CN112745931B - Process for desulfurization of heavy oil - Google Patents
Process for desulfurization of heavy oil Download PDFInfo
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- CN112745931B CN112745931B CN201911046949.4A CN201911046949A CN112745931B CN 112745931 B CN112745931 B CN 112745931B CN 201911046949 A CN201911046949 A CN 201911046949A CN 112745931 B CN112745931 B CN 112745931B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention relates to the field of heavy oil desulfurization, and discloses a method for desulfurizing heavy oil, which comprises the following steps: (a) In the presence of hydrogen, desulfurizing catalyst, promoter and heavy metalReacting the oil and optional recycle; (b) Separating the product obtained in the step (a) to obtain gas, low-sulfur heavy oil and catalyst-containing tail oil; and optionally (c) returning a part of the catalyst-containing tail oil to the step (a) as the circulating material, and throwing the other part of the catalyst-containing tail oil out; the catalyst slurry is a liquid desulfurization catalyst containing molybdenum ions and cobalt ions, wherein the liquid desulfurization catalyst contains an organic metal complex, a dispersion solvent and an auxiliary agent; wherein the organometallic complex comprises molybdenum ions, cobalt ions and C 7 ‑C 14 An organic anion. The method does not need a fixed bed reactor, the liquid desulfurization catalyst has better contact with the heavy oil, the catalytic efficiency is higher, and the desulfurization effect is more obvious.
Description
Technical Field
The invention relates to the field of heavy oil desulfurization, in particular to a heavy oil desulfurization method.
Background
The increasingly stricter environmental regulations in the world promote the use of clean and environment-friendly oil products to be increasingly widespread, and the requirements of China on the standard of sulfur content of finished oil are more and more strict. From various aspects, reducing the sulfur content of the product is a serious test which is faced by the oil refining industry in China.
The quality of crude oil exploitation in China is more and more serious, and meanwhile, the quality of crude oil resources in China is more and more aggravated due to the continuous increase of imported high-sulfur crude oil. The heavy oil including residual oil is pre-desulfurized, so that the utilization rate of the heavy oil is improved, the trend of energy supply shortage is relieved, environmental pollution can be reduced, and clean utilization of energy is achieved.
Most of the conventional desulfurization methods are fixed bed reactions, and most of the desulfurization methods are supported catalysts, so that the methods have good desulfurization effect and wide application for light oil.
CN107858173A discloses a hydrocracking desulfurization method for inferior heavy oil by using a suspension bed, wherein the inferior heavy oil and a hydrogenation catalyst are subjected to hydrogenation reaction. Wherein the hydrogenation catalyst can be composed of zinc oxide powder, sulfurized kaolin powder and sulfurized iron-containing ore powder, the content of the sulfurized kaolin powder is 15.0-60.0wt%, the content of the sulfurized iron-containing ore powder is 15.0-55.0wt%, and the content of the zinc oxide powder is 15.0-50.0wt%; or the material consists of 15.0 to 60.0 weight percent of zinc oxide powder, 15.0 to 55.0 weight percent of vulcanized kaolin powder, 15.0 to 50.0 weight percent of zinc oxide powder and 0.2 to 12 weight percent of vulcanized micro-mesoporous lanthanum ferrite; or the composite material consists of 15.0 to 60.0 weight percent of zinc oxide powder, 0.2 to 12 weight percent of vulcanized kaolin powder, 15.0 to 55.0 weight percent of vulcanized iron-containing powder, 15.0 to 50.0 weight percent of zinc oxide powder, 0.2 to 15 weight percent of vulcanized micro-mesoporous lanthanum ferrite and 0.2 to 15 weight percent of ZSM-5 molecular sieve. And the technology is complex. In this method, the hydrogenation catalyst is usually a solid powder and passes through a single pass, and the solid powder remains in the unconverted residue, resulting in the generation of a tail slag which is difficult to handle and environmental pollution. In addition, the catalyst is used in such a way that the activity is low and the dosage is large.
However, heavy oil, particularly inferior heavy oil having a high content of impurities such as sulfur, nitrogen, metals, etc., and a high content of carbon residue and asphaltene, has poor accessibility between heavy oil molecules and the active sites of the supported catalyst, is difficult to diffuse, is prone to local overheating due to heat generation by hydrogenation, is also prone to deactivation of the catalyst, and is difficult to handle in a fixed bed. In view of the above, it is desirable to develop a hydrodesulfurization process for heavy oils, as distinguished from fixed beds.
Disclosure of Invention
The invention aims to solve the problem of heavy oil desulfurization, and provides a heavy oil desulfurization method which is suitable for non-fixed bed hydrodesulfurization and can better realize heavy oil desulfurization.
In order to achieve the above object, the present invention provides a method for desulfurizing heavy oil, comprising:
(a) Reacting a liquid desulfurization catalyst, an accelerator, heavy oil and an optional cycle material in the presence of hydrogen;
(b) Separating the product obtained in the step (a) to obtain gas, low-sulfur heavy oil and catalyst-containing tail oil; and optionally
(c) Returning a part of the catalyst-containing tail oil to the step (a) as the circulating material, and throwing the other part of the catalyst-containing tail oil out;
the liquid desulfurization catalyst contains an organic metal complex, a dispersing solvent and an auxiliary agent; wherein the organometallic complex comprises molybdenum ions, cobalt ions and C 7 -C 14 An organic anion.
According to the technical scheme, the liquid desulfurization catalyst containing molybdenum ions and cobalt ions is used as the catalyst slurry to perform hydrodesulfurization reaction with heavy oil, a fixed bed type reactor is not needed, the operation is simple, the catalyst is good in contact with raw oil, the catalysis efficiency is high, the desulfurization effect is obvious, a large amount of tail oil is not generated, the environmental pollution can be reduced, and clean utilization of energy is realized.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for desulfurizing heavy oil, which comprises the following steps:
(a) Reacting a liquid desulfurization catalyst, an accelerant, heavy oil and an optional circulating material in the presence of hydrogen;
(b) Separating the product obtained in the step (a) to obtain gas, low-sulfur heavy oil and catalyst-containing tail oil; and optionally
(c) Returning a part of the catalyst-containing tail oil to the step (a) as the circulating material, and throwing the other part of the catalyst-containing tail oil out;
the liquid desulfurization catalyst contains an organic metal complex, a dispersing solvent and an auxiliary agent; wherein the organometallic complex comprises molybdenum ions, cobalt ions and C 7 -C 14 An organic anion.
In the present invention, preferably, in step (a), the reaction comprises: and pre-reacting the liquid desulfurization catalyst with a promoter.
In the present invention, preferably, the pre-reaction conditions include: the temperature is 300-380 deg.C, and the time is 0.5-3h. The volume ratio of the hydrogen to the liquid desulfurization catalyst is 300-3000Nm 3 /m 3 Preferably 500-2000Nm 3 /m 3 . If the accelerant is a sulfur-containing substance, the accelerant is used for pre-vulcanization, the accelerant is calculated by S, the liquid desulfurization catalyst is calculated by the total sum of Mo and Co elements, and the molar ratio of the accelerant to the liquid desulfurization catalyst is 0.5-4:1, preferably 1 to 3:1. if the promoter is ethylene glycol or oleylamine, and the addition amount of the promoter is 0.1-10wt% of the liquid desulfurization catalyst, the promoter is used for promoting the formation of better metal active elements (such as smaller size of formed metal sulfide and fewer layers), and further has better hydrodesulfurization activity.
In the present invention, preferably, in the step (a), the accelerator is at least one of sublimed sulfur, carbon disulfide, dimethyl sulfide, ethylene glycol and oleylamine.
In the present invention, preferably, the reaction further comprises: mixing the pre-reaction product, heavy oil and circulating material, and then carrying out hydrodesulfurization reaction.
In the present invention, it is preferable that the mixing temperature is 350 to 380 ℃ and the mixing time is 1 to 60min. The mixing ensures that the pre-reacted product is uniformly dispersed in the heavy oil, and the heavy oil is fully contacted with the pre-reacted product. Wherein the volume ratio of hydrogen to the heavy oil is 500-4000Nm 3 /m 3 Preferably 500-3000Nm 3 /m 3 。
In the present invention, preferably, the hydrodesulfurization reaction conditions include: the desulfurization temperature is more than 380 ℃ and less than 480 ℃, and is preferably 400-440 ℃; the desulfurization pressure is 11-30MPa, preferably 15-25MPa; the desulfurization time is 0.5 to 15 hours, preferably 1 to 10 hours. Wherein the volume ratio of hydrogen to the heavy oil is 500-4000Nm 3 /m 3 Preferably 500-3000Nm 3 /m 3 。
In the present invention, it is preferable that the liquid desulfurization catalyst is added in an amount of 500 to 30000 ppm by weight, preferably 1000 to 20000 ppm by weight, based on the total of the elements of Mo and Co, of the heavy oil. Can ensure that the heavy oil obtains good desulfurization effect.
The method provided by the invention is not carried out in a fixed bed reactor, does not need a solid catalyst, and can avoid the defects caused by using the fixed bed reactor in the prior art. The heavy oil is not particularly limited, and various sulfur-containing compounds may be used. Preferably, the heavy oil is selected from crude oils having a boiling range > 500 ℃, or a density > 1g/cm 3 The petroleum hydrocarbon oil of (1).
In the present invention, specifically, at least one selected from the group consisting of heavy crude oil, vacuum residue, catalytic cracking slurry oil, coal tar, ethylene tar, shale oil, heavy oil, oil sand pitch, fixed bed and ebullated bed residue hydrogenation tail oil, coal liquefaction tail oil, and heavy materials produced by refineries is preferable.
The method provided by the invention can be used for selectively recycling the catalyst-containing tail oil in the step (c). Part or all of the catalyst-containing tail oil may be returned to step (a).
In the present invention, the composition of the organometallic complex in the liquid desulfurization catalyst can be determined by GB/T17476-1998. The addition agent and the dispersion solvent can be calculated by feeding.
In the present invention, it is preferable that the content of the organometallic complex is 50 to 80wt%, the content of the dispersion solvent is 19 to 50wt%, and the content of the auxiliary agent is 0.1 to 2wt% based on the total amount of the liquid desulfurization catalyst.
In the invention, preferably, the dispersion solvent is distillate oil with a distillation range of 300-500 ℃, and is preferably catalytic cracking slurry oil and/or heavy diesel oil. The dispersion solvent enables the organometallic complex to be dissolved and dispersed in advance, providing an organometallic complex that can be better dissolved and dispersed in heavy oil.
According to the invention, the auxiliary agent can help to disperse asphaltenes in the heavy oil or provide a coking carrier when the liquid desulfurization catalyst is used for heavy oil desulfurization, so that the intermediate phase asphaltenes contained in the heavy oil in the desulfurization process are prevented from wrapping the components of the active phase of the catalyst, the catalyst is inactivated, and the service life of the catalyst is shortened. The auxiliary agent can also improve the dispersion degree of molybdenum element and cobalt element contained in the organic metal complex, and is helpful for improving the activity of the catalyst in desulfurization of heavy oil. Preferably, the auxiliary agent is selected from one or more of carbon powder, rare earth oxide, aluminum oxide, silicon oxide, alkylphenol, polyoxypropylene glycol, polyoxyethylene ether, alkylbenzene sulfonic acid, polyisobutylene succinic anhydride and butyl isoquinoline; preferably at least one selected from carbon powder, polyoxypropylene glycol, and alkylbenzenesulfonic acid.
In the present invention, it is preferable that the content of the + 6-valent molybdenum ions in the molybdenum ions is not more than 85% by weight. The content of the valence state of the molybdenum ion can be determined by X-ray photoelectron spectroscopy (XPS).
In the present invention, it is preferable that the molar ratio of the molybdenum ion to the cobalt ion in the organometallic complex is (0.1 to 10): 1, preferably (0.1-6): 1;
in the present invention, it is preferable that the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex. The rest is C 7 -C 14 An organic anion.
In the present invention, preferably, C is 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
In the present invention, in the step (b), the separation method may adopt solvent extraction or distillation under reduced pressure.
In the present invention, further, the liquid desulfurization catalyst is prepared by the following method:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing and contacting the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and obtaining a product and C 7 -C 14 Carrying out a complex reaction on organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
Some embodiments of the present invention provide that in step (1), the molybdenum-containing compound and the cobalt-containing compound are each prepared to form an acid solution. Dissolving and dispersing a molybdenum-containing compound in a solvent, and then carrying out acid liquor reaction with an acidic solution to obtain a molybdenum-containing acid liquor; dissolving and dispersing the cobalt-containing compound in a solvent, and then carrying out acid liquor reaction with an acidic solution to obtain the cobalt-containing acid liquor. Further, the conditions of the molybdenum-containing solution obtained by dissolving and dispersing the molybdenum-containing compound and the acidic solution for carrying out the acidic reaction comprise: the reaction temperature is 50-110 ℃, and the reaction time is 0.5-8h; the conditions of the acidic reaction between the cobalt-containing solution obtained by dissolving and dispersing the cobalt-containing compound and the acidic solution comprise: the reaction temperature is 70-110 ℃, and the reaction time is 1-10h.
In some embodiments provided herein, preferably, the molybdenum-containing compound is selected from at least one of molybdenum oxide, molybdic acid, and molybdate, and the cobalt-containing compound is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt oxide, cobalt hydroxide, basic cobalt carbonate, and cobalt halide.
In some embodiments provided herein, preferably, the solvent is selected from at least one of toluene, water, and ethanol.
In some embodiments provided herein, preferably, the acidic solution is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, propionic acid, and malonic acid.
In some embodiments provided herein, preferably, C is 7 -C 14 The organic acid is selected from at least one of 2-ethyl hexanoic acid, octanoic acid, 2-propyl heptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
In some embodiments provided by the present invention, in step (1), the molybdenum-containing compound and the cobalt-containing compound are dissolved and dispersed in the solvent respectively to obtain a molybdenum-containing compound solution and a cobalt-containing compound solution respectively. In the molybdenum-containing compound solution, the mass ratio of the solvent to molybdenum element is (2-30): 1; in the cobalt-containing compound solution, the mass ratio of the solvent to cobalt element is (2-30): 1. and (2) respectively carrying out acid liquor reaction on the molybdenum-containing compound solution and the cobalt-containing compound solution and an acid solution, wherein in the acid liquor reaction of the molybdenum-containing compound solution and the acid solution, the molar ratio of the acid solution to molybdenum element is (0.5-10): 1; in the acid liquor reaction of cobalt-containing compound solution and acid solution, the mole ratio of the acid solution to cobalt element is (0.5-10): 1.
in some embodiments provided by the present invention, in the step (2), the mixed molybdenum acid solution and cobalt acid solution is heated to 120-150 ℃ for reaction for 1-8h; the product obtained is reacted with C 7 -C 14 The organic acid reacts for 2 to 20 hours at a temperature of between 160 and 300 ℃.
In some embodiments provided herein, the sum of molybdenum and cobalt in the product and C are preferred 7 -C 14 The molar ratio of the organic acid is 1: (1-12). This ratio is sufficient to form a complex with the metal and does not reduce the metal content of the organometallic complex by adding too much organic acid.
In some embodiments of the present invention, in step (3), preferably, the organometallic complex is kept at 40 to 80 ℃ and then mixed with a dispersing solvent and an auxiliary agent at a temperature not higher than 80 ℃. The mixing mode can adopt stirring, and the rotating speed does not exceed 200rpm.
In some embodiments provided by the present invention, preferably, the dispersion solvent is distillate oil with a distillation range of 300-500 ℃, preferably catalytic cracking slurry oil and/or heavy diesel oil.
In some embodiments provided by the present invention, preferably, the auxiliary agent is selected from one or more of carbon powder, rare earth oxide, aluminum oxide, silicon oxide, alkylphenol, polyoxypropylene glycol, polyoxyethylene ether, alkylbenzene sulfonic acid, polyisobutylene succinic anhydride and butyl isoquinoline; preferably at least one selected from carbon powder, polyoxypropylene glycol, and alkylbenzenesulfonic acid. The polyoxypropylene diol may be commercially available from national drug companies.
In some embodiments, in step (3), based on the total amount of the organometallic complex, the dispersing solvent and the auxiliary, the organometallic complex is used in an amount of 50 to 80 parts by weight, the dispersing solvent is used in an amount of 19 to 50 parts by weight, and the auxiliary is used in an amount of 0.1 to 2 parts by weight.
The present invention will be described in detail below by way of examples.
In the examples and comparative examples, the composition of the organometallic complex was measured by the method of GB/T17476-1998.
The sulfur content analysis method is carried out according to GB/T17040-2008;
the heavy diesel oil is purchased from China petrochemical Qingdao refinery, and the distillation range is 350-410 ℃.
The desulfurization rate was calculated as follows:
preparation example 1
(1) Dissolving 25g of molybdenum oxide in 250g of toluene, adding 100g of nitric acid solution, and performing an acidic reaction for 3 hours at 80 ℃ to obtain a molybdenum-containing acid solution;
dissolving 5g of cobalt oxide in 50g of toluene, adding 30g of nitric acid solution, and carrying out an acidic reaction for 2 hours at 100 ℃ to obtain a cobalt-containing acid solution;
(2) Heating the molybdenum-containing acid solution and the cobalt-containing acid solution to 120 ℃ respectively, carrying out mixing reaction for 5h, adding octanoic acid, carrying out a complex reaction for 10h at 240 ℃ to obtain an organic metal complex, wherein the molar ratio of the sum of molybdenum and cobalt in the product of the mixing reaction to the octanoic acid is 1:9; the content of the + 6-valent molybdenum ions in the organometallic complex was determined to be 83wt%;
(3) And (3) keeping the temperature of the organic metal complex at 80 ℃, adding heavy diesel oil and carbon powder at 80 ℃, uniformly mixing, and cooling to obtain the liquid desulfurization catalyst A.
The composition of the liquid desulfurization catalyst A was measured, and the results are shown in Table 1.
Preparation example 2
(1) Dissolving 20g of molybdic acid in 150g of water, adding 100g of formic acid solution, and carrying out an acidic reaction for 3 hours at 100 ℃ to obtain a molybdic acid-containing solution;
dissolving 20g of cobalt nitrate in 200g of water, adding 150g of formic acid solution, and carrying out an acidic reaction for 5h at 100 ℃ to obtain cobalt-containing acid solution;
(2) Heating the molybdenum-containing acid solution and the cobalt-containing acid solution to 130 ℃ respectively, carrying out mixed reaction for 3h, adding 2-ethylhexanoic acid, and carrying out complex reaction for 8h at 220 ℃ to obtain an organic metal complex, wherein the molar ratio of the sum of molybdenum and cobalt in the product of the mixed reaction to 2-ethylhexanoic acid is 1:7; measuring the content of the + 6-valent molybdenum ions in the organometallic complex to be 75wt%;
(3) Keeping the temperature of the organic metal complex at 70 ℃, adding the heavy firewood and the polypropylene oxide glycol (national medicine company) at 80 ℃, uniformly mixing, and cooling to obtain the liquid desulfurization catalyst B.
The composition of the liquid desulfurization catalyst B was measured, and the results are shown in Table 1.
Preparation example 3
(1) Dissolving 15g of ammonium molybdate in 300g of ethanol, adding 150g of oxalic acid solution, and carrying out an acidic reaction for 5h at 100 ℃ to obtain a molybdenum-containing acid solution;
dissolving 20g of cobalt chloride in 400g of ethanol, adding 200g of oxalic acid solution, and carrying out an acid reaction at 100 ℃ for 8h to obtain a cobalt-containing acid solution;
(2) Heating the molybdenum-containing acid solution and the cobalt-containing acid solution to 130 ℃ respectively, carrying out mixed reaction for 2h, adding benzoic acid, and carrying out complex reaction for 8h at 260 ℃ to obtain an organic metal complex, wherein the molar ratio of the sum of molybdenum and cobalt in the product of the mixed reaction to the benzoic acid is 1:5; measuring the content of the + 6-valent molybdenum ions in the organometallic complex to be 70wt%;
(3) And (3) keeping the temperature of the organic metal complex at 70 ℃, adding catalytic cracking slurry oil and alkylbenzene sulfonic acid at 70 ℃, uniformly mixing, and cooling to obtain the liquid desulfurization catalyst C.
The composition of the liquid desulfurization catalyst C was measured, and the results are shown in Table 1.
Preparation example 4
The catalyst is a solid supported catalyst, marked as catalyst D, and the composition of the catalyst is measured, and the result is shown in Table 1.
TABLE 1
| Item | Catalyst A | Catalyst B | Catalyst C | Catalyst D |
| Molybdenum element (wt%) | 10.3 | 6.9 | 7.6 | 10 |
| Cobalt element (wt)% | 1.6 | 5.0 | 8.4 | 3 |
| Mo：Co | 3.98:1 | 0.83:1 | 0.56:1 | 2.04:1 |
| Organic metal complex, wt.% | 51 | 64.5 | 76 | Is free of |
| Dispersing solvent (wt%) | 48 | 35 | 22 | Is composed of |
| Auxiliary agent (wt%) | 1 | 0.5 | 2 | Is free of |
| Form of the composition | Liquid, method for producing the same and use thereof | Liquid, method for producing the same and use thereof | Liquid, method for producing the same and use thereof | Solid, loaded type |
Examples 1 to 6
Heavy oil desulfurization was carried out according to the conditions listed in table 2:
(i) Carrying out pre-reaction on a liquid desulfurization catalyst and an accelerant in the presence of hydrogen;
(ii) Mixing and reacting the pre-reacted product with heavy oil, optionally recycled material;
(iii) (iii) subjecting the product obtained in step (ii) to a hydrodesulphurisation reaction;
(iv) (iv) separating the product obtained in the step (iii), collecting the gas, and separating low-sulfur heavy oil with the boiling point less than 500 ℃ and tail oil containing the catalyst; the catalyst-containing tail oil is recycled to the hydrodesulfurization reaction or directly thrown outwards.
And analyzing and measuring the sulfur content in the low-sulfur heavy oil and calculating the desulfurization rate. The reaction results are shown in Table 3.
Comparative example 1
A batch type reaction kettle is adopted, the catalyst D is a supported catalyst, and the slag reduction, the catalyst, the vulcanizing agent and hydrogen are added into the high-pressure reaction kettle together for reaction according to the reaction conditions in the example 1. The reaction product is a mixture of gas and liquid and solid, after the toluene insoluble substance is separated from the mixture of liquid and solid, the toluene is removed by rotary evaporation to obtain a liquid product, the sulfur content of the liquid product is analyzed and measured, the desulfurization rate is calculated, and the reaction result is shown in table 3.
TABLE 2
Note: (1) The addition amount of the heavy oil to be treated is calculated by the total amount of Mo and Co elements;
(2) If the promoter is a sulfur-containing substance, the molar ratio of the promoter to the liquid desulfurization catalyst is calculated by S and the sum of Mo and Co elements; if the promoter is ethylene glycol or oleylamine, the addition amount (wt%) of the promoter is relative to the addition amount (wt%) of the liquid desulfurization catalyst calculated by the sum of Mo and Co elements;
(3) The volume ratio of hydrogen to liquid desulfurization catalyst;
(4) The volume ratio of hydrogen to heavy oil;
(5) The proportion of the tail oil containing the catalyst thrown to the middle and the outer parts;
(6) The heavy oil is vacuum residue oil, specifically vacuum residue oil of different refineries, such as vacuum residue oil from medium petrochemical and rare petrochemical, and other heavy oil with similar name.
Table 2 (continuation)
Note: (1) The addition amount of Mo and Co relative to the heavy oil to be treated;
(2) If the promoter is a sulfur-containing substance, the molar ratio of the promoter to the liquid desulfurization catalyst is calculated by S and the sum of Mo and Co elements; if the promoter is ethylene glycol or oleylamine, the addition amount (wt%) of the promoter is relative to the addition amount (wt%) of the liquid desulfurization catalyst calculated by the sum of Mo and Co elements;
(3) The volume ratio of hydrogen to liquid desulfurization catalyst;
(4) The volume ratio of hydrogen to heavy oil;
(5) The proportion of the catalyst-containing tail oil to the external throwing;
(6) The heavy oil is vacuum residue oil, specifically vacuum residue oil of different refineries, such as vacuum residue oil from medium petrochemical and rare petrochemical, and other heavy oil with similar name.
TABLE 3
| Numbering | Desulfurization rate/%) |
| Example 1 | 92.3 |
| Example 2 | 91.5 |
| Example 3 | 91.6 |
| Example 4 | 90.2 |
| Example 5 | 92.7 |
| Example 6 | 93.8 |
| Comparative example 1 | 53.2 |
The results in Table 3 show that the method provided by the invention has strong adaptability of raw materials, is suitable for heavy oil, in particular to inferior heavy oil with high content of impurities such as sulfur, nitrogen, metal and the like and high content of carbon residue and asphaltene, and has high desulfurization rate of the heavy oil which is more than 90 percent. The method is easy to operate and control, can realize the recycling of the catalyst and has good economical efficiency.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (59)
1. A method of desulfurizing heavy oil comprising:
(a) Reacting a liquid desulfurization catalyst, an accelerator, heavy oil and an optional cycle material in the presence of hydrogen;
(b) Separating the product obtained in the step (a) to obtain gas, low-sulfur heavy oil and catalyst-containing tail oil; and optionally
(c) Returning a part of the catalyst-containing tail oil to the step (a) as the circulating material, and throwing the other part of the catalyst-containing tail oil out;
wherein the liquid desulfurization catalyst contains an organometallic complex, a dispersion solvent, and an auxiliary; wherein the organometallic complex comprises molybdenum ions, cobalt ions and C 7 -C 14 An organic anion;
the auxiliary agent is one or more selected from carbon powder, rare earth oxide, aluminum oxide, silicon oxide, alkylphenol, polyoxypropylene glycol, polyoxyethylene ether, alkylbenzene sulfonic acid, polyisobutylene succinic anhydride and butyl isoquinoline.
2. The method of claim 1, wherein in step (a), the reacting comprises: pre-reacting the liquid desulfurization catalyst with a promoter;
the pre-reaction conditions include: the temperature is 300-380 ℃, the time is 0.5-3h, and the volume ratio of the hydrogen to the liquid desulfurization catalyst is 300-3000Nm 3 /m 3 。
3. A process as claimed in claim 2, wherein the volume ratio of hydrogen to the liquid desulphurisation catalyst is in the range 500-2000Nm 3 /m 3 。
4. The method of claim 2 or 3, wherein the reacting further comprises: mixing the pre-reaction product, heavy oil and circulating material for reaction, and then carrying out hydrodesulfurization reaction;
the conditions of the mixing reaction include: the mixing temperature is 350-380 deg.C, and the mixing time is 1-60min;
the hydrodesulfurization reaction conditions include: the desulfurization temperature is more than 380 ℃ and less than 480 ℃; the desulfurization pressure is 11-30MPa; the desulfurization time is 0.5-15h;
the volume ratio of hydrogen to the heavy oil is 500-4000Nm 3 /m 3 。
5. The method of claim 4, wherein the conditions of the hydrodesulfurization reaction comprise: the desulfurization temperature is 400-440 ℃; the desulfurization pressure is 12-25MPa; the desulfurization time is 1-10h;
the volume ratio of hydrogen to the heavy oil is 500-3000Nm 3 /m 3 。
6. The method according to any one of claims 1 to 3 and 5, wherein the liquid desulfurization catalyst is added in an amount of 500 to 30000 ppm by weight of the heavy oil, based on the sum of the elements Mo and Co.
7. The method of claim 6 wherein the liquid desulfurization catalyst is added in an amount of 1000 to 20000 ppm by weight of the heavy oil, based on the sum of the elements Mo and Co.
8. The method according to claim 4, wherein the liquid desulfurization catalyst is added in an amount of 500 to 30000 ppm by weight of the heavy oil, based on the sum of the elements Mo and Co.
9. The method of claim 8 wherein the liquid desulfurization catalyst is added in an amount of 1000 to 20000 ppm by weight of the heavy oil, based on the sum of the elements Mo and Co.
10. The process of any one of claims 1-3, 5, 7-9, wherein in step (a), the promoter is at least one of sublimed sulfur, carbon disulfide, dimethyl sulfide, ethylene glycol, and oleylamine.
11. The method of claim 4, wherein in step (a), the promoter is at least one of sublimed sulfur, carbon disulfide, dimethyl sulfide, ethylene glycol, and oleylamine.
12. The method of claim 6, wherein in step (a), the promoter is at least one of sublimed sulfur, carbon disulfide, dimethyl sulfide, ethylene glycol, and oleylamine.
13. The process according to any one of claims 1-3, 5, 7-9, 11-12, wherein the heavy oil is selected from crude oils with a distillation range > 500 ℃, or a density > 1g/cm 3 The petroleum hydrocarbon oil of (1).
14. The method of claim 13, wherein the heavy oil is selected from at least one of heavy crude oil, vacuum residuum, catalytic cracking slurry oil, coal tar, ethylene tar, shale oil, heavy oil, oil sand bitumen, fixed and ebullated bed residuum hydrogenation tails, and coal liquefaction tails.
15. The process of claim 4 wherein the heavy oil is selected from crude oils having a boiling range > 500 ℃, or a density > 1g/cm 3 The petroleum hydrocarbon oil of (1).
16. The method of claim 15, wherein the heavy oil is selected from at least one of heavy crude oil, vacuum residuum, catalytic cracking slurry oil, coal tar, ethylene tar, shale oil, heavy oil, oil sand bitumen, fixed and ebullated bed residuum hydrogenation tails, and coal liquefaction tails.
17. The process of claim 6 wherein the heavy oil is selected from crude oils having a boiling range > 500 ℃, or a density > 1g/cm 3 The petroleum hydrocarbon oil of (1).
18. The method of claim 17, wherein the heavy oil is selected from at least one of heavy crude oil, vacuum residuum, catalytic cracking slurry oil, coal tar, ethylene tar, shale oil, heavy oil, oil sands bitumen, fixed and ebullated bed residuum hydrogenation tails, and coal liquefaction tails.
19. The process according to claim 10, wherein the heavy oil is selected from crude oils with a distillation range > 500 ℃,or a density > 1g/cm 3 The petroleum hydrocarbon oil of (3).
20. The method of claim 19, wherein the heavy oil is selected from at least one of heavy crude oil, vacuum residuum, catalytically cracked slurry oil, coal tar, ethylene tar, shale oil, heavy oil, oil sand bitumen, fixed and ebullated bed residuum hydrogenation tails, and coal liquefaction tails.
21. The method according to any one of claims 1 to 3, 5, 7 to 9, 11 to 12, 14 to 20, wherein the content of the organometallic complex is 50 to 80wt%, the content of the dispersion solvent is 19 to 50wt%, and the content of the auxiliary is 0.1 to 2wt%, based on the total amount of the liquid desulfurization catalyst;
and/or the dispersion solvent is distillate oil with the distillation range of 300-500 ℃;
and/or the auxiliary agent is selected from at least one of carbon powder, polypropylene oxide glycol and alkyl benzene sulfonic acid.
22. The process of claim 21, wherein the dispersing solvent is a catalytic cracking slurry oil and/or a heavy diesel oil.
23. The method according to claim 4, wherein the organometallic complex is contained in an amount of 50 to 80wt%, the dispersion solvent is contained in an amount of 19 to 50wt%, and the auxiliary is contained in an amount of 0.1 to 2wt%, based on the total amount of the liquid desulfurization catalyst;
and/or the dispersion solvent is distillate oil with the distillation range of 300-500 ℃;
and/or the auxiliary agent is at least one selected from carbon powder, polyoxypropylene glycol and alkyl benzene sulfonic acid.
24. The process of claim 23, wherein the dispersing solvent is catalytic cracking slurry oil and/or heavy diesel oil.
25. The method according to claim 6, wherein the organometallic complex is contained in an amount of 50 to 80wt%, the dispersion solvent is contained in an amount of 19 to 50wt%, and the auxiliary is contained in an amount of 0.1 to 2wt%, based on the total amount of the liquid desulfurization catalyst;
and/or the dispersion solvent is distillate oil with the distillation range of 300-500 ℃;
and/or the auxiliary agent is at least one selected from carbon powder, polyoxypropylene glycol and alkyl benzene sulfonic acid.
26. The process of claim 25, wherein the dispersing solvent is catalytic cracking slurry oil and/or heavy diesel oil.
27. The method according to claim 10, wherein the organometallic complex is contained in an amount of 50 to 80wt%, the dispersion solvent is contained in an amount of 19 to 50wt%, and the auxiliary agent is contained in an amount of 0.1 to 2wt%, based on the total amount of the liquid desulfurization catalyst;
and/or the dispersion solvent is distillate oil with the distillation range of 300-500 ℃;
and/or the auxiliary agent is at least one selected from carbon powder, polyoxypropylene glycol and alkyl benzene sulfonic acid.
28. The process of claim 27, wherein the dispersing solvent is catalytic cracking slurry oil and/or heavy diesel oil.
29. The method according to claim 13, wherein the organometallic complex is contained in an amount of 50 to 80wt%, the dispersion solvent is contained in an amount of 19 to 50wt%, and the auxiliary is contained in an amount of 0.1 to 2wt%, based on the total amount of the liquid desulfurization catalyst;
and/or the dispersion solvent is distillate oil with the distillation range of 300-500 ℃;
and/or the auxiliary agent is at least one selected from carbon powder, polyoxypropylene glycol and alkyl benzene sulfonic acid.
30. The process of claim 29, wherein the dispersing solvent is catalytic cracking slurry oil and/or heavy diesel oil.
31. The method of any one of claims 1-3, 5, 7-9, 11-12, 14-20, 22-30, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85 wt%;
and/or, in the organic metal complex, the molar ratio of the molybdenum ion to the cobalt ion is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
32. The process of claim 31, wherein the molar ratio of molybdenum ions to cobalt ions in the organometallic complex is (0.1-6): 1.
33. the method of claim 4, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85% by weight;
and/or, in the organic metal complex, the molar ratio of the molybdenum ion to the cobalt ion is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
34. The process according to claim 33, wherein the molar ratio of the molybdenum ion to the cobalt ion in the organometallic complex is (0.1-6): 1.
35. the method of claim 6, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85% by weight;
and/or, in the organic metal complex, the molar ratio of the molybdenum ion to the cobalt ion is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
36. The process of claim 35, wherein the molar ratio of molybdenum ions to cobalt ions in the organometallic complex is (0.1-6): 1.
37. the method of claim 10, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85% by weight;
and/or, in the organic metal complex, the molar ratio of the molybdenum ions to the cobalt ions is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
38. The process of claim 37, wherein the molar ratio of molybdenum ions to cobalt ions in the organometallic complex is (0.1-6): 1.
39. the method of claim 13, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85% by weight;
and/or, in the organic metal complex, the molar ratio of the molybdenum ion to the cobalt ion is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
40. The process as claimed in claim 39, wherein the molar ratio of the molybdenum ion to the cobalt ion in the organometallic complex is (0.1-6): 1.
41. the method of claim 21, wherein the molybdenum ions have a +6 molybdenum ion content of no more than 85% by weight;
and/or, in the organic metal complex, the molar ratio of the molybdenum ion to the cobalt ion is (0.1-10): 1;
and/or, the total content of the molybdenum ion and the cobalt ion is 2 to 30wt% based on the total weight of the organometallic complex;
and/or, said C 7 -C 14 The organic anion is selected from at least one of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
42. The process as claimed in claim 41, wherein the molar ratio of the molybdenum ion to the cobalt ion in the organometallic complex is (0.1-6): 1.
43. the method of any one of claims 1-3, 5, 7-9, 11-12, 14-20, 22-30, 32-42, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on the organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
44. The method of claim 4, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
45. The method of claim 6, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on the organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
46. The method of claim 10, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdenum acid-containing liquid and the cobalt acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on the organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
47. The method of claim 13, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
48. The method of claim 21, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
49. The method of claim 31, wherein the method of preparing the liquid desulfurization catalyst comprises:
(1) Respectively dissolving and dispersing a molybdenum-containing compound and a cobalt-containing compound in a solvent, and then respectively carrying out acid liquor reaction with an acidic solution;
(2) Mixing the molybdic acid-containing liquid and cobaltic acid-containing liquid respectively obtained in the step (1), and mixing the obtained product with C 7 -C 14 Carrying out a complex reaction on the organic acid to obtain an organic metal complex;
(3) And uniformly mixing the organic metal complex with a dispersing solvent and an auxiliary agent to obtain the liquid desulfurization catalyst.
50. The method of any one of claims 44-49, wherein said molybdenum-containing compound is selected from at least one of molybdenum oxide, molybdic acid, molybdate, and said cobalt-containing compound is selected from at least one of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt oxide, cobalt hydroxide, cobalt hydroxycarbonate, and cobalt halide;
and/or, the solvent is at least one selected from toluene, water and ethanol;
and/or, the acidic solution is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, oxalic acid, propionic acid and malonic acid;
and/or, said C 7 -C 14 The organic acid is at least one selected from the group consisting of 2-ethylhexanoic acid, octanoic acid, 2-propylheptanoic acid, benzoic acid, phenylacetic acid, phthalic acid, isophthalic acid, and terephthalic acid.
51. The method as claimed in claim 43, wherein in the step (1), the conditions for carrying out the acidic reaction between the molybdenum-containing solution obtained by dissolving and dispersing the molybdenum-containing compound and the acidic solution comprise: the reaction temperature is 50-110 ℃, and the reaction time is 0.5-8h;
and/or the conditions of the cobalt-containing solution obtained by dissolving and dispersing the cobalt-containing compound and the acidic solution for carrying out the acidic reaction comprise: the reaction temperature is 70-110 ℃, and the reaction time is 1-10h;
and/or the mass ratio of the solvent to the molybdenum or cobalt element is (2-30): 1; the molar ratio of the acid solution to the molybdenum or cobalt element is (0.5-10): 1.
52. the method as claimed in any one of claims 44 to 49, wherein in the step (1), the conditions for carrying out the acidic reaction between the molybdenum-containing solution obtained by dissolving and dispersing the molybdenum-containing compound and the acidic solution comprise: the reaction temperature is 50-110 ℃, and the reaction time is 0.5-8h;
and/or the conditions of the cobalt-containing solution obtained by dissolving and dispersing the cobalt-containing compound and the acidic solution for carrying out the acidic reaction comprise: the reaction temperature is 70-110 ℃, and the reaction time is 1-10h;
and/or the mass ratio of the solvent to the molybdenum or cobalt element is (2-30): 1; the molar ratio of the acid solution to the molybdenum or cobalt element is (0.5-10): 1.
53. the method as claimed in claim 50, wherein in the step (1), the conditions for carrying out the acidic reaction of the molybdenum-containing solution obtained by dissolving and dispersing the molybdenum-containing compound with the acidic solution comprise: the reaction temperature is 50-110 ℃, and the reaction time is 0.5-8h;
and/or the conditions of the cobalt-containing solution obtained by dissolving and dispersing the cobalt-containing compound and the acidic solution for carrying out the acidic reaction comprise: the reaction temperature is 70-110 ℃, and the reaction time is 1-10h;
and/or the mass ratio of the solvent to the molybdenum or cobalt element is (2-30): 1; the molar ratio of the acid solution to the molybdenum or cobalt element is (0.5-10): 1.
54. the process as claimed in claim 43, wherein in step (2), the mixing and reacting are carried out by heating the molybdate-containing acid solution and cobaltate-containing acid solution to 120-150 ℃ for 1-8h; the product obtained is reacted with C 7 -C 14 The organic acid is subjected to the complex reaction for 2 to 20 hours at the temperature of between 160 and 300 ℃;
and/or the sum of the molybdenum element and the cobalt element in the product and C 7 -C 14 The molar ratio of the organic acid is 1: (1-12).
55. A process as claimed in any one of claims 44 to 49, wherein in step (2), the mixing and reaction is carried out by heating the molybdate-containing acid solution and cobaltate-containing acid solution to a temperature of 120 to 150 ℃ for 1 to 8 hours; the product obtained is reacted with C 7 -C 14 The organic acid is subjected to the complex reaction at 160-300 ℃ for 2-20h;
and/or the sum of the molybdenum element and the cobalt element in the product and C 7 -C 14 The molar ratio of organic acid is 1: (1-12).
56. The process as claimed in claim 50, wherein in step (2), the mixing and reacting are carried out by heating the molybdate-containing acid solution and cobaltate-containing acid solution to 120-150 ℃ for 1-8h; the product obtained is reacted with C 7 -C 14 The organic acid is subjected to the complex reaction for 2 to 20 hours at the temperature of between 160 and 300 ℃;
and/or the sum of the molybdenum element and the cobalt element in the product and C 7 -C 14 The molar ratio of the organic acid is 1: (1-12).
57. The process as claimed in claim 43, wherein, in the step (3), the organometallic complex is kept at 40 to 80 ℃ and mixed with the dispersion solvent and the auxiliary agent at not more than 80 ℃.
58. The process as claimed in any one of claims 44 to 49, wherein in the step (3), the organometallic complex is kept at 40 to 80 ℃ and mixed with a dispersing solvent and an auxiliary agent at not more than 80 ℃.
59. The method as claimed in claim 50, wherein, in the step (3), the organometallic complex is kept at 40 to 80 ℃ and mixed with the dispersing solvent and the auxiliary agent at not more than 80 ℃.
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