阅读说明：本技术 一种废加氢催化剂回收利用方法 (Method for recycling waste hydrogenation catalyst ) 是由 吕振辉 彭冲 朱慧红 杨涛 金浩 刘璐 杨光 于 2019-09-24 设计创作，主要内容包括：本发明公开了一种废加氢催化剂回收利用方法,包括如下内容：(1)将废加氢催化剂进行抽提除油,焙烧除碳,粉碎,筛分,然后与碱进行混合,焙烧,将焙烧处理后的废催化剂粉末用热水浸渍、过滤,得到滤液和残渣,然后在滤液中加入聚合物单体I,得到溶液I；(3)将残渣与酸混合反应,过滤,在滤液中加入聚合物单体II,得到溶液II；(4)溶液I和溶液II进行并流成胶反应,老化,老化后的悬浊液加入引发剂,进行聚合反应,物料经固液分离,挤条成型,然后干燥、焙烧,得到加氢催化剂。本方法可直接回收废剂中活性金属及氧化铝,制备出性能优异的新催化剂,实现了催化剂的循环利用,改善了环境状况,降低了催化剂的生产成本。(The invention discloses a method for recycling a waste hydrogenation catalyst, which comprises the following steps: (1) extracting the waste hydrogenation catalyst for removing oil, roasting for removing carbon, crushing, screening, mixing with alkali, roasting, soaking the roasted waste catalyst powder in hot water, filtering to obtain filtrate and residue, and adding a polymer monomer I into the filtrate to obtain a solution I; (3) mixing the residue with acid for reaction, filtering, and adding a polymer monomer II into the filtrate to obtain a solution II; (4) and (3) carrying out parallel flow gelling reaction on the solution I and the solution II, aging, adding an initiator into the aged suspension, carrying out polymerization reaction, carrying out solid-liquid separation on the materials, extruding and forming, drying and roasting to obtain the hydrogenation catalyst. The method can directly recover the active metal and the alumina in the waste agent, prepare the new catalyst with excellent performance, realize the recycling of the catalyst, improve the environmental condition and reduce the production cost of the catalyst.)

1. A method for recycling a waste hydrogenation catalyst is characterized by comprising the following steps: (1) extracting the waste hydrogenation catalyst containing active components of molybdenum and nickel to remove oil, drying, roasting to remove carbon, crushing and screening; wherein the hydrogenation catalyst takes alumina or modified alumina as a carrier; (2) mixing the screened waste catalyst powder with alkali, then roasting, soaking the roasted waste catalyst powder with hot water, filtering to obtain filtrate and residue, and then adding a certain amount of polymer monomer I into the filtrate to obtain solution I; (3) mixing the residue obtained in the step (2) with acid, reacting for a period of time under the condition of stirring, filtering, and then adding a certain amount of polymer monomer II into the filtrate to obtain a solution II; (4) adding a certain amount of bottom water into a reaction container, and performing parallel-flow gelling reaction by adopting the solution I and the solution II, wherein the gelling reaction comprises the following specific processes: firstly adjusting the pH value to be 2.0-3.0, crystallizing for 15-30 min, then adjusting the pH value to be 10.0-11.0, stabilizing for 5-10 min, then swinging for neutralization and gelling the pH value, after swinging for a certain number of times, adjusting the pH value to be 7.0-9.0 after gelling, aging for a period of time, adding an initiator into the aged suspension, carrying out polymerization reaction, and after the reaction is finished, carrying out solid-liquid separation on the material, and drying to obtain a catalyst precursor; (5) and extruding the catalyst precursor into strips, drying and roasting to obtain the hydrogenation catalyst.

2. The method of claim 1, wherein: the waste hydrogenation catalyst in the step (1) contains 70-90% of catalyst solid and 10-30% of petroleum fraction by weight.

3. The method of claim 1, wherein: the weight content of nickel oxide in the extracted catalyst in the step (1) is 2-10%, and the weight content of molybdenum oxide is 8-25%; the organic solvent adopted by the extraction is toluene, petroleum ether, ethanol and the like, and the extraction temperature is 80-110 ℃.

4. The method of claim 1, wherein: in the step (2), the molar ratio of the alkali to the crushed catalyst is 2.0-5.0 in terms of oxides: 1, preferably 2.0 to 3.5: 1.

5. the method of claim 1, wherein: in the step (2), the roasting temperature is 500-800 ℃, and the time is 0.5-4.0 h.

6. The method of claim 1, wherein: the hot water dipping treatment conditions in the step (2) are as follows: the temperature of the leaching water is 50-100 ℃, the leaching time is 30-120 min, and the liquid-solid mass ratio is 2: 1-10: 1: 1; after the hot water immersion treatment, the leaching rate of the molybdenum oxide is 90-98%, preferably 95-98%, and the leaching rate of the aluminum oxide is 35-55%, preferably 45-50%; the leaching rate was calculated as the ratio of the amount of oxide contained in the solid before leaching to the amount of oxide contained after leaching.

7. The method of claim 1, wherein: the polymer monomer I in the step (2) is organic alcohol and/or amino acid I; the organic alcohol is one or more of ethylene glycol, pentaerythritol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, sorbitol, dipropylene glycol, glycerol, xylitol, trimethylolpropane or diethylene glycol; the amino acid I is one or more of aspartic acid, glutamic acid, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine; the addition amount of the polymer monomer I is 1-5 wt% of the weight of the acidic salt solution, and the weight of the acidic salt solution is calculated by metal oxide.

8. The method of claim 1, wherein: the molar ratio of the acid to the solid residue in the step (3) is 2.0-4.0 in terms of oxides: 1, preferably 2.5 to 3.5: 1; the reaction time is 0.5-3.0 h, and the dissolving temperature is 80-150 ℃; the dissolution rate of molybdenum and/or nickel is 90-98%, preferably 95-95%, and the dissolution rate of alumina is 90-98%, preferably 90-95%; the dissolution rate calculation method is the ratio of the amount of the oxide contained in the solid before leaching to the amount of the oxide contained after leaching.

9. The method of claim 1, wherein: the polymer monomer II is organic amine and/or amino acid II, and the organic amine is one or more of 2-methyl-1, 5-pentanediamine 1, 9-nonanediamine, ethylenediamine, 1, 6-hexanediamine, 2-methyl-1, 8-neodiamine and 1, 10-decanediamine or urea; the amino acid II is one or more of arginine, lysine, histidine, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine; the addition amount of the polymer monomer II is 1-5 wt% of the weight of the alkaline salt solution, and the weight of the alkaline salt solution is calculated by metal oxide.

10. The method of claim 1, wherein: the gelling temperature in the step (4) is 50-100 ℃; in the step (4), the mass concentration of molybdenum in the solution I is 15-50 g/100mL calculated as molybdenum oxide, and the mass concentration of aluminum is 10-20 g/100mL calculated as aluminum oxide; in the solution II, the total mass concentration of nickel and/or cobalt is 5-10 g/100mL calculated as oxide, and the mass concentration of aluminum is 5-10 g/100mL calculated as alumina.

11. The concentration of the solution can be controlled and adjusted by heating and distilling or adding water for dilution.

12. The method of claim 1, wherein: in the step (4), the swing neutralization gelling temperature is 50-100 ℃, and preferably 70-100 ℃; in the swing neutralization gelling process, the acid pH value is 2.0-3.0, the alkaline pH value is 10.0-11.0, and the swing times are 3-8 times, preferably 3-5 times.

13. The method of claim 1, wherein: and (4) aging at 50-100 ℃, preferably 70-100 ℃, for 0.5-2.5 h, preferably 1.0-2.0 h.

14. The method of claim 1, wherein: the initiator in the step (4) is a peroxide initiator, an azo initiator or a redox initiator.

15. The method of claim 13, wherein: the peroxide initiator in the step (4) is benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, potassium persulfate, sodium persulfate or ammonium persulfate, preferably ammonium persulfate and potassium persulfate.

16. The method of claim 13, wherein: the azo initiator in the step (4) is azobisisobutyronitrile or azobisisoheptonitrile, preferably azobisisobutyronitrile.

17. The method of claim 13, wherein: the redox initiator in the step (4) is benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, n-dimethylaniline, ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide// N, n-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/mercaptan, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride or cumene hydroperoxide/tetraethylene imine.

18. The method of claim 1, wherein: the polymerization reaction temperature in the step (4) is 100-350 ℃, preferably 150-250 ℃, and the polymerization reaction time is 1.0-4.0 h, preferably 1.0-3.0 h.

19. The method of claim 1, wherein: the hydrogenation catalyst prepared by the method has the following properties: the pore volume is 0.5 to 1.0 mL/g^-1(ii) a The aperture is 15-25 nm; the bulk density is 0.45-0.75 g/mL; the pore size distribution is as follows: the proportion of the aperture less than 50nm is 1-2%, the proportion of the aperture 50-100 nm is 10-20%, and the proportion of the aperture more than 10nm is 80-85%.

20. Use of a hydrogenation catalyst prepared according to any one of claims 1 to 18 in a wax oil, residual oil, coal tar, or coal liquefaction oil hydrotreating process.

Technical Field

The invention relates to a method for recycling a waste hydrogenation catalyst.

Background

In modern oil refining and chemical industry, more than 90% of chemical reactions are realized through a catalytic process, and a catalyst becomes a key for developing new products of new processes for realizing oil refining and chemical industry. However, when the catalyst is changed into a waste catalyst, certain harm is caused to the environment. At present, the basic service life of a residual oil hydrogenation catalyst is 8000 hours, each set of residual oil hydrogenation device generates hundreds of tons of waste catalysts every year, more than ten sets of residual oil hydrogenation devices are in existence at home at present, and the quantity of the residual oil waste catalysts in China can reach thousands of tons every year. The molybdenum-nickel active metal content on the residual oil hydrogenation catalyst is lower than that of other catalysts, the metal recovery problem is mainly considered by catalyst recovery enterprises at present, and the utilization rate of the carrier is too low for alumina carriers which are basically used as waste residues for cement or ceramic enterprises. The recovery and reuse of active metals and alumina is an important direction of the current catalyst research.

CN201611011637.6 discloses a method for recycling hydrotreating catalyst, which comprises the following steps: (1) extracting, roasting and crushing the molybdenum-nickel system waste catalyst; (2) mixing the crushed catalyst powder with alkali, and then carrying out microwave treatment; (3) adding an acid solution into the molybdate solution obtained in the step (2) to obtain molybdic acid; (4) crushing the alumina filter residue obtained in the step (2), mixing with alkali again, roasting, dipping in hot water, and filtering to obtain an aluminate solution and a nickel oxide solid; (5) introducing carbon dioxide into the aluminate solution obtained in the step (4), preparing pseudo-boehmite by using a carbonization method, mixing the pseudo-boehmite with an adhesive, and preparing a carrier by molding, drying and roasting; (6) adding acid into the nickel oxide obtained in the step (4) to prepare a nickel solution, and adding carbonate to prepare basic nickel carbonate; (7) and (4) preparing molybdic acid in the step (3) and the basic nickel carbonate in the step (6) into a molybdenum-nickel-phosphorus solution, then impregnating the molybdenum-nickel-phosphorus solution on the carrier in the step (5), and drying and roasting the molybdenum-nickel-phosphorus solution to prepare the catalyst. The method is particularly suitable for recovering the molybdenum-nickel spent catalyst to prepare a new catalyst, but the process is complex.

CN201410738197.9 discloses a preparation method of a residual oil hydrogenation monolithic catalyst, which comprises the following steps: (1) mixing and tabletting the mixed powder with different dosages, dilute nitric acid and superfine fiber to prepare the monolithic catalyst carrier with the three-dimensional through-hole channel. (2) Soaking the carrier in Tween-80 solution of certain concentration, drying, roasting, soaking the treated carrier in Mo-Ni-P solution in different Mo-Ni-P ratio, drying, roasting to obtain the residual oil hydrogenating integral catalyst. The method adopts multiple dipping, drying and roasting processes, the plugging of the pore structure of the catalyst and the damage of the pore channel are easily caused by the multiple dipping and roasting of the active metal, and the preparation process is complex, time-consuming and labor-consuming.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a method for recycling a waste hydrogenation catalyst. The method can directly recover the active metal and the alumina in the waste catalyst, prepare the new catalyst with excellent performance, realize the recycling and economic utilization of the catalyst, improve the environmental condition and greatly reduce the production cost of the catalyst.

The method for recycling the waste hydrogenation catalyst comprises the following steps:

(1) extracting the waste hydrogenation catalyst containing active components of molybdenum and nickel to remove oil, drying, roasting to remove carbon, crushing and screening; wherein the hydrogenation catalyst takes alumina or modified alumina as a carrier;

(2) mixing the screened waste catalyst powder with alkali, then roasting, soaking the roasted waste catalyst powder with hot water, filtering to obtain filtrate and residue, and then adding a certain amount of polymer monomer I into the filtrate to obtain solution I;

(3) mixing the residue obtained in the step (2) with acid, reacting and dissolving for a period of time under the condition of stirring, filtering, and then adding a certain amount of polymer monomer II into the filtrate to obtain a solution II;

(4) adding a certain amount of bottom water into a reaction container, and performing parallel-flow gelling reaction by adopting the solution I and the solution II, wherein the gelling reaction comprises the following specific processes: firstly adjusting the pH value to be 2.0-3.0, crystallizing for 15-30 min, then adjusting the pH value to be 10.0-11.0, stabilizing for 5-10 min, then swinging for neutralization and gelling the pH value, after swinging for a certain number of times, adjusting the pH value to be 7.0-9.0 after gelling, aging for a period of time, adding an initiator into the aged suspension, carrying out polymerization reaction, and after the reaction is finished, carrying out solid-liquid separation on the material, and drying to obtain a catalyst precursor;

(5) and extruding the catalyst precursor into strips, drying and roasting to obtain the hydrogenation catalyst.

In the method, the waste hydrogenation catalyst in the step (1) contains 70-90% of catalyst solid and 10-30% of petroleum fraction by weight, wherein the weight content of nickel oxide in the extracted catalyst is 2-10%, and the weight content of molybdenum oxide is 8-25%. The organic solvent adopted for extraction is toluene, petroleum ether, ethanol and the like, and the extraction temperature is 80-110 ℃; the drying temperature is 100-150 ℃, preferably 120-150 ℃, and the drying time is 1-10 hours; the roasting temperature is 500-700 ℃, preferably 600-650 ℃, and the roasting time is 1-5 hours; after crushing and screening, the granularity is 200-400 meshes, preferably 300-400 meshes.

In the method of the invention, the alkali in the step (2) is sodium hydroxide, sodium carbonate and the like, preferably sodium carbonate; the molar ratio of the alkali to the crushed catalyst is 2.0-5.0 in terms of oxides: 1, preferably 2.0 to 3.5: 1.

in the method, the roasting temperature in the step (2) is 500-800 ℃, preferably 550-750 ℃, and the time is 0.5-4.0 h, preferably 0.5-3.0 h; the roasting atmosphere is one or more of air, nitrogen and the like. The hot water dipping treatment conditions are as follows: the temperature of the leaching water is 50-100 ℃, and preferably 80-100 ℃; the leaching time is 30-120 min, preferably 30-90 min; the liquid-solid mass ratio is 2: 1-10: 1, preferably 4: 1-8: 1; after the hot water immersion treatment, the leaching rate of the molybdenum oxide is 90-98%, preferably 95-98%, and the leaching rate of the aluminum oxide is 35-55%, preferably 45-50%. The leaching rate was calculated as the ratio of the amount of oxide contained in the solid before leaching to the amount of oxide contained after leaching.

In the method, the polymer monomer I in the step (2) is organic alcohol and/or amino acid I; the organic alcohol is one or more of ethylene glycol, pentaerythritol, 2-propylene glycol, 1, 4-butanediol, neopentyl glycol, sorbitol, dipropylene glycol, glycerol, xylitol, trimethylolpropane or diethylene glycol; the amino acid I is one or more of aspartic acid, glutamic acid, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine. The addition amount of the polymer monomer I is 1-5 wt% of the weight of the acidic salt solution, and the weight of the acidic salt solution is calculated by metal oxide.

In the method of the present invention, the acid in step (3) is a nitric acid solution, sulfuric acid or hydrochloric acid, preferably sulfuric acid or nitric acid.

In the method, the molar ratio of the acid in the step (3) to the solid residue is 2.0-4.0 in terms of oxides: 1, preferably 2.5 to 3.5: 1. the reaction time is 0.5-3.0 h, preferably 1.0-3.0 h, and the dissolution temperature is 80-150 ℃, preferably 100-120 ℃. In the process, the dissolution rate of molybdenum and/or nickel is 90-98%, preferably 95-95%, and the dissolution rate of alumina is 90-98%, preferably 90-95%. The dissolution rate calculation method is the ratio of the amount of the oxide contained in the solid before leaching to the amount of the oxide contained after leaching.

In the method, the polymer monomer II in the step (3) is organic amine and/or amino acid II, and the organic amine is one or more of 2-methyl-1, 5-pentanediamine 1, 9-nonanediamine, ethylenediamine, 1, 6-hexanediamine, 2-methyl-1, 8-neodiamine, 1, 10-decanediamine or urea; the amino acid II is one or more of arginine, lysine, histidine, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine. The addition amount of the polymer monomer II is 1-5 wt% of the weight of the alkaline salt solution, and the weight of the alkaline salt solution is calculated by metal oxide.

In the method, the adding amount of the bottom water in the step (4) is generally added according to the reaction requirement and the size of a reaction container, generally accounts for 1/2-2/3 of the volume of the reaction container, and the gelling temperature is 50-100 ℃.

In the method, the mass concentration of molybdenum in the solution I in the step (4) is 15-50 g/100mL calculated as molybdenum oxide, and the mass concentration of aluminum is 10-20 g/100mL calculated as aluminum oxide; in the solution II, the total mass concentration of nickel and/or cobalt is 5-10 g/100mL calculated as oxide, and the mass concentration of aluminum is 5-10 g/100mL calculated as alumina. The concentration of the solution can be controlled and adjusted by heating and distilling or adding water for dilution.

In the method, the swing neutralization gelling temperature in the step (4) is 50-100 ℃, and preferably 70-100 ℃; the stirring speed is 20-100 rad/min, preferably 20-50 rad/min; in the swing neutralization gelling process, the acid pH value is 2.0-3.0, the alkaline pH value is 10.0-11.0, and the swing times are 3-8 times, preferably 3-5 times.

In the method, the aging temperature in the step (4) is 50-100 ℃, preferably 70-100 ℃, and the aging time is 0.5-2.5 h, preferably 1.0-2.0 h.

In the method, the initiator in the step (4) can be a peroxide initiator, an azo initiator, a redox initiator and the like according to the reaction requirement, wherein the peroxide initiator is divided into an organic peroxide initiator and an inorganic peroxide initiator. The organic peroxide initiator may be selected from: (1) acyl peroxides (benzoyl peroxide, lauroyl peroxide); (2) hydroperoxides (cumene hydroperoxide, tert-butyl hydroperoxide); (3) dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide); (4) ester peroxides (tert-butyl peroxybenzoate, tert-butyl peroxypivalate); (5) ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide); (6) dicarbonate peroxides (diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate). The inorganic peroxy compound may be selected from persulfates, such as potassium persulfate, sodium persulfate, ammonium persulfate, preferably ammonium persulfate and potassium persulfate. Azo initiators may be selected from azobisisobutyronitrile and azobisisoheptonitrile, preferably azobisisobutyronitrile. The redox initiator can be selected from benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium metabisulfite, benzoyl peroxide/N, N-dimethylaniline. Ammonium persulfate/sodium bisulfite, potassium persulfate/sodium bisulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/ferrous sulfate, benzoyl peroxide// N, N-diethylaniline, benzoyl peroxide/ferrous pyrophosphate, potassium persulfate/silver nitrate, persulfate/thiol, cumene hydroperoxide/ferrous chloride, potassium persulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, cumene hydroperoxide/tetraethyleneimine, and the like. Tert-butyl hydroperoxide/sodium metabisulphite is preferred.

In the method, the polymerization reaction temperature in the step (4) is 100-350 ℃, preferably 150-250 ℃, and the polymerization reaction time is 1.0-4.0 h, preferably 1.0-3.0 h.

In the method of the present invention, the extrusion molding in step (5) is well known to those skilled in the art, and extrusion aids, binders, etc. are generally added.

In the method, in the step (5), the drying temperature is 100-200 ℃, preferably 120-150 ℃, the drying time is 1-10 hours, the roasting temperature is 300-800 ℃, preferably 350-550 ℃, and the roasting time is 2.0-5.0 hours, preferably 2.0-4.0 hours.

The hydrogenation catalyst prepared by the method has the following properties: the pore volume is 0.5 to 1.0 mL/g^-1(ii) a The aperture is 15-25 nm; the bulk density is 0.45-0.75 g/mL; the pore size distribution is as follows: the proportion of the aperture less than 50nm is 1-2%, and the proportion of the aperture between 50 and 100nmFor example, 10-20%, and the proportion of the aperture larger than 10nm is 80-85%.

The hydrogenation catalyst prepared by the method can be used for the hydrogenation treatment process of wax oil, residual oil, coal tar, coal liquefied oil and the like.

Compared with the prior art, the method has the following advantages: the method dissolves and removes the molybdenum and part of the alumina in the waste catalyst in the step (2), dissolves and removes the nickel and part of the alumina in the solid residue by acidification in the step (3), can recycle the required active metal and the alumina to the maximum extent by the process, and improves the recovery rate. The active metal salt is precipitated under the acidic pH value condition in the step (4), the active metal salt with strong polarity and small particles is used as a seed crystal, the seed crystal has higher directional speed and is easy to form crystal form precipitates or colloidal particles with a crystal structure, on one hand, the crystals grow directionally, the crystal crystallinity is high, the crystals are more complete, on the other hand, the phase inversion temperature of a precursor is reduced, the roasting temperature of the catalyst can be obviously reduced, the strength of the catalyst product can be improved at low temperature, and simultaneously, the low-temperature roasting reduces the phenomena of inactive nickel-aluminum spinel and active metal agglomeration, so that the interaction between the active metal and a carrier and the active metal is weakened, the catalyst is easier to be sulfurized into a high-activity II-type active phase, the activity is higher, and the activity is higher. The hydrogenation catalyst prepared by the waste catalyst can directly recover active metal and alumina in the waste catalyst, and is an environment-friendly catalyst preparation method; the utilization rate of active metal and alumina can be obviously improved, the recycling economy of the catalyst is realized, the environmental condition is improved, and the production cost of the catalyst is greatly reduced. The method adopts the polymer monomer as the polar dispersant, so that the particle agglomeration is reduced; and then, the continuous through-channels are formed by copolymerization of different polymer monomers, so that the problems of difficulty in passing residual oil macromolecular colloids and asphaltene micelles through the channels and high diffusion resistance and reaction pressure in the prior art are solved, and the deactivation speed of the catalyst in the heavy oil hydrotreating process is slowed down. The polymer monomer is adopted as a coordination agent to be chelated with the metal component, so that the effects of metal, a carrier and metal can be obviously reduced, the catalyst is easier to vulcanize, and the activity is higher; and the surface phase active metal site density is higher, the utilization rate of the hydrogenation active metal is higher, the surface phase active metal is easier to be vulcanized into a II-type active phase with higher hydrogenation activity, and the formation of spinel without hydrogenation activity is reduced.

Detailed Description

In the method, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption method. The content of the active metal in the catalyst surface phase is determined by X-ray photoelectron spectroscopy (XPS). The content of active metal in the catalyst bulk phase is measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). The strength of the alumina carrier was measured by a lateral pressure densitometer. The alumina carrier abrasion was measured using a rotary abrader.

The ratio of the weight content of the surface-phase active metal component NiO to the weight content of the bulk-phase active metal component NiO is 2.0: 1-6.0: 1, preferably 2.0-5.0: 1, and the surface-phase active metal component MoO₃With the bulk active metal component MoO₃The weight ratio of (A) to (B) is 2.0:1 to 8.0:1, preferably 2.0:1 to 6.0: 1.

The preparation process of the hydrogenation catalyst of the present invention is described in more detail below by way of specific examples. The examples are merely illustrative of specific embodiments of the process of the present invention and do not limit the scope of the invention.

Example 1

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 90 ℃, drying at 120 ℃ for 3 hours, roasting at 650 ℃ for 2 hours, screening and crushing to 350 meshes; weighing 150g of catalyst and 200g of sodium carbonate, uniformly mixing, and roasting at 650 ℃ for 3.0 h; leaching with 250g of hot water at 90 ℃, filtering, wherein the leaching rate of molybdenum oxide is 95 percent, and the leaching rate of aluminum oxide is 45 percent, so as to obtain an alkaline solution containing sodium molybdate and sodium metaaluminate and about 80g of solid residue containing nickel and aluminum; adding 180mL of 50% concentrated sulfuric acid into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water and 25g of ethylene glycol to adjust the concentration of molybdenum oxide in the alkaline solution to be 20g/100mL and the concentration of aluminum oxide to be 15g/100 mL; water and 10g of oxalic acid are added to adjust the concentration of nickel oxide in the acid solution to be 7g/100mL and the concentration of aluminum oxide to be 8g/100 mL.

5L of purified water was added to a 10L gelling tank and heated to 80 ℃. Adding sulfuric acid into the neutralization and gel forming tank to adjust the pH value to 2.0, stabilizing for 5min, then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; then using the acid solution to adjust the pH value to 2.0, stabilizing for 5min, then using the alkaline solution to adjust the pH value to 10.0, repeating for 4 times, adjusting the pH value to 8.0, aging at 70 ℃, then transferring the mixed slurry into a high-pressure kettle, adding 20g of sodium persulfate, carrying out polymerization reaction at 210 ℃ for 2h, filtering, washing, drying at 100 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain the hydrogenation catalyst A, wherein the properties of the hydrogenation catalyst A are shown in Table 2.

Example 2

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 100 ℃, drying the molybdenum-nickel catalyst for 2 hours at 150 ℃, roasting the molybdenum-nickel catalyst for 3 hours at 600 ℃, screening and crushing the molybdenum-nickel catalyst to 400 meshes; weighing 300g of catalyst and 300g of sodium carbonate, uniformly mixing, and roasting at 650 ℃ for 2.5 hours; leaching with 350g of 100 ℃ hot water, filtering, wherein the leaching rate of molybdenum oxide is 97 percent, and the leaching rate of aluminum oxide is 49 percent, so as to obtain an alkaline solution containing sodium molybdate and sodium metaaluminate and about 120g of solid residue containing nickel and aluminum; adding 300mL of concentrated sulfuric acid with the concentration of 50% into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 3.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water and 15g of ethylene glycol to adjust the concentration of molybdenum oxide in the alkaline solution to be 18g/100mL and the concentration of aluminum oxide to be 12g/100 mL; water and 20g of glutamic acid were added to adjust the concentration of nickel oxide in the acidic solution to 8g/100mL and the concentration of alumina to 9g/100 mL.

7L of purified water was added to a 10L gel forming tank and heated to 90 ℃. Adding sulfuric acid into the neutralization and gelling tank to adjust the pH value to 2.0, stabilizing for 5min, and then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; then using the acidic solution to adjust the pH value to 2.0, stabilizing for 5min, then using the alkaline solution to adjust the pH value to 10.0, repeating for 6 times, adjusting the pH value to 8.0, aging at 80 ℃, then transferring the mixed slurry into a high-pressure kettle, adding 15g of potassium persulfate, carrying out polymerization reaction at 190 ℃ for 4h, filtering, washing, drying at 120 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain a hydrogenation catalyst B, wherein the properties of the hydrogenation catalyst B are shown in Table 2.

Example 3

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 90 ℃, drying the molybdenum-nickel catalyst at 130 ℃ for 2 hours, roasting the molybdenum-nickel catalyst at 650 ℃ for 2.5 hours, screening and crushing the molybdenum-nickel catalyst to 350 meshes; weighing 500g of catalyst and 650g of sodium carbonate, uniformly mixing, and roasting at 620 ℃ for 3.0 h; leaching with 600g of hot water at 100 ℃, filtering, wherein the leaching rate of molybdenum oxide is 98 percent, and the leaching rate of aluminum oxide is 47 percent, so as to obtain an alkaline solution containing sodium molybdate and sodium metaaluminate and about 210g of solid residue containing nickel and aluminum; adding 500mL of concentrated sulfuric acid with the concentration of 50% into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water and 30g of oxalic acid to adjust the concentration of molybdenum oxide in the alkaline solution to be 20g/100mL and the concentration of aluminum oxide to be 15g/100 mL; water and 20g of 1, 6-hexanediamine were added to adjust the concentration of nickel oxide to 10g/100mL and the concentration of alumina to 12g/100mL in the acidic solution.

8L of purified water was added to a 15L gelling tank and heated to 100 ℃. Adding sulfuric acid into the neutralization and gelling tank to adjust the pH value to 2.0, stabilizing for 5min, and then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 6 times, adjusting the pH value to 8.0, aging at 100 ℃, transferring the mixed slurry into a high-pressure kettle, adding 25g of ammonium persulfate/sodium bisulfite, carrying out polymerization reaction at 200 ℃ for 2h, filtering, washing, drying at 130 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain a hydrogenation catalyst C, wherein the properties of the hydrogenation catalyst C are shown in Table 2.

Example 4

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 100 ℃, drying the molybdenum-nickel catalyst for 2 hours at 150 ℃, roasting the molybdenum-nickel catalyst for 2 hours at 620 ℃, screening and crushing the molybdenum-nickel catalyst to 350 meshes; weighing 1000g of catalyst and 1100g of sodium carbonate, uniformly mixing, and roasting at 600 ℃ for 2.5 h; leaching with hot water of 1200g at 90 ℃, filtering, wherein the leaching rate of molybdenum oxide is 98 percent, and the leaching rate of aluminum oxide is 45 percent, so as to obtain an alkaline solution containing sodium molybdate and sodium metaaluminate and about 620g solid residue containing nickel and aluminum; adding 600mL of 50% concentrated sulfuric acid into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water and 30g of diglycol to adjust the concentration of molybdenum oxide in the alkaline solution to 21g/100mL and the concentration of aluminum oxide to 20g/100 mL; water and 20g of glycine were added to adjust the concentration of nickel oxide to 9g/100mL and the concentration of alumina to 10g/100mL in the acidic solution.

15L of purified water was added to a 20L gelling tank and heated to 90 ℃. Adding sulfuric acid into the neutralization and gelling tank to adjust the pH value to 2.0, stabilizing for 5min, and then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 9 times, adjusting the pH value to 8.0, aging at 90 ℃, transferring the mixed slurry into a high-pressure kettle, adding 30g of ammonium persulfate/sodium bisulfite, carrying out polymerization reaction at 200 ℃ for 2h, filtering, washing, drying at 130 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain a hydrogenation catalyst D, wherein the properties of the hydrogenation catalyst D are shown in Table 2.

Comparative example 1

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 100 ℃, drying the molybdenum-nickel catalyst for 3 hours at 120 ℃, roasting the molybdenum-nickel catalyst for 2 hours at 650 ℃, screening and crushing the molybdenum-nickel catalyst to 350 meshes; weighing 200g of catalyst and 250g of sodium carbonate, uniformly mixing, and roasting at 750 ℃ for 300 h; leaching with 400g of hot water at 90 ℃, filtering, wherein the leaching rate of molybdenum oxide is 95% and the leaching rate of aluminum oxide is 45%, and obtaining an alkaline solution containing sodium molybdate and sodium metaaluminate and about 120g of solid residue containing nickel and aluminum; adding 200mL of concentrated sulfuric acid with the concentration of 80% into the solid residue containing nickel and aluminum, stirring and reacting at 95 ℃ for 1.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water to adjust the concentration of the molybdenum oxide in the alkaline solution to 31g/100mL and the concentration of the aluminum oxide in the alkaline solution to 18g/100 mL; the concentration of nickel oxide in the acidic solution was 10g/100mL and the concentration of alumina was 8g/100 mL.

5L of purified water is added into the gel forming tank, and the mixture is heated to 90 ℃. And then adding the alkaline solution and the acidic solution into a neutralization and gel-forming tank at the same time, adjusting the pH value to 8.5, aging at the aging temperature of 90 ℃ for 2.0h, filtering, and drying to obtain the required catalyst precursor.

Mixing the catalyst precursor with an adhesive, molding, drying at 120 ℃, and roasting at 500 ℃ for 3h to obtain a catalyst E, wherein the properties of the catalyst E are shown in Table 2.

Comparative example 2

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 100 ℃, drying the molybdenum-nickel catalyst for 3 hours at 1120 ℃, roasting the molybdenum-nickel catalyst for 2 hours at 600 ℃, screening and crushing the molybdenum-nickel catalyst to 300 meshes; (ii) a Weighing 200g of catalyst and 400g of sodium carbonate, uniformly mixing, and roasting at 600 ℃ for 4.0 h; leaching with hot water of 300g at 90 ℃, filtering, wherein the leaching rate of molybdenum oxide is 95 percent, and the leaching rate of aluminum oxide is 49 percent, so as to obtain alkaline solution containing sodium molybdate and sodium metaaluminate and about 250g solid residue containing nickel and aluminum; adding 200mL of concentrated sulfuric acid with the concentration of 50% into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water to adjust the concentration of molybdenum oxide in the alkaline solution to be 20g/100mL and the concentration of aluminum oxide to be 15g/100 mL; the concentration of nickel oxide in the acidic solution was 7g/100mL and the concentration of alumina was 8g/100 mL.

5L of purified water is added into the gelling tank, and the mixture is heated to 70 ℃. Adding a certain amount of the alkaline solution into a neutralization and gelling tank, adding sulfuric acid to adjust the pH value to be 2.0, precipitating a small amount of molybdenum oxide and aluminum oxide to be used as seed crystals and crystallizing for 20min, then adding the alkaline solution to adjust the pH value to be 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 4 times, adjusting the pH value to 8.0, aging at the temperature of 70 ℃, aging for 1.0h, filtering, and drying to obtain the required catalyst precursor.

Mixing the catalyst precursor with an adhesive, molding, drying at 120 ℃, and roasting at 350 ℃ for 3h to obtain a catalyst F, wherein the properties of the catalyst F are shown in Table 2.

Comparative example 3

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 100 ℃, drying the molybdenum-nickel catalyst for 2 hours at 150 ℃, roasting the molybdenum-nickel catalyst for 2.5 hours at 620 ℃, screening and crushing the molybdenum-nickel catalyst to 350 meshes; weighing 1000g of catalyst and 1100g of sodium carbonate, uniformly mixing, and roasting at 600 ℃ for 2.5 h; leaching with hot water of 1200g at 90 ℃, filtering, wherein the leaching rate of molybdenum oxide is 95 percent, and the leaching rate of aluminum oxide is 45 percent, so as to obtain alkaline solution containing sodium molybdate and sodium metaaluminate and about 620g solid residue containing nickel and aluminum; adding 600mL of 50% concentrated sulfuric acid into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water and 30g of diglycol to adjust the concentration of molybdenum oxide in the alkaline solution to 21g/100mL and the concentration of aluminum oxide to 20g/100 mL; water and 20g of glycine were added to adjust the concentration of nickel oxide to 9g/100mL and the concentration of alumina to 10g/100mL in the acidic solution.

15L of purified water was added to a 20L gelling tank and heated to 90 ℃. Adding sulfuric acid into the neutralization and gelling tank to adjust the pH value to 2.0, stabilizing for 5min, and then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 9 times, adjusting the pH value to 8.0, aging at 90 ℃, transferring the mixed slurry into a high-pressure kettle, adding 30G of ammonium persulfate/sodium bisulfite, carrying out polymerization reaction at 200 ℃ for 2h, filtering, washing, drying at 130 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain the hydrogenation catalyst G, wherein the properties of the hydrogenation catalyst G are shown in Table 2.

Comparative example 4

Extracting and deoiling the molybdenum-nickel catalyst after industrial operation at 90 ℃, drying at 130 ℃ for 2 hours, roasting at 650 ℃ for 3 hours, screening and crushing to 350 meshes; weighing 500g of catalyst and 650g of sodium carbonate, uniformly mixing, and roasting at 620 ℃ for 3.0 h; leaching with 600g of hot water at 100 ℃, filtering, wherein the leaching rate of molybdenum oxide is 95 percent, and the leaching rate of aluminum oxide is 45 percent, so as to obtain an alkaline solution containing sodium molybdate and sodium metaaluminate and about 210g of solid residue containing nickel and aluminum; adding 500mL of concentrated sulfuric acid with the concentration of 50% into the solid residue containing nickel and aluminum, stirring and reacting at 100 ℃ for 2.0h, and filtering to obtain an acidic solution containing nickel sulfate and aluminum sulfate. Finally, adding water to adjust the concentration of molybdenum oxide in the alkaline solution to be 20g/100mL and the concentration of aluminum oxide to be 15g/100 mL; water is added to adjust the concentration of nickel oxide in the acid solution to be 10g/100mL and the concentration of aluminum oxide to be 12g/100 mL.

8L of purified water was added to a 15L gelling tank and heated to 100 ℃. Adding sulfuric acid into the neutralization and gelling tank to adjust the pH value to 2.0, stabilizing for 5min, and then adding the alkaline solution to adjust the pH value to 10.0, and stabilizing for 5 min; and then adjusting the pH value to 2.0 by using the acidic solution, stabilizing for 5min, adjusting the pH value to 10.0 by using the alkaline solution, repeating for 6 times, adjusting the pH value to 8.0, aging at 100 ℃, transferring the mixed slurry into a high-pressure kettle, adding 25g of ammonium persulfate/sodium bisulfite, carrying out polymerization reaction at 200 ℃ for 2H, filtering, washing, drying at 130 ℃ to obtain a required catalyst precursor, mixing the catalyst precursor with an adhesive, forming, drying at 120 ℃, and roasting at 300 ℃ to obtain the hydrogenation catalyst H, wherein the properties of the hydrogenation catalyst H are shown in Table 2.

TABLE 1 hydrogenation catalyst Properties prepared in examples and comparative examples

As can be seen from the data in Table 1, the method of the present invention can prepare a hydrogenation catalyst with large specific surface area, pore volume and pore diameter under a lower temperature condition, and is very suitable for preparing a hydrogenation catalyst for heavy and poor raw materials.

Example 5

This example is a comparative test of the activity of the catalysts of examples 1, 2, 3, 4 and comparative examples 1, 2, 3, 4 on a 100mL fixed bed small scale hydrogenation unit, the feed mode being the bottom feed. The properties of the stock oils were evaluated as shown in Table 3; the evaluation conditions are shown in Table 4; the catalyst evaluation results are shown in Table 5.

TABLE 2 Properties of the feed oils

Table 3 evaluation of Process conditions

TABLE 4 catalyst combination evaluation results

It can be seen from the data in table 4 that the catalyst prepared by the method of the present invention can effectively improve the hydrogenation activity of the catalyst under the same process conditions.