CN112517022B

CN112517022B - Preparation method of hydrotreating catalyst

Info

Publication number: CN112517022B
Application number: CN201910875862.1A
Authority: CN
Inventors: 吕振辉; 朱慧红; 金浩; 刘璐; 杨涛; 杨光; 彭冲
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2019-09-17
Filing date: 2019-09-17
Publication date: 2023-02-03
Anticipated expiration: 2039-09-17
Also published as: CN112517022A

Abstract

The invention discloses a preparation method of a hydrotreating catalyst, which comprises the following steps: (1) Adding a certain amount of bottom water into a reaction container, heating to a gelling temperature, adding a certain amount of nano metal oxide particles, uniformly stirring, then adding an acidic salt solution containing a polymer monomer I and a basic salt solution containing a polymer monomer II in a concurrent flow manner, neutralizing and gelling for a period of time, and then aging; (2) And (3) transferring the aged material to a high-pressure reaction kettle, adding a certain amount of initiator, reacting for a period of time under certain temperature and pressure conditions, and filtering, drying and roasting the material at low temperature to obtain the hydrotreating catalyst. The method of the invention overcomes the problem that the catalyst is difficult to be vulcanized due to the aggregation of active metals in the process of preparing the bulk phase catalyst by a coprecipitation method, and the catalyst prepared by the method has good mechanical strength and pore distribution and is particularly suitable for the hydrogenation conversion process of heavy and residual oil.

Description

Preparation method of hydrotreating catalyst

Technical Field

The invention relates to a preparation method of a hydrotreating catalyst.

Background

The coprecipitation method is to add an alkali substance (precipitant) into an aqueous solution of a metal salt under stirring, and then to wash, filter, dry, mold and calcine the generated precipitate to obtain the catalyst and the carrier. However, most of the initial crystal nucleus in the coprecipitation method are silica gel, silica alumina gel and Fe (OH) ₃ 、AL(OH) ₃ The combined hydroxyl groups are multiple, the structure is complex, the molecular polarity is small, the directional arrangement is difficult, the directional rate is small, so the aggregation rate is far greater than the directional rate, and amorphous gel is easy to generateThe precipitate, which is used as a crystal nucleus, is difficult to perfect in crystal form after aging for a while, thereby resulting in low crystallinity. Secondly, the technology of preparing a bulk phase catalyst by a coprecipitation method generally achieves the transformation of a gamma-alumina crystalline phase through high-temperature roasting, so that a catalyst product has better strength, however, the high-temperature roasting easily causes the formation of nickel aluminate spinel and the aggregation of active metal, so that the interaction between the active metal and a carrier and the active metal is enhanced, the catalyst is difficult to sulfide, and the hydrogenation activity is obviously reduced.

CN106315642B relates to a preparation method of pseudoboehmite and a preparation method of gamma-alumina, the preparation method of the pseudoboehmite comprises the steps of contacting a sodium metaaluminate or sodium aluminate solution with a gas containing carbon dioxide, gelling in a continuous or intermittent manner, concentrating a mixture obtained after gelling, and then aging an obtained concentrated solution after adding water or without adding water. The method can easily obtain the gamma-alumina with the pore volume of more than 0.6 ml/g, but the roasting temperature of the method reaches 550-850 ℃, and the high roasting temperature causes certain loss of the pore structure.

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 preparation method of a hydrotreating catalyst. The method of the invention overcomes the problem that the catalyst is difficult to be vulcanized due to the aggregation of active metals in the process of preparing the bulk phase catalyst by a coprecipitation method, and the catalyst prepared by the method has good mechanical strength and pore distribution and is particularly suitable for the hydroconversion process of heavy residual oil.

The preparation method of the hydrotreating catalyst comprises the following steps:

(1) Adding a certain amount of bottom water into a reaction container, heating to a gelling temperature, adding a certain amount of nano metal oxide particles, uniformly stirring, then adding an acidic salt solution containing a polymer monomer I and a basic salt solution containing a polymer monomer II in a concurrent flow manner, neutralizing and gelling for a period of time, and then aging;

(2) And (3) transferring the aged material to a high-pressure reaction kettle, adding a certain amount of a copolymerization reaction initiator, reacting for a period of time under certain temperature and pressure conditions, and filtering, drying and roasting the material at low temperature to obtain the hydrotreating catalyst.

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

In the method of the present invention, the nano metal oxide in the step (1) may be one or more of nano magnesium oxide, nano titanium oxide, nano zirconium oxide, nano molybdenum oxide, nano nickel oxide, nano tungsten oxide, nano cobalt oxide, nano iron oxide, nano zinc oxide, etc., and preferably one or more of nano molybdenum oxide, nano nickel oxide, nano tungsten oxide, nano cobalt oxide and nano iron oxide. The nano metal oxide particles can be prepared by themselves according to the prior art or can be prepared by using a commercial product.

In the method, the adding amount of the nano metal oxide particles in the step (1) accounts for 0.1-1% of the weight of the catalyst, and preferably 0.1-0.5%.

In the method, the polymer monomer I in the step (1) 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, the polymer monomer II in the step (1) 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-new diamine, 1, 10-decamethylene diamine 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 acidic salt solution in the step (1) is a mixed solution of acidic aluminum salt and acidic active metal salt, wherein the acidic aluminum salt is AlCl ₃ 、Al ₂ (SO ₄ ) ₃ Or Al (NO) ₃ One or more, preferably Al ₂ (SO ₄ ) ₃ Concentration of the acidic aluminum salt aqueous solution is calculated as Al ₂ O ₃ The metal oxide is 10-100 g/100mL, the concentration of the acidic active metal solution is 10-30 g/100mL, and the metal oxide is taken as the basis; the flow rate of the acidic salt solution is 10-80 mL/min.

In the method, the alkaline salt solution in the step (1) is a mixed solution of alkaline aluminum salt and alkaline active metal salt, wherein the alkaline aluminum salt is NaAlO ₂ And/or KAlO ₂ Preferably NaAlO ₂ Concentration of alkali aluminate aqueous solution as Al ₂ O ₃ 10-100 g/100mL, the concentration of the alkaline active metal solution is 10-30 g/100mL, calculated by metal oxide(ii) a The flow rate of the alkaline salt solution is 10-80 mL/min.

In the method of the present invention, the active metal in the acidic active metal solution is selected from one or more of metal elements in group VIII and/or group VIB, preferably one or more of tungsten oxide, molybdenum oxide, cobalt oxide or nickel oxide. The preparation method of the acidic active metal solution belongs to the content well known to those skilled in the art, and is illustrated by taking the molybdenum-nickel-phosphorus aqueous solution as an example, and the preparation method is as follows: putting molybdenum oxide and basic nickel carbonate into a multi-mouth flask, adding a certain amount of deionized water, stirring until substances in the flask are in a slurry state, slowly adding phosphoric acid, slowly heating after the initial reaction, keeping the temperature of the solution at 90-110 ℃ for 1-3 hours, filtering the obtained solution while the solution is hot after stopping heating, and then adding phosphoric acid to adjust the pH value of the solution to 1.0-4.0 to obtain the molybdenum-nickel-phosphorus aqueous solution.

In the method of the present invention, the active metal in the alkaline active metal solution is selected from one or more of group VIII and/or group VIB metal elements, preferably one or more of tungsten oxide, molybdenum oxide, cobalt oxide or nickel oxide. The preparation method of the alkaline active metal solution belongs to the content well known to those skilled in the art, and is illustrated by taking an aqueous solution of molybdenum-nickel-ammonium as an example, and the preparation method is as follows: putting ammonium heptamolybdate into a multi-mouth flask, adding a certain amount of deionized water, stirring until substances in the flask are in a slurry state, slowly adding ammonia water, slowly heating after the initial reaction, keeping the temperature of the solution at 90-110 ℃ for 1-3 hours, stopping heating, adding needed nickel nitrate while hot, dissolving, and filtering the obtained solution to obtain the molybdenum-nickel-ammonium aqueous solution.

In the method of the invention, the pH value adjustment in the step (1) generally adopts acidic salt solution or alkaline salt solution; the neutralization gelling time is 0.5-3 h, and the reaction pH is adjusted to 7.0-9.0; the aging temperature is 60-100 ℃, and the aging time is 1-5 hours.

In the method of the invention, the initiator in the step (2) can be selected from peroxide initiators, azo initiators, redox initiators and the like according to the reaction requirements, wherein the peroxide initiators are divided into organic peroxide initiators and inorganic peroxide initiators. 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 (t-butyl peroxybenzoate, t-butyl peroxypivalate); (5) Ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide); (6) Dicarbonate peroxides (diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate). The inorganic peroxide compound can be selected from persulfate salts, 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 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, cumene hydroperoxide/tetraethylene imine, and the like. Tert-butyl hydroperoxide/sodium metabisulphite is preferred.

In the method, the solid-liquid separation process in the step (2) can adopt conventional filtration, centrifugation and other modes, and the solid-liquid separation process washes the materials according to the requirement to remove impurities such as salts and the like.

In the method of the invention, the drying conditions in the step (2) are as follows: the drying temperature is 100-200 ℃, and the drying time is 1-5 h. The roasting conditions are as follows: the roasting temperature is 300-350 ℃, and the roasting time is 2-5 hours. Calcination is carried out in an oxygen-containing atmosphere, typically with an oxygen content greater than 10v%, preferably air.

In the method, the forming process in the step (2) can adopt extrusion forming, and the catalyst with different shapes, such as a cylinder shape, a clover shape or a clover shape, can be prepared according to the requirement. The dried alumina precursor can also be directly roasted to obtain the spherical catalyst.

The hydrotreating catalyst prepared by the method of the invention has the following properties: the specific surface area is 200 to 300m ² The pore volume is 0.90-1.20 mL/g ^-1 (ii) a The pore diameter can be several 50-150 nm, wherein the pore distribution of less than 50nm accounts for 1-5% of the total pore volume, the pore distribution of 50-100 nm accounts for 80-85% of the total pore volume, and the pore distribution of more than 100nm accounts for 10-15% of the total pore volume; the bulk density is 0.55-1.15 g/mL; the abrasion is 0.1 to 0.5 percent; the support strength is from 100 to 350N/mm, preferably from 150 to 300N/mm.

The hydrogenation catalyst comprises an alumina carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, preferably 1.0wt% -5.0 wt%, the VIB group metal is 5wt% -25 wt%, preferably 10wt% -20 wt%, and the balance is an alumina carrier. The VIII group metal is selected from cobalt and/or nickel, and the VIB group metal is selected from molybdenum or tungsten.

The hydrotreating catalyst prepared by the method is suitable for the hydrogenation process of oil products such as residual oil, wax oil, coal tar, coal liquefaction oil, diesel oil, gasoline and the like, and is particularly suitable for the hydrogenation conversion process of heavy residual oil.

Compared with the prior art, the preparation method of the hydrogenation catalyst provided by the invention has the following advantages:

1. the method takes the active metal nano particles as the seed crystals, the seed crystals have small molecules, large polarity and larger directional speed, and are easy to form crystal form precipitates or colloidal particles with crystal structures, so that the crystal grows directionally and the crystallinity of the crystal is high, the phase inversion temperature of a precursor converted into gamma-alumina 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 the requirements of various hydrogenation catalyst products can be well met;

2. the method reduces the phenomena of inactive nickel aluminate spinel and active metal agglomeration by low-temperature roasting, thereby weakening the interaction between active metal and carrier and active metal, enabling the catalyst to be easier to be vulcanized into a high-activity II-type active phase, having higher activity and higher activity, effectively improving the surface acidity of the catalyst, slowing down the inactivation speed of the catalyst in the heavy oil hydrotreating process, and being very suitable for being used as a high-activity and high-stability hydrotreating catalyst;

3. in the method, the polymer monomer is used as the polar dispersant, and in the preparation process of the catalyst, due to the polar dispersion effect and the chelation effect of the polymer monomer, on one hand, the agglomeration among catalyst particles can be reduced, so that the sizes of seed crystals are more concentrated, and the particle crystallinity is higher; on the other hand, the active metal and the polymerization monomer wrap the active metal through chelation, and the active metal can be exposed in a surface phase after roasting, so that the surface utilization rate of the active metal is improved, and the activity of the catalyst is improved;

4. in the method, the continuous through-channels are formed by copolymerization of different polymer monomers, so that the problems of difficulty in passing the poor-quality raw material macromolecular colloid and asphaltene micelle through the channels and high diffusion resistance and reaction pressure in the prior art are solved, and the inactivation speed of the catalyst in the heavy oil hydrotreating process is slowed down;

5. in the method, in the preparation process of the catalyst, the pore structure of the catalyst can be effectively improved by controlling the polymerization degree of the polymerization reaction, the uneven distribution of micropores, mesopores and macropores of the catalyst can be solved, the occurrence of side reactions is reduced, and the selectivity is improved.

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 is measured by inductively coupled plasma atomic emission spectrometry (ICP-AES). The strength of the alumina carrier was measured using 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 in the invention is 2.0 to 6.0, preferably 2.0 to 5.0, and the MoO of the surface-phase active metal component ₃ With the bulk active metal component MoO ₃ The weight content ratio of (A) is (A) 2.0 to (B) 8.0, preferably (B) 2.0.

In the method of the present invention, the nano metal oxide is selected from Shanghai Chaowei nano technology Co., ltd. The properties of the nano metal oxide particles are shown in Table 1 below.

TABLE 1 nanometer Metal oxide Properties

	CoO	NiO	MoO ₃	WO ₃
					Content of%	99.9	99.9	99.9	99.9
Average particle diameter, nm	30	30	50	40
					Specific surface area, m ² /g	40～70	50～100	30～100	20～50
Bulk density, g/cm ³	0.57	0.80	0.91	1.5
					True density, g/cm ³	6.11	6.67	6.79	7.16

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

Adding 3L of bottom water into a 6L reaction kettle, heating to 70 ℃, adding 10g of nano-metal molybdenum oxide, and uniformly stirring; then, a mixed solution of aluminum sulfate with a concentration of 50g/100mL containing 10g/100mL of ethylene glycol and 15g/100mL of Mo-Ni acidic active metal solution is added dropwise at a flow rate of 20mL/min, and simultaneously, a mixed solution of sodium metaaluminate with a concentration of 100g/100mL containing 10g/100mL of ethylenediamine and 20g/100mL of Mo-Ni alkaline active metal is added dropwise, the pH value is adjusted to 7.5, the mixed solution is aged at 70 ℃ for 2h after being neutralized into gel for 1h, then the mixed slurry is transferred to an autoclave, 20g of sodium persulfate is added, the polymerization reaction is carried out at 200 ℃ for 1h, and after filtration and washing, QA is dried at 100 ℃ to obtain the required catalyst precursor, and QA is calcined at 300 ℃ to obtain the microspherical hydrogenation catalyst A, wherein the properties of the catalyst are shown in Table 2.

Example 2

Adding 5L of bottom water into an 8L reaction kettle, heating to 80 ℃, adding 8g of nano-metal molybdenum oxide, and uniformly stirring; then, a mixed solution of aluminum sulfate with the concentration of 100g/100mL and containing 15g/100mL of glycol and 10g/100mL of Mo-Ni acid active metal solution is dripped at the flow rate of 35mL/min, a mixed solution of sodium metaaluminate with the concentration of 50g/100mL and containing 10g/100mL of glutamic acid and 10g/100mL of Mo-Ni alkali active metal solution is dripped at the same time, the pH value is adjusted to be 8.0, the mixed solution is aged at 80 ℃ for 2h after being neutralized into gel, then the mixed slurry is transferred into an autoclave, 15g of potassium persulfate is added, polymerization reaction is carried out at 250 ℃ for 2h, filtration and washing are carried out, a required catalyst precursor QB is obtained after drying at 100 ℃, and then, a microspherical hydrogenation catalyst B is obtained after roasting at 350 ℃, and the properties of the microspherical hydrogenation catalyst B are shown in Table 2.

Example 3

Adding 2L of bottom water into a 4L reaction kettle, heating to 90 ℃, adding 5g of nano-metal molybdenum oxide, and uniformly stirring; then, a mixed solution of aluminum sulfate containing 10g/100mL of oxalic acid and having a concentration of 100g/100mL and 10g/100mL of Mo-Ni acidic active metal solution is added dropwise at a flow rate of 40mL/min, and a mixed solution of sodium metaaluminate containing 10g/100mL1, 6-hexamethylenediamine and having a concentration of 50g/100mL and 10g/100mL of Mo-Ni alkaline active metal solution is added dropwise at the same time, the pH value is adjusted to 7.0, the mixed solution is aged at 80 ℃ for 2 hours after being neutralized to form colloid, then the mixed slurry is transferred to an autoclave, 20g of azobisisobutyronitrile is added, the mixture is polymerized at 350 ℃ for 2 hours, filtered and washed, dried at 100 ℃ to obtain a required catalyst precursor QC, and then calcined at 320 ℃ to obtain the microspherical hydrogenation catalyst C, wherein the properties of the catalyst C are shown in Table 2.

Example 4

Adding 5L of bottom water into an 8L reaction kettle, heating to 100 ℃, adding 15g of nano-metal molybdenum oxide, and uniformly stirring; then, a mixed solution of aluminum sulfate with a concentration of 80g/100mL containing 15g/100mL of oxalic acid and 15g/100mL of Mo-Ni acidic active metal solution is dripped at a flow rate of 50mL/min, and a mixed solution of sodium metaaluminate with a concentration of 80g/100mL containing 17g/100mL of glycine and 15g/100mL of Mo-Ni alkaline active metal solution is simultaneously dripped, the pH value is adjusted to be 7.5, the mixed solution is aged at 90 ℃ for 1.5h after being neutralized into gel, then the mixed slurry is transferred to an autoclave, 30g of ammonium persulfate/sodium bisulfite is added, the polymerization reaction is carried out at 350 ℃ for 2.5h, the filtration and washing are carried out, the drying is carried out at 100 ℃ to obtain a required catalyst precursor QD, and the sintering is carried out at 320 ℃ to obtain a microspherical hydrogenation catalyst D, wherein the properties of the catalyst D are shown in Table 2.

Example 5

The alumina precursors QA, QB, QC and QD of examples 1, 2, 3 and 4 were added with a certain amount of binder to form a plastic mass, which was then extruded in a plodder, dried at 120 ℃ and calcined at 300 ℃ to obtain cylindrical hydrogenation catalysts A-1,B-1,C-1 and D-1, the properties of which are shown in Table 2.

Comparative example 1

Adding 5L of bottom water into a 10L reaction kettle, heating to 100 ℃, adding 15g of nano-metal molybdenum oxide, and uniformly stirring; then, a mixed solution of aluminum sulfate with the concentration of 80g/100mL and Mo-Ni acidic active metal solution with the concentration of 15g/100mL is dripped at the flow rate of 50mL/min, a mixed solution of sodium metaaluminate with the concentration of 80g/100mL and Mo-Ni alkaline active metal solution with the concentration of 15g/100mL is dripped at the same time, the pH value of neutralization is adjusted to be 7.5, the mixed solution is aged for 1.5h at the temperature of 90 ℃ after being neutralized into gel, a required catalyst precursor QE is obtained after filtering and washing and drying at the temperature of 100 ℃, and then the microspherical hydrogenation catalyst E is obtained after roasting at the temperature of 320 ℃, wherein the properties of the microspherical hydrogenation catalyst E are shown in Table 2.

Comparative example 2

The catalyst precursor QE of comparative example 1 was added with a certain binder to form a plastic mass, which was extruded in an extruder, dried at 180 ℃ and calcined at 300 ℃ to obtain a cylindrical hydrogenation catalyst E-1.

Comparative example 3

The same as example 1 except that the calcination temperature was 600 ℃ and the hydrogenation catalyst was designated by the reference numeral F.

Comparative example 4

The same as example 1, except that the nano-metal molybdenum oxide was not added and the hydrogenation catalyst was labeled G.

Comparative example 5

The same as example 1, except that 100g of nano-metal molybdenum oxide was added and the hydrogenation catalyst was numbered H.

TABLE 2 Properties of hydrogenation catalysts 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 the condition of low temperature, and the catalyst has the advantages of high strength, low abrasion and high dispersion degree of the active metal surface phase.

Example 6

This example is a comparative test of the activity of the catalysts of examples 1, 2, 3, 4, 5 and comparative examples 1, 2, 3, 4, 5 on a 100ml fixed bed small scale hydrogenation unit, the feed mode being the following 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 3 Properties of the feed oils

Table 4 evaluation of process conditions

TABLE 5 evaluation results of catalyst combinations

Claims

1. A preparation method of a hydrotreating catalyst is characterized by comprising the following steps: (1) Adding a certain amount of bottom water into a reaction container, heating to a gelling temperature, adding a certain amount of nano metal oxide particles, uniformly stirring, then adding an acidic salt solution containing a polymer monomer I and a basic salt solution containing a polymer monomer II in a concurrent flow manner, neutralizing and gelling for a period of time, and then aging; (2) Transferring the aged material to a high-pressure reaction kettle, adding a certain amount of initiator, reacting for a period of time under certain temperature and pressure conditions, and filtering, drying and roasting the material at low temperature to obtain a hydrotreating catalyst; wherein the polymer monomer I in the step (1) is organic alcohol and/or amino acid I; the polymer monomer II in the step (1) is organic amine and/or amino acid II; the nano metal oxide is one or more of nano molybdenum oxide, nano nickel oxide, nano tungsten oxide, nano cobalt oxide and nano iron oxide, and the addition amount of the nano metal oxide particles accounts for 0.1-1% of the weight of the catalyst;

the resulting catalyst had the following properties: the specific surface area is 200 to 300m ² The pore volume is 0.90-1.20 mL/g ^-1 (ii) a The pore diameter can be several 50-150 nm, wherein the pore distribution of less than 50nm accounts for 1-5% of the total pore volume, the pore distribution of 50-100 nm accounts for 80-85% of the total pore volume, and the pore distribution of more than 100nm accounts for 10-15% of the total pore volume; the bulk density is 0.55-1.15 g/mL; the abrasion is 0.1 to 0.5 percent; the strength of the carrier is 100-350N/mm.

2. The method of claim 1, wherein: the gelling temperature in the step (1) is 50-100 ℃.

3. The method of claim 1, wherein: the organic alcohol in the step (1) 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.

4. The method of claim 1, wherein: the amino acid I in the step (1) 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.

5. The method of claim 1, wherein: the addition amount of the polymer monomer I in the step (1) 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.

6. The method of claim 1, wherein: the organic amine in the step (1) is one or more of 2-methyl-1,5-pentanediamine 1,9-nonanediamine, ethylenediamine, 1,6-hexanediamine, 2-methyl-1,8-octanediamine and 1, 10-decanediamine or urea.

7. The method of claim 1, wherein: the amino acid II in the step (1) is one or more of arginine, lysine, histidine, glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine or threonine.

8. The method of claim 1, wherein: the addition amount of the polymer monomer II in the step (1) 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.

9. The method of claim 1, wherein: the acidic salt solution in the step (1) is a mixed solution of acidic aluminum salt and acidic active metal salt, wherein the acidic aluminum salt is AlCl ₃ 、Al ₂ (SO ₄ ) ₃ Or Al (NO) ₃ ) ₃ One or more of the acidic aluminum salt aqueous solution is in Al concentration ₂ O ₃ The metal oxide concentration is 10-100 g/100mL, and the concentration of the acidic active metal solution is 10-30 g/100mL, calculated by the metal oxide.

10. The method of claim 1, wherein the first and second light sources are selected from the group consisting of,the method is characterized in that: the alkaline salt solution in the step (1) is a mixed solution of alkaline aluminum salt and alkaline active metal salt, wherein the alkaline aluminum salt is NaAlO ₂ And/or KAlO ₂ Concentration of alkali aluminum salt aqueous solution as Al ₂ O ₃ The concentration of the alkaline active metal solution is 10 to 100g/100mL, and the concentration of the alkaline active metal solution is 10 to 30g/100mL calculated by metal oxide.

11. The method of claim 1, wherein: the active metal in the acidic active metal solution is selected from one or more of VIII group and/or VIB group metal elements.

12. The method of claim 11, wherein: the active metal in the acidic active metal solution is selected from VIII group and/or VIB group metal elements and is selected from one or more of tungsten oxide, molybdenum oxide, cobalt oxide or nickel oxide.

13. The method of claim 1, wherein: the active metal in the alkaline active metal solution is selected from one or more of VIII group and/or VIB group metal elements.

14. The method of claim 13, wherein: the active metal in the alkaline active metal solution is selected from VIII group and/or VIB group metal elements and is selected from one or more of tungsten oxide, molybdenum oxide, cobalt oxide and nickel oxide.

15. The method of claim 1, wherein: the neutralization gelling time is 0.5-3 h, and the reaction pH is adjusted to 7.0-9.0; the aging temperature is 60-100 ℃, and the aging time is 1-5 hours.

16. The method of claim 1, wherein: the initiator in the step (2) is a peroxide initiator, an azo initiator or a redox initiator.

17. The method of claim 16, wherein: the peroxide initiator in the step (2) 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.

18. The method of claim 16, wherein: the azo initiator in the step (2) is azobisisobutyronitrile or azobisisoheptonitrile.

19. The method of claim 16, wherein: the redox initiator in the step (2) 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/rongalite, 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/tetraethenimine.

20. The method of claim 1, wherein: the roasting conditions in the step (2) are as follows: the roasting temperature is 300-350 ℃, the roasting time is 2-5 hours, and the roasting is carried out in an oxygen-containing atmosphere.

21. A hydroprocessing catalyst prepared by the process of any one of claims 1 to 20, characterized by the following properties: the strength of the carrier is 150-300N/mm.

22. A hydroprocessing catalyst prepared by the method according to any one of claims 1 to 20, characterized in that: the hydrogenation catalyst comprises an alumina carrier and active metals, wherein the active metals are selected from one or more of VIII group and/or VIB group metal elements; based on the weight of the catalyst, the active metal is calculated by oxide, the VIII group metal is 1wt% -9 wt%, the VIB group metal is 5wt% -25 wt%, and the balance is an alumina carrier; the VIII group metal is selected from cobalt and/or nickel, and the VIB group metal is selected from molybdenum or tungsten.