CN116060059B - Hydrodesulfurization catalyst and preparation method and application thereof - Google Patents

Hydrodesulfurization catalyst and preparation method and application thereof Download PDF

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CN116060059B
CN116060059B CN202111279340.9A CN202111279340A CN116060059B CN 116060059 B CN116060059 B CN 116060059B CN 202111279340 A CN202111279340 A CN 202111279340A CN 116060059 B CN116060059 B CN 116060059B
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hydrodesulfurization catalyst
solution
drying
active metal
mass
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CN116060059A (en
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刘文洁
隋宝宽
穆福军
袁胜华
耿新国
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a hydrodesulfurization catalyst and a preparation method and application thereof. The preparation method comprises the following steps: (1) Mixing biomass raw materials with asphaltene powder, high polymer and inorganic matters containing potassium to obtain a mixture, kneading, forming and then carrying out heat treatment; (2) Carbonizing the material obtained in the step (1), and then carrying out steam treatment; (3) Repeating the step (2) for 1-5 times to obtain an intermediate, washing and drying; (4) Spraying and soaking the carrier obtained in the step (3) with a regulator, and drying to obtain a carbon carrier; (5) preparing microemulsion containing active metal; (6) And (3) dipping the carbon carrier obtained in the step (4) into the microemulsion obtained in the step (5), and then drying and roasting to obtain the hydrodesulfurization catalyst. The hydrodesulfurization catalyst prepared by the invention has proper pore property and surface acid property, has better carbon deposit resistance, and has excellent hydrodesulfurization performance in residual oil hydrogenation reaction.

Description

Hydrodesulfurization catalyst and preparation method and application thereof
Technical Field
The invention relates to a hydrodesulfurization catalyst, a preparation method and application thereof.
Background
Residuum is the heaviest fraction of petroleum, and the proportion of residuum in petroleum is usually greater than 50%. Solves the problem of light processing of a large amount of residual oil, and is a technical problem which is faced by refineries for improving comprehensive economic benefits. The residuum lightening process mainly adopts two methods of hydrogenation and decarbonization to improve the H/C ratio, wherein the decarbonization technology is represented by a coking scheme. Although coking routes are accepted by oil refining enterprises for a long time, more and more users select hydrogenation routes due to the defects of low liquid yield, poor product quality and the like.
In the processing process of the residual oil, the hydrogenation process can improve the lightening degree of the residual oil on one hand and better improve the product quality on the other hand. Particularly for heavy raw materials with high sulfur, nitrogen and heavy metal content and poor quality, the hydrotreating process is an indispensable processing scheme. Wherein, the fixed bed residuum hydrogenation is still a main trend of residuum hydrogenation technology development in a quite long time due to the advantages of mature technical level, low investment in device construction and the like. The residual oil hydrodesulfurization catalyst is positioned at the rear section of the catalyst system and is mainly used for deep desulfurization and moderate hydroconversion. Typical hydrodesulfurization catalysts generally use alumina as a carrier, tungsten and molybdenum as main active metals, and cobalt and nickel as auxiliary active components. The catalyst taking alumina as the carrier is roasted after being loaded with active metal, and part of active metal and the carrier act to generate spinel structure substances in the roasting process, so that the utilization rate of the active metal is reduced.
CN103657736a discloses an active carbon/alumina composite catalyst carrier, its preparation and application, the method uses 20% -35% hydrochloric acid, and circularly washes in boiling state, the mass ratio of hydrochloric acid and active carbon is (5-20): 1, a step of; oxidizing with 10-50% nitric acid at room temperature, wherein the mass ratio of the oxidant to the active carbon is (20-40): 1, a step of; kneading the activated carbon, the alumina and the auxiliary agent into a cake shape under a kneader; extruding the kneaded cake by a strip extruder to form; and drying the extruded carrier, and roasting in a nitrogen protective atmosphere to prepare the active carbon/alumina composite carrier. The composite carrier prepared by the method can be used as a residual oil hydrodemetallization catalyst carrier for fixed bed residual oil hydrogenation, but the residual oil hydrodemetallization catalyst carrier prepared by adopting active carbon and alumina in a composite way is mentioned in the method, so that the catalyst is prepared, the catalyst prepared by the method still contains alumina, and part of active metal and the carrier act to generate spinel structure substances after the catalyst is roasted, so that the utilization rate of the active metal is reduced.
CN111195525A discloses a residual oil hydrodesulfurization catalyst using active carbon as carrier and its preparation method. The method comprises the following steps: firstly preparing an active carbon carrier, washing active carbon particles to be neutral, then adopting an oven to dry the active carbon particles at 80-120 ℃, and treating the active carbon particles for 3-20 hours at a high temperature of 1800-2000 ℃ under the protection of inert gas, so that the active carbon is fully graphitized to ensure that the hardness of the active carbon is more than 15N/mm. Then acidizing, treating at 300-500 ℃ in the atmosphere of mixed gas containing oxygen and inert gas to obtain an active carbon carrier; and loading active components, preparing an impregnating solution by adopting soluble salts of nickel, molybdenum and phosphorus, impregnating an active carbon carrier in the impregnating solution, drying and roasting to obtain the residual oil hydrodesulfurization catalyst. The catalyst needs to be treated at the temperature of more than 1000 ℃ in the preparation process, and has high energy consumption.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a hydrodesulfurization catalyst and a preparation method and application thereof. The hydrodesulfurization catalyst prepared by the method has proper pore properties and surface acid properties, has better carbon deposit resistance, and has excellent hydrodesulfurization performance in residual oil hydrogenation reaction.
The invention provides a preparation method of a hydrodesulfurization catalyst, which comprises the following steps:
(1) Mixing biomass raw materials with asphaltene powder, high polymer and inorganic matters containing potassium to obtain a mixture, kneading, forming and then carrying out heat treatment;
(2) Carbonizing the material obtained in the step (1), and then carrying out steam treatment;
(3) Repeating the step (2) for 1-5 times to obtain an intermediate, washing and drying;
(4) Spraying and soaking the carrier obtained in the step (3) with a regulator, and drying to obtain a carbon carrier;
(5) Preparing microemulsion containing active metal;
(6) And (3) dipping the carbon carrier obtained in the step (4) into the microemulsion obtained in the step (5), and then drying and roasting to obtain the hydrodesulfurization catalyst.
Further, in the step (1), the biomass raw material is one or more of wood, straw, shell, starch and bamboo. The biomass raw material is subjected to drying and crushing treatment, and the drying conditions are as follows: drying at 100-240 deg.c for 4-10 hr to obtain crushed wood chip of 100-400 mesh, preferably 200-400 mesh.
Further, in the step (1), the polymer is one or more of cellulose and resin, preferably one or more of hydroxypropyl cellulose, methyl cellulose, phenolic resin and ethylene-vinyl acetate resin.
Further, in the step (1), the inorganic matter containing potassium is one or more of potassium carbonate, potassium hydroxide and potassium oxide.
Further, in the step (1), the mass ratio of the biomass in the mixture obtained in the step (1) is 70% -90%, the mass ratio of the asphaltene in the mixture obtained in the step (1) is 1% -10%, and the mass ratio of the high polymer in the mixture obtained in the step (1) is 8% -20%. The addition amount of the potassium-containing inorganic matters meets the requirement that the addition mass of potassium elements accounts for 0.03-3.00% of the mass of the mixture.
Further, the heat treatment condition in the step (1) is a programmed heating heat treatment, the heating rate is 20-80 ℃/h, and the temperature is kept between 150 ℃ and 350 ℃ for 1-8.0 h.
Further, in the step (2), the condition of the carbonization treatment is: treating under protective gas at 300-800 deg.c, preferably 450-700 deg.c for 1-8 hr; the shielding gas is inert gas and/or nitrogen, wherein the inert gas is one or more of argon and helium.
Further, in the step (2), the conditions of the steam treatment are as follows: the temperature is 150-700 ℃, the time is 1-6 h, and the preferable temperature is 350-650 ℃.
Further, in step (3), the washing is water washing, wherein the water washing is performed by conventional means in the art, and the drying conditions are as follows: drying for 4-10 h under the atmosphere of inert gas and/or nitrogen at 120-200 ℃.
Further, in the step (4), the regulator is a solution containing one or more of fluorine, phosphorus, silicon or boron, or a solution selected from soluble organic acid and/or organic alcohol, and the organic acid and/or organic alcohol is preferably at least one of citric acid, ethylene glycol and polyethylene glycol. Wherein, when the regulator is a solution of one or more of fluorine, phosphorus, silicon or boron contained, the added mass of the one or more of fluorine, phosphorus, silicon or boron is 1.0-10.0% of the mass of the regulator; when the regulator is a solution of a soluble organic acid and/or organic alcohol, the mass concentration of the solution is 1.0wt% to 20.0wt%. The fluorine source can be selected from hydrofluoric acid, the phosphorus source can be selected from phosphoric acid, and the boron source can be selected from boric acid. The amount of solvent sprayed is the amount of solution required for saturated impregnation.
Further, in the step (4), the spray-immersed product is dried for 5 to 12 hours at 60 to 180 ℃ under the atmosphere of inert gas and/or nitrogen.
Further, in step (5), the active metal-containing microemulsion is prepared from an active metal solution and an emulsifier. Wherein the active metal solution is a molybdenum nickel phosphorus solution, the content of molybdenum oxide in the solution is 10.0-45.0 g/100mL, the content of nickel oxide is 1.0-10.0 g/100mL, and the content of phosphorus is 0.1-4.5 g/100mL.
Further, in the step (5), the emulsifier is a nonionic emulsifier, preferably one or more selected from polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide block copolymer, polyoxyethylene ester, polyol fatty acid ester, polyvinyl alcohol and polysorbate. The addition amount of the emulsifier is 1-20% of the volume of the active metal solution in the step (5).
Further, in the step (6), the carbon carrier obtained in the step (4) is immersed in the microemulsion containing the active metal component obtained in the step (5), the immersion method adopts a saturated immersion method or a supersaturation immersion method, preferably, the amount of the immersion solution containing the active metal is 100% -150% of the saturated water absorption amount of the carbon carrier obtained in the step (4), the immersion time is 2-6 hours, preferably, after the immersion, ultrasonic treatment is adopted, and the conditions of the ultrasonic treatment are as follows: the ultrasonic frequency is 10-80 kHz, preferably 20-60 kHz, and the time is 2-8 hours.
Further, in the step (6), the drying condition is that the drying is carried out for 2 to 15 hours at 80 to 150 ℃ under the atmosphere of inert gas and/or nitrogen. The roasting conditions are as follows: roasting for 2-5 h at 300-600 ℃ under inert gas and/or nitrogen atmosphere.
In a second aspect, the present invention provides a hydrodesulphurisation catalyst obtainable by the above process.
Further, the hydrodesulfurization catalyst comprises molybdenum oxide, nickel oxide and a carrier; wherein, the mass content of the molybdenum oxide is 5 to 28.0 percent, and the mass content of the nickel oxide is 1 to 6.5 percent.
Further, the hydrodesulfurization catalyst also comprises phosphorus element, and the mass content of the phosphorus element is 0.4-3.0%.
Further, the total acid amount of the hydrodesulfurization catalyst is 0.375mmol/g to 0.525mmol/g.
Further, the hydrodesulfurization catalyst has an average pore diameter of 11.0nm to 15.0nm, preferably 11.5nm to 13.0nm.
Further, the specific surface area of the hydrodesulfurization catalyst is 225m 2/g～300m2/g.
Further, the pore volume of the hydrodesulfurization catalyst is 0.55 mL/g-0.70 mL/g.
Further, the side pressure strength of the hydrodesulfurization catalyst is more than 16N/mm, preferably 18N/mm to 25N/mm.
In a third aspect, the present invention provides the use of the above hydrodesulphurisation catalyst in residuum hydrogenation processes.
Further, the residuum and hydrogen-containing gas are contacted and reacted under hydrogenation reaction conditions in the presence of the above-described hydrodesulfurization catalyst or hydrodesulfurization catalyst obtained according to the above-described production method.
In the residuum hydrogenation process, the residuum material is selected from one of atmospheric residuum, vacuum residuum and high-temperature coal tar.
In the residuum hydrogenation process, the residuum hydrogenation operating conditions are as follows: the reaction pressure is 8.0-20.0 MPa, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.1-3.0 h -1, and the hydrogen-oil volume ratio is 100-1000.
Compared with the prior art, the invention has the following advantages:
(1) The method adopts biomass raw materials, asphaltene, high polymer and potassium salt as carbonization raw materials, is easy to control the pore size distribution of the carrier and improves the specific surface area of the carrier. Meanwhile, the carbonized raw material is alternately treated by adopting the shielding gas and the water vapor, so that the addition amount of potassium salt in the carbon carrier is reduced, and the pore diameter of the prepared carrier is easy to control.
(2) Asphaltene is added into carbonized raw materials, a small amount of hetero atoms are introduced, and the acidity of the carbon carrier is primarily regulated. The preparation method comprises the steps of spraying and dipping a regulator on a carbon carrier before dipping active metal, and subsequently dipping the carbon carrier by adopting microemulsion containing the active metal, wherein the catalyst has proper surface acid property through the synergistic effect of the steps, and the prepared catalyst has better deep desulfurization performance and certain anti-carbon deposition performance.
(3) The hydrodesulfurization catalyst prepared by the method has proper surface acid property and proper pore diameter, so that the catalyst has better carbon deposit resistance and good desulfurization hydrogenation performance.
Detailed Description
The technical scheme and effect of the present invention are further described below by examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
In the present invention, the total acid amount on the surface of the catalysts of the examples and comparative examples was measured by using a chemical adsorption apparatus of the American Michael type Micromeritics TriStar 2920; the specific surface area, pore volume and pore diameter of the catalysts of the examples and comparative examples were measured using a physical adsorption analyzer of a U.S. microphone Micromeritics TriStar 2420; the contents of the metal elements in the solutions and catalysts in the examples and comparative examples were analyzed by an inorganic method.
In the invention, the pressure measurement intensity is tested by adopting a ZQJ-III intelligent particle intensity tester manufactured by Dalian Chi taking tester, and the average value of the side pressure intensity of ten crushed carriers is tested.
The technical scheme and technical effects of the present invention will be further described with reference to the following examples, but are not limited thereto.
Example 1
(1) Drying Phyllostachys Pubescens raw material at 180deg.C for 4 hr, and pulverizing into 300 mesh powder; 880g of moso bamboo powder, 20g of asphaltene powder, 100g of hydroxypropyl cellulose and 5g of potassium hydroxide are respectively weighed, mixed and kneaded, and molded; heating to 270 ℃ at a heating rate of 30 ℃/h, and performing heat treatment for 3h at 270 ℃; then carbonizing for 4 hours in nitrogen atmosphere at 550 ℃, then carrying out steam treatment on the carbonized material at 550 ℃ for 4 hours, and repeating the carbonization and steam treatment for 2 times, namely carrying out the carbonization and steam treatment steps for 3 times respectively, so as to obtain an intermediate; the obtained intermediate is dried for 6 hours at 120 ℃ in nitrogen atmosphere after being subjected to water purification washing treatment, and a carbon carrier is obtained;
(2) Saturated spraying and soaking the carbon carrier with regulator containing ethylene glycol 5%, and drying at 100deg.C under nitrogen atmosphere for 4 hr to obtain modified carbon carrier;
(3) Preparing a molybdenum-nickel-phosphorus solution, wherein the content of molybdenum oxide in the solution is 18.3g/100mL, the content of nickel oxide is 4.2g/100mL, and the content of phosphorus is 1.8g/100mL. 15g of polysorbate 80 was added to 300mL of the molybdenum nickel phosphorus solution to prepare a microemulsion containing the active metal.
(4) The carbon carrier is impregnated for 2 hours according to the supersaturation of 110 percent of the saturated water absorption capacity of the carbon carrier, the ultrasonic wave (the ultrasonic frequency is 30 kHz) is carried out for 3 hours after the impregnation, the carbon carrier is dried for 3 hours at 120 ℃ under the nitrogen atmosphere, and then the carbon carrier is roasted for 3 hours at 500 ℃ under the nitrogen atmosphere, so that the hydrodesulfurization catalyst A of the invention is prepared.
Example 2
The hydrodesulfurization catalyst B of the present invention was prepared by separately weighing 800g of coconut shell powder, 50g of asphaltene powder, 150g of hydroxypropyl cellulose and 5g of potassium hydroxide and mixing them, instead of 880g of moso bamboo powder, 20g of asphaltene powder, 100g of hydroxypropyl cellulose and 5g of potassium hydroxide, under the same conditions as in example 1.
Example 3
The hydrodesulfurization catalyst C of the present invention was produced as in example 1 except that the carbonization treatment and the steam treatment were each conducted 4 times instead of 3 times, and the other conditions were unchanged.
Example 4
The hydrodesulfurization catalyst D of the invention was prepared as in example 1 except that the 5% by weight of the modifier containing boric acid was saturated spray-impregnated instead of the 5% by weight of the modifier containing ethylene glycol before the impregnation of the active metal, and the other conditions were unchanged.
Example 5
The hydrodesulfurization catalyst E of the invention was prepared as in example 1 except that 20g polysorbate 80 was used instead of 15g polysorbate 80 in 300mL molybdenum nickel phosphorus solution to produce an active metal containing microemulsion under otherwise unchanged conditions.
Comparative example 1
The hydrodesulfurization catalyst F was prepared as in example 1 except that the carbon support was not impregnated with the regulator, but only with the common molybdenum-nickel-phosphorus solution, without adding the emulsifier, and without changing other conditions.
Comparative example 2
The technical grade pseudo-boehmite, 2wt% acetic acid and 2wt% sesbania powder are mixed, molded, dried at 130 ℃ for 3 hours and baked at 750 ℃ for 3 hours to prepare an alumina carrier (carrier liquid absorption rate is 0.87), the carrier is saturated and immersed into an impregnating solution containing molybdenum and nickel (wherein the content of the molybdenum oxide is 22.5G/100mL, the content of the nickel oxide is 5.2G/100mL, and the content of the phosphorus is 2.2G/100 mL), dried at 150 ℃ for 4 hours, and then baked at 500 ℃ for 3 hours to prepare the hydrodesulfurization catalyst G.
Comparative example 3
(1) Drying Phyllostachys Pubescens raw material at 180deg.C for 4 hr, and pulverizing into 300 mesh powder; 880g of moso bamboo powder, 20g of asphaltene powder, 100g of hydroxypropyl cellulose and 5g of potassium hydroxide are respectively weighed, mixed and kneaded, and molded; heating to 210 ℃ at a heating rate of 30 ℃/h, and performing heat treatment for 3h at 210 ℃; carbonizing at 270 ℃ for 4 hours in nitrogen atmosphere, and then performing steam treatment on carbonized materials at 270 ℃ for 4 hours to obtain an intermediate; the obtained intermediate is subjected to water purification washing treatment and then is dried for 3 hours at 120 ℃ in nitrogen atmosphere to obtain a carbon carrier; the remaining preparation steps were the same as in example 1 to prepare hydrodesulfurization catalyst H.
The physicochemical properties of the catalysts obtained in the above examples and comparative examples are listed in table 1.
Table 1 properties of the example and comparative catalysts
Catalyst numbering A B C D E F G H
Specific surface area, m 2/g 279 285 268 289 284 291 183 208
Pore volume, mL/g 0.62 0.61 0.63 0.60 0.61 0.66 0.50 0.43
Average pore diameter, nm 12.31 12.22 12.91 12.17 12.27 13.82 9.48 8.14
Side pressure strength, N/mm 21.15 22.32 20.87 23.38 22.04 12.58 22.65 11.34
Total acid, mmol/g 0.434 0.458 0.439 0.483 0.452 0.292 0.572 0.276
MoO3，wt％ 15.2 15.1 15.2 15.2 15.1 15.2 15.2 15.1
NiO，wt％ 3.5 3.5 3.5 3.6 3.5 3.5 3.5 3.5
P，wt％ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
Example 6
The hydrodesulfurization catalysts prepared in examples 1 to 5 and comparative examples 1 to 3 were used to hydrotreat residuum under the same process conditions, respectively, and the properties of the used residuum feedstock are shown in Table 2. The fixed bed process was used and table 3 shows the process conditions evaluated.
TABLE 2 Properties of raw oil
Properties of the feedstock
S，wt％ 3.96
Ni+V，μg/g 106.7
Ni，μg/g 28.2
V，μg/g 78.5
CCR，wt％ 11.8
Asphaltene content, wt% 3.1
Table 3 evaluation of the process conditions
Reaction conditions Parameters (parameters)
Temperature, DEG C 385
The pressure, the MPa, 15.0
Hydrogen to oil volume ratio 700:1
Liquid hourly space velocity, h -1 1.0
Table 4 shows the removal rates obtained after a specified operating hour for the raw oils of Table 2 by hydrotreating the catalysts obtained in example 1 and comparative example under the process conditions of Table 3, as shown in Table 4.
TABLE 4 desulfurization percentage after operation
As can be seen from the evaluation results of the catalysts in Table 4, the catalyst prepared by the method has good deep desulfurization performance, good carbon deposition resistance and good running stability.
Table 5 evaluation conditions and evaluation results of the hydrogenation catalysts obtained in examples after 1000 hours of operation
As can be seen from Table 5, the catalyst prepared by the method of the present invention has good deep desulfurization performance, good carbon residue removal performance, and certain asphaltene conversion capability.

Claims (18)

1. A method of preparing a hydrodesulfurization catalyst comprising:
(1) Mixing biomass raw materials with asphaltene powder, high polymer and inorganic matters containing potassium to obtain a mixture, kneading, forming and then carrying out heat treatment;
(2) Carbonizing the material obtained in the step (1), and then carrying out steam treatment;
(3) Repeating the step (2) for 1-5 times to obtain an intermediate, washing and drying;
(4) Spraying and soaking the carrier obtained in the step (3) with a regulator, and drying to obtain a carbon carrier;
(5) Preparing microemulsion containing active metal;
(6) Impregnating the carbon carrier obtained in the step (4) into the microemulsion obtained in the step (5), and then drying and roasting to obtain the hydrodesulfurization catalyst;
in the step (1), the high polymer is one or more of hydroxypropyl cellulose, methyl cellulose, phenolic resin and ethylene-vinyl acetate resin; the potassium-containing inorganic matter is one or more of potassium carbonate, potassium hydroxide and potassium oxide;
The heat treatment condition in the step (1) is a programmed heating heat treatment, wherein the heating rate is 20-80 ℃/h, and the temperature is kept at 150-350 ℃ for 1-8.0 h;
In the step (1), the mass ratio of the biomass in the mixture obtained in the step (1) is 70% -90%, the mass ratio of the asphaltene in the mixture obtained in the step (1) is 1% -10%, and the mass ratio of the high polymer in the mixture obtained in the step (1) is 8% -20%; the addition amount of the potassium-containing inorganic matters meets the requirement that the addition mass of potassium element accounts for 0.03% -3.00% of the mass of the mixture;
in the step (2), the condition of the carbonization treatment is as follows: treating under a protective gas;
in the step (2), the conditions of the steam treatment are as follows: the temperature is 150-700 ℃ and the time is 1-6 h;
In the step (4), the regulator is a solution containing one or more of fluorine, phosphorus, silicon or boron, or a solution selected from soluble organic acid and/or organic alcohol; when the regulator is a solution of one or more of fluorine, phosphorus, silicon or boron, the added mass of the one or more of fluorine, phosphorus, silicon or boron is 1.0% -10.0% of the mass of the regulator; when the regulator is a solution of soluble organic acid and/or organic alcohol, the mass concentration of the solution is 1.0-20.0 wt%;
In the step (5), the microemulsion containing the active metal is prepared from an active metal solution and an emulsifier; wherein the active metal solution is a molybdenum nickel phosphorus solution, and the emulsifier is a nonionic emulsifier.
2. The method according to claim 1, wherein in the step (1), the biomass raw material is one or more of wood, straw, fruit shell and bamboo; the biomass raw material is subjected to drying and crushing treatment, and the drying conditions are as follows: drying for 4-10 hours at 100-240 ℃, and grinding to obtain the wood chips with the granularity of 100-400 meshes.
3. The method according to claim 1, wherein in the step (2), the condition of the carbonization treatment is: treating under protective gas at 300-800 ℃ for 1-8 hours; the shielding gas is inert gas and/or nitrogen, wherein the inert gas is one or more of argon and helium.
4. The method according to claim 1, wherein in the step (2), the conditions of the steam treatment are: the temperature is 350-650 ℃.
5. The method according to claim 1, wherein in the step (4), the organic acid and/or the organic alcohol in the regulator is at least one of citric acid, ethylene glycol and polyethylene glycol.
6. The preparation method according to claim 1, wherein in the step (4), the spray-immersed product is dried at 60-180 ℃ for 5-12 hours under an inert gas and/or nitrogen atmosphere.
7. The method of claim 1, wherein in step (5), the active metal-containing microemulsion is prepared from an active metal solution and an emulsifier; the active metal solution is a molybdenum-nickel-phosphorus solution, wherein the content of molybdenum oxide in the solution is 10.0-45.0 g/100mL, the content of nickel oxide is 1.0-10.0 g/100mL, and the content of phosphorus is 0.1-4.5 g/100mL.
8. The method according to claim 1, wherein in the step (5), the emulsifier is one or more of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide block copolymer, polyoxyethylene ester, polyol fatty acid ester, polyvinyl alcohol, and polysorbate; the addition amount of the emulsifier is 1% -20% of the volume of the active metal solution in the step (5).
9. The preparation method of claim 1, wherein in the step (6), the carbon carrier obtained in the step (4) is immersed in the microemulsion containing the active metal component obtained in the step (5), the immersion method adopts a saturated immersion method or a supersaturation immersion method, the consumption of the immersion solution containing the active metal is 100% -150% of the saturated water absorption capacity of the carbon carrier obtained in the step (4), and the immersion time is 2-6 hours; after impregnation, ultrasonic treatment was used, and the conditions of the ultrasonic treatment were as follows: the ultrasonic frequency is 10-80 kHz, and the time is 2-8 hours.
10. The method according to claim 9, wherein the conditions of the ultrasonic treatment are as follows: the ultrasonic frequency is 20-60 kHz.
11. The method according to claim 1, wherein in the step (6), the drying condition is that the drying is performed for 2 to 15 hours at 80 to 150 ℃ under an inert gas and/or nitrogen atmosphere; the roasting conditions are as follows: roasting for 2-5 h at 300-600 ℃ in inert gas and/or nitrogen atmosphere.
12. A hydrodesulfurization catalyst obtainable by the process of any one of claims 1 to 11.
13. The hydrodesulfurization catalyst according to claim 12, characterized in that it comprises molybdenum oxide, nickel oxide and a support; wherein the mass content of the molybdenum oxide is 5% -28.0%, and the mass content of the nickel oxide is 1% -6.5%.
14. The hydrodesulfurization catalyst according to claim 13, characterized in that the hydrodesulfurization catalyst further comprises phosphorus element in an amount of 0.4 to 3.0% by mass.
15. The hydrodesulfurization catalyst according to claim 12 or 13, characterized in that the total acid amount of the hydrodesulfurization catalyst is 0.375 mmol/g to 0.525mmol/g; the average pore diameter of the hydrodesulfurization catalyst is 11.0 nm-15.0 nm; the specific surface area is 225m 2/g~300m2/g, the pore volume is 0.55 mL/g-0.70 mL/g, and the side pressure strength is more than 16N/mm.
16. The hydrodesulfurization catalyst according to claim 12 or 13, characterized in that the average pore diameter of the hydrodesulfurization catalyst is 11.5nm to 13.0nm; the side pressure strength is 18N/mm-25N/mm.
17. Use of the hydrodesulfurization catalyst of any one of claims 12 to 16 in a residuum hydrogenation process.
18. The use according to claim 17, wherein the residuum hydroprocessing conditions are: the reaction pressure is 8.0-20.0 MPa, the reaction temperature is 280-400 ℃, the liquid hourly space velocity is 0.1-3.0 -1, and the hydrogen-oil volume ratio is 100-1000.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106622308A (en) * 2015-10-29 2017-05-10 中国石油化工股份有限公司 Hydrodesulfurization catalyst, preparation method and applications thereof
CN109718797A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 A kind of preparation method of hydrotreating catalyst

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FR3022159B1 (en) * 2014-06-13 2018-04-27 IFP Energies Nouvelles MESOPOROUS AND MACROPOROUS CATALYST OF RESIDUAL HYDROCONVERSION AND METHOD OF PREPARATION
CN106807419B (en) * 2017-03-09 2019-07-02 武汉凯迪工程技术研究总院有限公司 The method that infusion process prepares hydrotreating catalyst
CN111195525A (en) * 2018-11-19 2020-05-26 中国石油天然气股份有限公司 Residual oil hydrodesulfurization catalyst and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106622308A (en) * 2015-10-29 2017-05-10 中国石油化工股份有限公司 Hydrodesulfurization catalyst, preparation method and applications thereof
CN109718797A (en) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 A kind of preparation method of hydrotreating catalyst

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