric acid after the reaction is completely acidified, reacting, controlling the reaction temperature to be 90 ℃ and the reaction time to be 3 hours;
and after the reaction is finished, cooling to room temperature, filtering to separate the catalyst, washing the crude product for 3 times, dehydrating, and removing the solvent through reduced pressure distillation to obtain the final oil-soluble molybdenum catalyst. The catalyst is marked C-3, and the mass percentages of molybdenum and sulfur in the catalyst, as measured by atomic emission spectroscopy and a sulfur determinator, are 8.9% and 15.6%, respectively.
The oil soluble catalyst of the invention is mainly applied to the hydrogenation of a heavy oil suspension bed, and the applicable heavy oil mainly comprises inferior crude oil, coal tar, atmospheric residue oil, vacuum residue oil and other inferior heavy oil and mixed raw materials thereof. The raw materials are mainly characterized by high sulfur and nitrogen content, high carbon residue and high metal content. The proportion of the catalyst added into the inferior heavy oil is 100-300ug/g according to the different properties of the heavy oil.
Performance testing
Examples 1, 2, 3, 4, 5, 6, the catalysts prepared were used in the upgrading of the vacuum residue slurry bed hydrogenation experiments and were compared with the catalysts prepared in comparative example 1, comparative example 2, comparative example 3. The specific method comprises the following steps: preheating vacuum residue to 100 ℃, adding 200 mu g/g (calculated by metal) of catalyst, and stirring at the speed of 400rad/min for 0.5h to ensure that the catalyst is uniformly dispersed; then heating to 370 ℃, and keeping for 0.5h to complete the in-situ sulfuration decomposition of the catalyst; then heating to the reaction temperature for hydrocracking reaction, wherein the specific reaction conditions are hydrogen initial pressure of 12.0MPa, reaction temperature of 440 ℃ and reaction time of 1 h. And after the reaction is finished, performing simulated distillation analysis on the liquid phase product, and dividing the liquid phase product into four parts, namely gasoline (C5-180 ℃), diesel oil (180-350 ℃), wax oil (350-500 ℃) and hydrogenated tail oil (500 ℃) according to different temperature points to determine the yield of each fraction. Collecting a liquid phase product and a wall product of a stirring paddle of the reaction kettle and the kettle wall, respectively cleaning the liquid phase product and the wall product with toluene, filtering, collecting residues, performing Soxhlet extraction, finally performing vacuum drying on the extracted residues at 120 ℃, removing residual solvent, respectively obtaining liquid phase coke and wall coke, respectively calculating the liquid phase coke yield and the wall coke yield, respectively, and calculating the total coke yield by using a subtraction method to obtain the gas yield.
The final purpose of the residual oil suspension bed hydrogenation process is to reduce the green coke as much as possible on the premise of ensuring high conversion rate, so the actual evaluation of the catalyst should be integrated to show the capability of the catalyst in the two aspects. In this study, the catalyst activity was examined mainly with the conversion and coke formation rates as indicators. The coking rate refers to the ratio of the coking amount to the mass of the raw oil, and comprises the coking rates of wall coke and liquid-phase coke. The conversion rate refers to the ratio of the sum of the amount of the fraction with boiling point lower than 500 ℃ converted from the residual oil raw material to the raw oil quality.
TABLE 1 vacuum residuum Property parameters
TABLE 2 evaluation of the slag-reducing suspension bed hydrogenation catalyst
From the viewpoint of catalyst performance, the yields of comparative gas and gasoline fractions were lower for HC series catalysts and monometallic oil-soluble C-1, C-2 catalysts than for the catalyst of comparative example C-3. Compared with the yield of diesel oil and wax oil fractions, the HC series catalyst and the C-1 and C-2 catalyst have higher yield compared with the C-3 catalyst. The HC series catalyst has better coking inhibition effect on the coking inhibition performance, and is reflected in that the coke yield is lower, and particularly, the content of wall coke is not more than 1.0 percent; the C-1, C-2 catalyst is the next time, wherein the coke inhibiting effect of the C-1 oil-soluble molybdenum catalyst is better than that of the C-2 oil-soluble tungsten catalyst; the C-3 oil-soluble catalyst has the worst coking inhibition effect. The oil yield of the comparison is less than 500 ℃, and the HC series catalyst yield is greater than that of the comparative example series catalyst. Therefore, the molybdenum-tungsten composite oil-soluble catalyst has better hydrocracking effect when being used for refining slag-reducing suspension bed. Compared with HC series catalysts, the HC-5 catalyst has the best hydrocracking effect when being used for refining the slag-reducing suspension bed, ensures the lowest coke yield while ensuring high conversion rate, and basically has no generation of wall coke.
Claims (10)
1. The preparation method of the molybdenum-tungsten composite oil-soluble residual oil suspended bed hydrogenation catalyst is characterized by comprising the following steps of:
1) under the protection of nitrogen, heating phenols to a molten state, adding the phenols into phosphorus pentasulfide in batches for reaction, controlling the molar ratio of the phenols to the phosphorus pentasulfide to be 3.5:1-4.5:1, the reaction temperature to be 90-130 ℃, and the reaction time to be 2-4h to obtain aryl thiophosphoric acid;
2) sequentially adding water, sodium molybdate, sodium tungstate and sulfuric acid into a reactor, adding a solvent, an acidic cation exchange catalyst and aryl thiophosphoric acid for reaction after the reaction is completed, wherein the reaction temperature is 70-120 ℃, and the reaction time is 2-4 hours;
3) after the reaction is finished, cooling to room temperature, washing, dehydrating and drying the crude product, and then removing the solvent to obtain the final Mo-W composite oil-soluble catalyst;
the solvent is one of petroleum ether, benzene and toluene;
the catalyst comprises, by weight, 1-10% of molybdenum, 1-15% of tungsten, 15-20% of sulfur, 6-10% of oxygen and 4-6% of phosphorus.
2. The method according to claim 1, wherein the phenol is one or two of phenol, alkyl-substituted phenol, and naphthol.
3. The method of claim 1, wherein the molar ratio of the active metal precursor sodium molybdate to sodium tungstate is from 1:5 to 5:1.
4. The method of claim 1, wherein the molar ratio of the total molar amount of the active metal precursors sodium molybdate and sodium tungstate to the molar amount of water and sulfuric acid is 1:5:1.5 to 1:2: 1.
5. The method of claim 1, wherein the molar ratio of the total molar amount of the active metal precursors sodium molybdate and sodium tungstate to the solvent and the aryl thiophosphoric acid is 1:1:5 to 1:0.5: 2.5.
6. The process according to claim 1, wherein the acidic cation exchange catalyst is a hydrogen type resin catalyst and is added in an amount of 8 to 12% by mass based on the total mass of the molybdenum and tungsten atoms as the active metal precursor.
7. The molybdenum-tungsten composite oil-soluble residue suspended bed hydrogenation catalyst prepared by the preparation method of any one of claims 1 to 6.
8. The molybdenum-tungsten composite oil-soluble residue suspended bed hydrogenation catalyst of claim 7, which is used for hydrogenation of inferior heavy oil.
9. The use as claimed in claim 8, wherein the catalyst is added to the inferior heavy oil in a ratio of 100-300 ug/g.
10. The use of claim 8, wherein the low-grade heavy oil is low-grade crude oil, coal tar, atmospheric residue, vacuum residue, or a mixture thereof.
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