CN114984985B - Hydrodesulfurization catalyst and preparation method and application thereof - Google Patents

Hydrodesulfurization catalyst and preparation method and application thereof Download PDF

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Publication number
CN114984985B
CN114984985B CN202210787586.5A CN202210787586A CN114984985B CN 114984985 B CN114984985 B CN 114984985B CN 202210787586 A CN202210787586 A CN 202210787586A CN 114984985 B CN114984985 B CN 114984985B
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boehmite
pseudo
pore
stirring
catalyst
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CN114984985A (en
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甄涛
宋君辉
焦祖凯
金吉海
严金龙
张铎
张翠侦
许海龙
姚秀杰
郭莎莎
徐岩峰
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China National Offshore Oil Corp CNOOC
CNOOC Oil and Petrochemicals Co Ltd
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Oil and Petrochemicals Co Ltd
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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)

Abstract

The invention provides a hydrodesulfurization catalyst and a preparation method and application thereof, wherein the preparation method adopts a wetting agent and a pore-expanding agent to modify a carrier, so that the adsorption capacity of the carrier to a solution is enhanced; the obtained catalyst carrier is subjected to primary impregnation, drying and roasting to obtain a hydrodesulfurization catalyst; the preparation process is simple and the production cost is low. The hydrodesulfurization catalyst obtained by the invention has a good pore structure and certain acidity, and can effectively remove complex thiophene sulfur-containing compounds in needle coke raw materials and simultaneously retain as much tricyclic and tetracyclic aromatic hydrocarbons in the needle coke raw materials as possible.

Description

Hydrodesulfurization catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a hydrodesulfurization catalyst and a preparation method and application thereof.
Background
Needle coke is a high-quality carbon raw material developed in carbon materials of the sixties to seventies of the 20 th century, and has the advantages of low CTE, low heteroatom content, low ash content, high resistivity and the like. At present, the productivity of needle coke in the domestic market is rapidly increased, but the high-end needle coke still needs to be imported, and the profit margin is huge.
The composition and properties of the feedstock are critical to determine whether needle coke can be produced, and the proportions of the components in the feedstock determine the direction of formation of mesophase pellets. The heteroatom oxygen, sulfur, nitrogen and heterocyclic compounds have great influence on the reaction, have high thermal reactivity, accelerate the generation of mesophase spherule, easily generate fine grain mosaic structure and are not beneficial to the generation of needle coke. The flatness of aromatic hydrocarbon molecules and the size of Van der Waals force among the molecules greatly influence the directional arrangement of small spheres, and in general, the larger the branched chain is, the stronger the intermolecular attraction is, so that the regular arrangement of the molecules in the same rectangular direction is facilitated; the branched chain is too long, the tail molecule distance is long, the acting force is weakened, and the regular arrangement becomes difficult. The short-branched polycyclic aromatic hydrocarbon forms an sp2 hybridization orbit during reaction, free radicals are mutually connected in the same plane through the sp2 hybridization orbit, and then the layers are overlapped through a large pi bond to form a complete graphite structure. A small amount of colloid component is also needed in the raw materials, so that the formation and growth of the pellets are promoted; and proper amount of alkyl component is favorable for hydrogen transfer reaction in the pyrolysis process, the reaction activity is controlled, and the fluidity of the intermediate phase is stabilized.
Stock. C.A et al have been studied to suggest that needle coke feedstock should meet the following conditions:
Density >1.02g/cm 3; ash content is less than or equal to 0.05%; sulfur is less than or equal to 0.5 percent; QI < 1%; vanadium is less than or equal to 50mg/kg; nickel is less than or equal to 50mg/kg; the American mineral related index (BMCI) is more than or equal to 120.
CN112552959a discloses a pretreatment method and apparatus for raw material for producing needle coke, the hydrodesulfurization catalyst is a metal sulfide, the metal is selected from Ni, mo, fe, co, W and combinations thereof, preferably a combination of molybdenum sulfide and nickel sulfide, and the ratio of molybdenum sulfide and nickel sulfide is 1:1 (weight ratio of metal atoms). The sulfur content of the refined oil is reduced to below 0.5%, and the total aromatic hydrocarbon content is above 85%, so that the requirements of needle coke raw materials are met.
CN1325938a discloses a process for producing needle petroleum coke from sulfur-containing atmospheric residuum, the hydrogenation process is: the sulfur-containing normal-pressure residual oil is subjected to hydrofining, hydrodemetallization and hydrodesulfurization in sequence, and then the hydrogenated heavy distillate oil is separated to be used as needle coke raw material. The hydrodesulfurization catalyst consists of active components such as nickel-tungsten, nickel-molybdenum or cobalt-molybdenum and an alumina carrier. The sulfur content of the refined oil is controlled to be about 0.5%, so that the high-power petroleum coke can be produced.
CN103013567a discloses a method for producing needle coke raw material from catalytic cracking slurry oil, which comprises the following steps: (1) The catalytic cracking slurry oil firstly enters a protection zone to absorb most catalyst dust; (2) The de-solidified slurry oil enters a hydrogenation reaction zone to remove most of sulfur, and needle coke raw materials are obtained. The hydrodesulfurization catalyst comprises an alumina carrier, molybdenum and/or tungsten supported on the carrier, and nickel and/or cobalt. The pore distribution of the carrier is that the pore diameter is 100-200A accounting for 70-98% of the total pore volume. The content of molybdenum or tungsten is 0.5-18%, and the content of nickel or cobalt is 0.3-8%. The sulfur content of the refined oil is reduced to below 0.3%, and the content of the tricyclic tetracyclic aromatic hydrocarbon is above 25%, so that the refined oil can be used as a high-quality needle coke raw material.
However, the needle coke raw material hydrodesulfurization catalysts used in the method are all universal hydrogenation catalysts, and the desulfurization rate of the catalysts is low under mild reaction conditions; under severe conditions, the retention of tricyclic and tetracyclic aromatics is low.
Therefore, developing a hydrodesulfurization catalyst and a preparation method thereof have important significance in realizing desulfurization of needle coke raw materials and simultaneously retaining as much tricyclic and tetracyclic aromatic hydrocarbons as possible.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hydrodesulfurization catalyst, a preparation method and application thereof, wherein a wetting agent and a pore-expanding agent are adopted to modify a carrier, so that the adsorption capacity of the carrier to a solution is enhanced; the obtained catalyst carrier is subjected to primary impregnation, drying and roasting to obtain a hydrodesulfurization catalyst; the preparation process is simple and the production cost is low. The hydrodesulfurization obtained by the invention has a good pore structure and certain acidity, and can effectively remove complex thiophene sulfur-containing compounds in needle coke raw materials and simultaneously retain as much tricyclic and tetracyclic aromatic hydrocarbons as possible.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a hydrodesulfurization catalyst, said method comprising the steps of:
(1) Mixing a wetting agent and deionized water, and stirring to obtain a modified solution A; mixing small-pore pseudo-boehmite, a pore-enlarging agent, a peptizing agent and water, and stirring to obtain a modified solution B;
(2) Mixing macroporous pseudo-boehmite, an extrusion aid, a modified solution A and a modified solution B, uniformly stirring, rolling to be plastic, extruding strips for molding, and sequentially performing first drying and first roasting treatment to obtain a catalyst carrier;
(3) Mixing nickel salt, molybdenum salt, phosphoric acid and water, stirring and heating to obtain an impregnating solution;
(4) And (3) impregnating the catalyst carrier in the step (2) with the impregnating solution in the step (3), and sequentially carrying out health maintenance, second drying and second roasting treatment to obtain the hydrodesulfurization catalyst.
According to the preparation method of the hydrodesulfurization catalyst, the impregnating solution is a Mo-Ni-P solution with high phosphorus and high metal content, and the modified solution A containing a wetting agent and the modified solution B containing a pore-expanding agent are adopted to modify the carrier pseudo-boehmite, wherein the wetting agent improves the wettability of the surface of the carrier, and enhances the adsorption capacity of the carrier to the impregnating solution; the pore canal structure distribution of the carrier is increased by the pore-enlarging agent, the total pore volume is increased, and the problems of high viscosity of the high-phosphorus-content molybdenum-nickel-phosphorus solution, slow impregnation process, adhesion and agglomeration in the catalyst curing and drying processes are solved. Deionized water is used to mix with the wetting agent in the invention to prevent the introduction of impurities.
The catalyst carrier can be subjected to primary impregnation, health preserving, secondary drying and secondary roasting treatment to obtain the hydrodesulfurization catalyst without pretreatment of the catalyst carrier, multiple impregnation of the carrier, post-treatment of the catalyst and other processes. The hydrodesulfurization catalyst provided by the invention has the advantages of simple preparation flow, reduced production complexity and low production cost, and is suitable for large-scale popularization and application.
Preferably, the wetting agent of step (1) comprises any one or a combination of at least two of ammonia fluoride, potassium fluoride, ammonium acetate, diethanolamine, or polyethylene glycol, wherein typical but non-limiting combinations include combinations of ammonia fluoride and potassium fluoride, combinations of ammonium acetate and diethanolamine, combinations of polyethylene glycol and ammonia fluoride, combinations of potassium fluoride and diethanolamine, or combinations of polyethylene glycol, ammonia fluoride, and potassium fluoride.
Preferably, the mass ratio of the wetting agent to water is 0.01 (0.20-0.25), for example, 0.01:0.2, 0.01:0.21, 0.01:0.22, 0.01:0.23, 0.01:0.24 or 0.01:0.25, etc., but not limited to the recited values, other non-recited values within the range of values are equally applicable.
Preferably, the small pore pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by an aluminum alkoxide method.
Preferably, kong Rong 0.45.45 mL/g of the pseudo-boehmite can be, for example, 0.45mL/g, 0.43mL/g, 0.4mL/g, 0.37mL/g, 0.3mL/g or 0.1mL/g, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the specific surface area is not more than 250m 2/g, and may be, for example, 250m 2/g、240m2/g、230m2/g、220m2/g、200m2/g or 150m 2/g, etc., but is not limited to the values recited, and other values not recited in the range are applicable.
Preferably, the pore expanding agent comprises carbon black and/or silica, preferably silica.
Preferably, the peptizing agent comprises any one or a combination of at least two of nitric acid, citric acid, or acetic acid, wherein typical but non-limiting combinations include combinations of nitric acid and citric acid, combinations of acetic acid and nitric acid, or combinations of acetic acid, nitric acid, and citric acid, preferably nitric acid.
Preferably, the mixing sequence of the small pore pseudo-boehmite, the pore-expanding agent, the peptizing agent and the water is as follows:
firstly adding a pore-expanding agent and water, uniformly stirring, then adding the small-pore pseudo-boehmite, uniformly stirring, and then adding a peptizing agent.
Preferably, the macroporous pseudo-boehmite of step (2) comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by a carbonization method.
Preferably, the pore volume of the macroporous pseudo-boehmite is more than or equal to 1.0mL/g, for example, 1.0mL/g, 2.0mL/g, 3.5mL/g, 5.0mL/g or 8.0mL/g, etc., but the macroporous pseudo-boehmite is not limited to the recited values, and other non-recited values in the range of the values are equally applicable; the specific surface area is not less than 380m 2/g, and may be, for example, 380m 2/g、400m2/g、410m2/g、450m2/g or 500m 2/g, etc., but is not limited to the values recited, and other values not recited in the range are applicable.
Preferably, the extrusion aid comprises any one or a combination of at least two of sesbania powder, starch or methyl cellulose, wherein typical but non-limiting combinations include a combination of sesbania powder and starch, a combination of methyl cellulose and sesbania powder or a combination of methyl cellulose, sesbania powder and starch, preferably sesbania powder.
Preferably, the ratio of the water in the macroporous pseudo-boehmite, the pore-enlarging agent, the wetting agent, the peptizing agent, the extrusion aid, the modified solution A and the modified solution B is 1 (0.35-0.42): (0.03-0.04): (0.01-0.02): (0.05-0.07): (0.02-0.04): (0.20-0.30): (0.75-0.85), such as 1:0.35:0.03:0.01:0.05:0.02:0.20:0.75、1:0.36:0.031:0.01:0.05:0.024:0.21:0.77、1:0.37:0.035:0.015:0.053:0.029:0.27:0.78、1:0.38:0.038:0.017:0.058:0.03:0.23:0.80、1:0.4:0.039:0.01:0.06:0.035:0.20:0.81 or 1:0.42:0.04:0.02:0.07:0.04:0.30:0.85, etc., but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The invention preferably comprises the steps of (0.35-0.42), (0.03-0.04), (0.01-0.02), (0.05-0.07), (0.02-0.04), (0.20-0.30) and (0.75-0.85), wherein when the proportion of the wetting agent is too high or too low, the catalyst carrier is adhered and agglomerated in the rolling process, and the formed hydrodesulfurization catalyst cannot be prepared; when the proportion of the pore-expanding agent is too high or too low, the performance of the hydrodesulfurization catalyst is deteriorated, and the desulfurization effect is lowered.
Preferably, the mixing sequence of the macroporous pseudo-boehmite, the extrusion aid, the modifying solution A and the modifying solution B is as follows:
Adding macroporous pseudo-boehmite and an extrusion aid, stirring uniformly, adding the modified solution A, stirring uniformly, and then adding the modified solution B.
The invention preferably adds macroporous pseudo-boehmite and extrusion aid, adds the modified solution A after stirring uniformly, and adds the modified solution B after stirring uniformly, thus saving rolling time, and the obtained catalyst carrier has good impregnating effect in the impregnating process and excellent desulfurization performance finally.
The temperature of the first drying in the step (2) is preferably 120 to 150 ℃, and may be 120 ℃, 125 ℃,130 ℃,140 ℃, 145 ℃,150 ℃ or the like, for example, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The first drying time is preferably 3 to 6 hours, and may be, for example, 3 hours, 3.5 hours, 4 hours, 4.6 hours, 5 hours, or 6 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The temperature of the first firing is preferably 550 to 800 ℃, and may be 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like, for example, but the temperature is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
The time for the first firing is preferably 2 to 6 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, etc., but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the shape of the catalyst support comprises any one or a combination of at least two of cylindrical, clover-shaped or clover-shaped, wherein typical but non-limiting combinations include a combination of cylindrical and clover-shaped, a combination of clover-shaped and cylindrical, or a combination of clover-shaped, cylindrical and clover-shaped, preferably clover-shaped.
The pore volume of the catalyst support is preferably 0.70 to 0.90mL/g, and may be, for example, 0.70mL/g, 0.75mL/g, 0.80mL/g, 0.85mL/g, 0.88mL/g, or 0.90mL/g, etc., but is not limited to the values recited, and other values not recited in the range are equally applicable.
The specific surface area of the catalyst support is preferably 300 to 350m 2/g, and may be 300m 2/g、305m2/g、310m2/g、320m2/g、330m2/g or 350m 2/g, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the side pressure strength of the catalyst support is not less than 100N/cm, and may be, for example, 100N/cm, 110N/cm, 130N/cm, 150N/cm, 180N/cm, 200N/cm, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
The water absorption rate of the catalyst carrier is preferably 0.85 to 0.95mL/g, and may be, for example, 0.85mL/g, 0.86mL/g, 0.88mL/g, 0.90mL/g, 0.93mL/g, or 0.95mL/g, etc., but the catalyst carrier is not limited to the values recited, and other values not recited in the range are applicable.
Preferably, the nickel salt of step (3) comprises any one or a combination of at least two of nickel nitrate, basic nickel carbonate, nickel carbonate or nickel acetate, wherein typical but non-limiting combinations include a combination of nickel nitrate and basic nickel carbonate, a combination of nickel carbonate and nickel acetate, a combination of basic nickel carbonate and nickel carbonate or a combination of nickel acetate, nickel nitrate and basic nickel carbonate, preferably basic nickel carbonate.
The nickel salt is preferably added in an amount of 4 to 6% by oxide, for example, 4%, 4.5%, 5%, 5.5% or 6%, but is not limited to the listed values, and other values not listed in the range are equally applicable.
Preferably, the molybdenum salt comprises ammonium heptamolybdate and/or molybdenum oxide, preferably molybdenum oxide.
The molybdenum salt is preferably added in an amount of 23 to 26% in terms of oxide, for example, 23%, 24.5%, 25% or 26%, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The phosphoric acid is preferably added in a proportion of 2.5 to 3.5% based on the phosphorus element, for example, 2.5%, 2.8%, 3%, 3.3% or 3.5%, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the stirring and heating are carried out to 101-105 ℃, the temperature is kept for 30-70 min, and the heating is stopped after the immersion liquid becomes clear and transparent; the stirring and heating to 101 to 105℃may be, for example, 101℃102℃103℃104℃or 105℃but is not limited to the values listed, and other values not listed in the range are equally applicable; the holding time is 30 to 70 minutes, and may be, for example, 30 minutes, 35 minutes, 40 minutes, 50 minutes, 60 minutes, or 70 minutes, but is not limited to the values listed, and other values not listed in the range are applicable.
Preferably, the impregnation in step (4) is performed by means of an equal volume impregnation.
Preferably, the time for the curing is 3 to 6 hours, for example, 3 hours, 4 hours, 4.5 hours, 5 hours, or 6 hours, etc., but the curing is not limited to the listed values, and other non-listed values within the range are applicable.
The term "curing" as used herein means that the impregnating solution is allowed to sufficiently and uniformly permeate into the catalyst carrier, and the curing means may be, for example, standing.
The second drying temperature is preferably 120 to 150 ℃, and may be 120 ℃, 130 ℃, 140 ℃, 145 ℃, 150 ℃ or the like, for example, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The second drying time is preferably 6 to 10 hours, and may be, for example, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The temperature of the second firing is preferably 450 to 600 ℃, and may be, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are applicable.
The second baking time is preferably 2 to 6 hours, and may be, for example, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing a wetting agent and deionized water with the mass ratio of 0.01 (0.20-0.25), and stirring to obtain a modified solution A; mixing small-pore pseudo-boehmite, a pore-enlarging agent, a peptizing agent and water, and stirring to obtain a modified solution B; the wetting agent comprises any one or a combination of at least two of ammonia fluoride, potassium fluoride, ammonium acetate, diethanolamine or polyethylene glycol;
The small-pore pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by an aluminum alkoxide method; kong Rong 0.45.45 mL/g of the small-pore pseudo-boehmite, and the specific surface area is less than or equal to 250m 2/g; the pore-expanding agent comprises carbon black and/or silicon dioxide; the peptizing agent comprises any one or a combination of at least two of nitric acid, citric acid and acetic acid; the mixing sequence of the pore pseudo-boehmite, the pore-enlarging agent, the peptizing agent and the water is that the pore-enlarging agent and the water are added firstly, the pore-enlarging agent and the water are stirred uniformly, then the pore pseudo-boehmite is added, and the peptizing agent is added after the uniform stirring;
(2) Mixing macroporous pseudo-boehmite, an extrusion aid, a modified solution A and a modified solution B, uniformly stirring, rolling to be plastic, extruding to form strips, and sequentially carrying out first drying at 120-150 ℃ for 3-6 h and first roasting at 550-800 ℃ for 2-6 h to obtain a catalyst carrier;
The macroporous pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by a carbonization method; the pore volume of the macroporous pseudo-boehmite is more than or equal to 1.0mL/g, and the specific surface area is more than or equal to 380m 2/g; the extrusion aid comprises any one or a combination of at least two of sesbania powder, starch or methyl cellulose, and is preferably sesbania powder; the ratio of the water in the modified solution A to the water in the modified solution B is 1 (0.35-0.42), 0.03-0.04, 0.01-0.02, 0.05-0.07, 0.02-0.04, 0.20-0.30 and 0.75-0.85; the mixing sequence of the macroporous pseudo-boehmite, the extrusion aid, the modified solution A and the modified solution B is as follows: firstly adding macroporous pseudo-boehmite and an extrusion aid, uniformly stirring, then adding the modified solution A, uniformly stirring, and then adding the modified solution B;
The shape of the catalyst carrier comprises any one or a combination of at least two of a cylindrical shape, a clover shape or a clover shape; the pore volume of the catalyst carrier is 0.70-0.90 mL/g, the specific surface area is 300-350 m 2/g, the side pressure strength is more than or equal to 100N/cm, and the water absorption rate is 0.85-0.95 mL/g;
(3) Mixing nickel salt, molybdenum salt, phosphoric acid and water, stirring and heating to obtain an impregnating solution; the nickel salt comprises any one or a combination of at least two of nickel nitrate, basic nickel carbonate, nickel carbonate or nickel acetate; the nickel salt is added in an amount of 4-6% in terms of oxide; the molybdenum salt comprises ammonium heptamolybdate and/or molybdenum oxide; the molybdenum salt is added in an amount of 23-26% based on oxide; the phosphoric acid is calculated by phosphorus simple substance, and the adding proportion is 2.5-3.5%; stirring and heating to 101-105 ℃, keeping for 30-70 min, and stopping heating after the impregnating solution becomes clear and transparent;
(4) Soaking the catalyst carrier in the step (2) by using the soaking liquid in the step (3), and sequentially carrying out second drying at 120-150 ℃ for 6-10 h and second roasting at 450-600 ℃ for 2-6 h to obtain the hydrodesulfurization catalyst; the impregnation mode is equal volume impregnation.
In a second aspect, the present invention also provides a hydrodesulfurization catalyst prepared by the method for preparing a hydrodesulfurization catalyst according to the first aspect; the metal active components of the hydrodesulfurization catalyst comprise Mo and Ni, and the acidic auxiliary agent is P; the hydrodesulfurization catalyst comprises 23-26% of MoO 3, 4.0-6.0% of NiO and 2.5-3.5% of P by mass percent.
The hydrodesulfurization catalyst has a good pore structure and proper acidity, and can efficiently remove complex thiophene sulfur-containing compounds and simultaneously retain a certain amount of tricyclic and tetracyclic aromatic hydrocarbons.
23 To 26% MoO 3, for example, 23%, 24.5%, 25%, 25.7% or 26%, etc., but the present invention is not limited to the values recited, and other values not recited in the range are equally applicable;
NiO is 4.0 to 6.0%, for example, 4.0%, 4.5%, 5.0%, 5.5% or 6.0%, but is not limited to the values recited, and other values not recited in the range are equally applicable;
P is 2.5 to 3.5%, and may be, for example, 2.5%, 2.6%, 2.8%, 3% or 3.5%, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The pore volume of the hydrodesulfurization catalyst is preferably 0.40 to 0.55mL/g, and may be, for example, 0.40mL/g, 0.41mL/g, 0.42mL/g, 0.5mL/g, or 0.55mL/g, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The specific surface area of the hydrodesulfurization catalyst is preferably 180 to 250m 2/g, and may be 180m 2/g、190m2/g、200m2/g、210m2/g、230m2/g or 250m 2/g, for example, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The side pressure strength of the hydrodesulfurization catalyst is preferably not less than 100N/cm, and may be, for example, 100N/cm, 105N/cm, 110N/cm, 115N/cm, 120N/cm, 150N/cm, etc., but is not limited to the values recited, and other values not recited in the range of the values are equally applicable.
In a third aspect, the present invention also provides the use of a hydrodesulphurisation catalyst as described in the second aspect for treating needle coke feedstock.
The hydrodesulfurization catalyst disclosed by the invention can be used for selectively removing sulfur-containing compounds in needle coke raw materials and keeping a certain amount of tricyclic and tetracyclic aromatic hydrocarbons.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method of the hydrodesulfurization catalyst provided by the invention does not need the pretreatment of the carrier, the processes of repeated impregnation of the carrier, post-treatment of the catalyst and the like, has simple preparation flow and low production cost, and has a large-scale popularization and application prospect;
(2) The hydrodesulfurization catalyst provided by the invention has a good pore structure and certain acidity, is favorable for adsorbing and removing complex thiophene sulfur-containing compounds in needle coke raw materials, and can retain as much tricyclic and tetracyclic aromatic hydrocarbons in the needle coke raw materials as possible.
Drawings
FIG. 1 is a pore distribution diagram of the hydrodesulfurization catalyst obtained in example 1.
FIG. 2 is a graph showing the temperature-programmed desorption of ammonia from the hydrodesulfurization catalyst obtained in example 1.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The embodiment provides a method for preparing a hydrodesulfurization catalyst, which comprises the following steps:
(1) Respectively weighing 5.15g of ammonia fluoride and 105g of water, mixing and stirring to completely dissolve the ammonia fluoride to obtain a modified solution A; weighing 385.0g of water, adding 15.0g of silicon dioxide, stirring uniformly, adding 175.0g of pore volume 0.402mL/g, adding 198m 2/g of small pore pseudo-boehmite (dry basis 72%), stirring uniformly, adding 46.2g of nitric acid (mass concentration 65%), and stirring fully to uniformly mix to obtain a modified solution B;
(2) Weighing 500.0g of macroporous pseudo-boehmite (dry basis 72%) with a pore volume of 1.21mL/g and a specific surface area of 432m 2/g, and mixing 15.0g of sesbania powder uniformly to obtain a mixed material; adding the mixed material into a rolling machine, gradually adding a modifying solution A in the slow rotation process, rotating for 10min at a rotating speed of 10r/min, adding a modifying solution B, increasing the rotating speed of the rolling machine to 40r/min, rolling for 40min, discharging, drying at 120 ℃ for 5 hours after extrusion molding, and roasting at 550 ℃ for 3 hours to obtain a clover-shaped catalyst carrier, and marking as a carrier Z-1; the carrier has the characteristics of pore volume of 0.815mL/g, specific surface area of 366m 2/g and water absorption of 0.92mL/g;
(3) Respectively weighing 31.8g of basic nickel carbonate and 75.6g of molybdenum oxide, adding 120g of water into a three-neck flask, uniformly stirring, adding 32.5g of phosphoric acid (with the concentration of 85 percent), and uniformly stirring; transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 101 ℃, keeping for 40min, and stopping heating after the impregnating solution becomes clear and transparent; the impregnating solution is fixed to 184mL for standby, and is named as R-1;
(4) 200g of Z1 carrier is taken, the soaking solution 184mLR-1 is soaked in an equal volume, the health is maintained for 4 hours at 20 ℃, the drying is carried out for 6 hours at 120 ℃, and the roasting is carried out for 4 hours at 550 ℃, thus obtaining the hydrodesulfurization catalyst named Cat-1.
The pore distribution diagram of the hydrodesulfurization catalyst Cat-1 prepared in the embodiment is shown in figure 1, and as can be seen from figure 1, cat-1 has a good pore structure; as can be seen from FIG. 2, cat-1 has a certain acidity, and the ammonia temperature programmed desorption graph of Cat-1 is shown in FIG. 2.
Example 2
The embodiment provides a method for preparing a hydrodesulfurization catalyst, which comprises the following steps:
(1) Respectively weighing 10.0g of ammonium acetate and 105.0g of water, mixing and stirring to completely dissolve the ammonium acetate to obtain a modified solution A; 385.0g of water is weighed, 15.0g of carbon black is added, after uniform stirring, 175.0g of pore volume of 0.402mL/g and specific surface area of 198m 2/g of small pore pseudo-boehmite (dry basis of 72%) are added, after uniform stirring, 23.1g of nitric acid (mass concentration of 65%), 20.0g of acetic acid (mass concentration of 75%) are added, and after full stirring, the mixture is uniformly mixed to obtain a modified solution B;
(2) Weighing 500.0g of macroporous pseudo-boehmite (dry basis 72%) with a pore volume of 1.21mL/g and a specific surface area of 432m 2/g, and mixing 15.0g of sesbania powder uniformly to obtain a mixed material; firstly, adding the mixed material into a rolling machine, gradually adding a modified solution A in the slow rotation process, rotating for 10min at a rotating speed of 10r/min, adding a modified solution B, increasing the rotating speed of the rolling machine to 40r/min, rolling for 50min, and discharging; drying at 120deg.C for 5 hr after extrusion molding, and roasting at 600deg.C for 3 hr to obtain clover-shaped catalyst carrier, denoted as carrier Z-2; the carrier has the characteristics of pore volume of 0.805mL/g, specific surface area of 350m 2/g and water absorption of 0.90mL/g;
(3) Respectively weighing 31.8g of basic nickel carbonate and 75.6g of molybdenum oxide, adding 120g of water into a three-neck flask, uniformly stirring, adding 32.5g of phosphoric acid (with the concentration of 85 percent), and uniformly stirring; transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 105 ℃, keeping for 40min, and stopping heating after the impregnating solution becomes clear and transparent; the impregnating solution is fixed to 180mL for standby, and is named as R-2;
(4) 200g of Z-2 carrier is taken, 180mLR-2 impregnating solution is impregnated in an equal volume, the mixture is subjected to health maintenance for 4 hours at 20 ℃, dried for 6 hours at 120 ℃, and then baked for 4 hours at 600 ℃ to obtain the hydrodesulfurization catalyst which is named Cat-2.
Example 3
The embodiment provides a method for preparing a hydrodesulfurization catalyst, which comprises the following steps:
(1) Respectively weighing 10.0g of ammonium fluoride and 105.0g of water, mixing and stirring to completely dissolve the ammonium fluoride to obtain a modified solution A; 385.0g of water is weighed, 20.0g of silicon dioxide is added, after uniform stirring, 200.0g of pore volume of 0.402mL/g and specific surface area of 198m 2/g of small pore pseudo-boehmite (dry basis of 72%) are added, after uniform stirring, 46.2g of nitric acid (mass concentration of 65%) are added, and the mixture is fully stirred to be uniformly mixed to obtain a modified solution B;
(2) Weighing 500.0g of macroporous pseudo-boehmite (dry basis 72%) with a pore volume of 1.21mL/g and a specific surface area of 432m 2/g, and mixing 20.0g of sesbania powder uniformly to obtain a mixed material; firstly, adding the mixed material into a rolling machine, gradually adding a modifying solution 2 in the slow rotation process, rotating for 10min at a rotating speed of 10r/min, adding the modifying solution 1, increasing the rotating speed of the rolling machine to 40r/min, rolling for 45min, and discharging; drying at 120deg.C for 5 hr after extrusion molding, and roasting at 600deg.C for 3 hr to obtain clover-shaped catalyst carrier, denoted as carrier Z-3; the carrier has the characteristics of pore volume 0.831mL/g, specific surface area 373m 2/g and water absorption rate of 0.95mL/g;
(3) Respectively weighing 32.9g of basic nickel carbonate and 81.6g of molybdenum oxide, adding 120g of water into a three-neck flask, uniformly stirring, adding 36.1g of phosphoric acid (with the concentration of 85 percent), and uniformly stirring; transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 102 ℃, keeping for 40min, and stopping heating after the impregnating solution becomes clear and transparent; the impregnating solution is fixed to 190mL for standby, and is named as R-3;
(4) 200g of Z-3 carrier is taken, 190mLR-3 impregnating solution is impregnated in an equal volume, the mixture is preserved for 4 hours at 20 ℃, dried for 6 hours at 120 ℃, and then baked for 4 hours at 500 ℃ to obtain the hydrodesulfurization catalyst named Cat-3.
Example 4
The embodiment provides a method for preparing a hydrodesulfurization catalyst, which comprises the following steps:
(1) Respectively weighing 4.21g of polyethylene glycol, 5.05g of potassium fluoride and 100g of water, and mixing and stirring to completely dissolve the polyethylene glycol to obtain a modified solution A; 405.0g of water is weighed, 15g of carbon black and 5g of silicon dioxide are added, after uniform stirring, 204g of pore volume 0.402mL/g and specific surface area 198m 2/g of small pore pseudo-boehmite (dry basis 72%) are added, after uniform stirring, 47.7g of nitric acid (mass concentration 65%) are added, and the mixture is fully stirred to be uniformly mixed to obtain a modified solution B;
(2) Weighing 500.0g of macroporous pseudo-boehmite (dry basis 72%) with a pore volume of 1.21mL/g and a specific surface area of 432m 2/g, and mixing 15.0g of sesbania powder uniformly to obtain a mixed material; firstly, adding the mixed material into a rolling machine, gradually adding a modified solution A in the slow rotation process, rotating for 10min at a rotating speed of 10r/min, adding a modified solution B, increasing the rotating speed of the rolling machine to 40r/min, rolling for 50min, and discharging; drying at 120deg.C for 5 hr after extrusion molding, and roasting at 600deg.C for 3 hr to obtain clover-shaped catalyst carrier, which is denoted as carrier Z-4; the carrier has the characteristics of pore volume of 0.819mL/g, specific surface area of 370m 2/g and water absorption of 0.92mL/g;
(3) Respectively weighing 32.9g of basic nickel carbonate and 81.6g of molybdenum oxide, adding 120g of water into a three-neck flask, uniformly stirring, adding 36.1g of phosphoric acid (with the concentration of 85 percent), and uniformly stirring; transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 101 ℃, keeping for 60min, and stopping heating after the impregnating solution becomes clear and transparent; the impregnating solution was set to 184mL for use and designated R-4
(4) 200G of Z-4 carrier is taken, the equal volume of 184mLR-4 impregnating solution is impregnated, the curing is carried out for 4 hours at 20 ℃, the drying is carried out for 6 hours at 120 ℃, and the roasting is carried out for 4 hours at 600 ℃ to obtain the hydrodesulfurization catalyst which is named Cat-4.
Example 5
The embodiment provides a method for preparing a hydrodesulfurization catalyst, which comprises the following steps:
(1) Respectively weighing 10.0g of ammonia fluoride and 120g of water, mixing and stirring to completely dissolve the ammonia fluoride to obtain a modified solution A; 365.0g of water is weighed, 20.0g of silicon dioxide is added, after uniform stirring, 180g of pore volume of 0.402mL/g and specific surface area of 198m 2/g of small pore pseudo-boehmite (dry basis of 72%) are added, after uniform stirring, 49.1g of nitric acid (mass concentration of 65%) are added, and the mixture is fully stirred to be uniformly mixed to obtain a modified solution B;
(2) Weighing 500.0g of macroporous pseudo-boehmite (dry basis 72%) with a pore volume of 1.21mL/g and a specific surface area of 432m 2/g, and mixing 15.0g of sesbania powder uniformly to obtain a mixed material; firstly, adding the mixed material into a rolling machine, gradually adding a modified solution A in the slow rotation process, rotating for 10min at a rotating speed of 10r/min, adding a modified solution B, increasing the rotating speed of the rolling machine to 40r/min, rolling for 45min, and discharging; drying at 120deg.C for 5 hr after extrusion molding, and roasting at 600deg.C for 3 hr to obtain clover-shaped catalyst carrier, which is denoted as carrier Z-5; the carrier has the characteristics of pore volume 0.817mL/g, specific surface area 370m 2/g and water absorption rate 0.92mL/g;
(3) Respectively weighing 22.4g of basic nickel carbonate and 73.2g of molybdenum oxide, adding 120g of water into a three-neck flask, uniformly stirring, adding 43.4g of phosphoric acid (with the concentration of 85 percent), and uniformly stirring; transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 101 ℃, keeping for 40min, and stopping heating after the impregnating solution becomes clear and transparent; the impregnating solution is fixed to 184mL for standby, and is named as R-5;
(4) 200g of Z-5 carrier is taken, the equal volume of 184mLR-5 impregnating solution is impregnated, the curing is carried out for 4 hours at 20 ℃, the drying is carried out for 6 hours at 120 ℃, and the roasting is carried out for 4 hours at 550 ℃, thus obtaining the hydrodesulfurization catalyst which is named Cat-5.
Example 6
This example provides a method of preparing a hydrodesulfurization catalyst that is the same as example 1 except that 0.2g of the wetting agent ammonia fluoride is weighed.
In example 6, the addition ratio of the wetting agent of ammonia fluoride is too low, so that the catalyst strips adhere to each other and are agglomerated in the impregnation process, and the formed hydrodesulfurization catalyst cannot be prepared.
Example 7
This example provides a method for preparing a hydrodesulfurization catalyst, which is the same as example 1 except that 5g of silica as a pore-expanding agent is weighed, and the obtained hydrodesulfurization catalyst is named Cat-7.
Example 8
This example provides a method of preparing a hydrodesulfurization catalyst that is the same as example 1 except that 40g of the pore-expanding agent silica is weighed.
In example 8, the SiO 2 content was too high, so that the material was difficult to form during rolling, and the catalyst carrier meeting the index requirement could not be obtained during extrusion.
Comparative example 1
This comparative example provides a method for preparing a hydrodesulfurization catalyst comprising the steps of:
(1) Respectively weighing 500g (dry basis 72%) of pseudo-boehmite with a specific surface area of 190m 2/g, 22.5g (65%) of nitric acid, 15.0g of sesbania powder and 650g of deionized water, adding into a rolling machine, rolling and mixing, extruding, drying at 120 ℃ for 5 hours after strip extrusion molding, and roasting at 550 ℃ for 3 hours to obtain a clover-shaped catalyst carrier for later use; the carrier has the characteristics of pore volume of 0.712mL/g, specific surface area of 303m2/g and water absorption rate of 0.82mL/g;
(2) Respectively weighing 21.6g of basic nickel carbonate and 70.7g of molybdenum oxide, adding 105g of water into a three-neck flask, stirring uniformly, and adding 16.3g of phosphoric acid (with the concentration of 85 percent); transferring the three-neck flask into an electric heating sleeve, starting stirring and heating to 101 ℃, keeping for 30min, and stopping heating after the impregnating solution becomes clear and transparent; cooling to 166mL for standby;
(3) 200g of carrier is taken, 164mL of impregnating solution is impregnated in an equal volume, the temperature is kept for 8 hours at room temperature, the carrier is dried for 6 hours at 120 ℃, and then the carrier is roasted for 4 hours at 600 ℃ to obtain the hydrodesulfurization catalyst which is named CAT-0.
Physical and chemical properties of the hydrodesulfurization catalysts obtained in examples 1 to 5 and example 7 and comparative example 1 are shown in Table 1.
TABLE 1
As can be seen from table 1:
the hydrodesulfurization catalysts prepared in examples 1 to 5 have large pore volume, large specific surface area, high MoO 3, high NiO and P contents and good desulfurization performance. Example 7 the performance of the hydrodesulfurization catalyst prepared was slightly reduced due to the too low addition of the pore-expanding agent.
In comparative example 1, since the modified solution A containing the wetting agent and the modified solution B containing the pore-enlarging agent are not added, macroporous pseudo-boehmite, peptizing agent nitric acid, extrusion aid sesbania powder and deionized water are directly mixed to prepare a catalyst carrier, and then Mo-Ni-P solution is used for impregnation, the performance of the finally obtained hydrodesulfurization catalyst is greatly reduced, the pore volume is only 0.367mL/g, the specific surface area is only 143m 2/g,MoO3, and the content of NiO and P is also greatly reduced.
The hydrodesulfurization catalysts obtained in examples 1 to 5 and example 7 and comparative example 1 were evaluated using a certain refinery catalytic slurry deasphalted oil as a raw material, the raw material properties are shown in Table 2 below, the evaluation conditions are shown in Table 3, and the evaluation results are shown in Table 4.
TABLE 2
Analysis item Hydrogenation raw material
Density at 20 ℃ kg/m 3 1100
Carbon residue, wt% 6.4
Ash, wt% 0.005
Tricyclic and tetracyclic aromatics, wt% 57.8
Sulfur content, μg/g 8020
Nitrogen content, μg/g 1910
Simulated distillation, wt%, /
IBP/10/30 357.2/365.2/381.2
50/70/90 405.6/436.7/477.4
FBP 589.6
TABLE 3 Table 3
Project Index (I)
Reaction pressure, MPa 10
Reaction temperature, DEG C 290～310
Airspeed, h -1 1.0
Hydrogen to oil volume ratio 1000:1
TABLE 4 Table 4
As can be seen from Table 4, the hydrodesulfurization catalysts prepared in examples 1 to 5 treat the catalytic slurry deasphalted oil at a reaction temperature of 290℃and 300℃and 310℃respectively, and have a very high desulfurization rate while maintaining high amounts of tricyclic and tetracyclic aromatic hydrocarbons in the catalytic slurry deasphalted oil. Example 7 the performance of the hydrodesulfurization catalyst prepared was slightly deteriorated due to the excessively low addition amount of the pore-expanding agent.
The hydrodesulfurization catalyst obtained in comparative example 1 has a poor desulfurization effect although it catalyzes higher amounts of tricyclic and tetracyclic aromatics in slurry deasphalted oil.
In summary, the preparation method of the hydrodesulfurization catalyst provided by the invention has the advantages of simple preparation flow and low production cost, and the prepared hydrodesulfurization catalyst has good desulfurization performance and simultaneously retains as much tricyclic and tetracyclic aromatic hydrocarbons in the raw materials as possible.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (40)

1. A process for preparing a hydrodesulfurization catalyst for treating a needle coke feedstock, said process comprising the steps of:
(1) Mixing a wetting agent and deionized water, and stirring to obtain a modified solution A; mixing small-pore pseudo-boehmite, a pore-enlarging agent, a peptizing agent and water, and stirring to obtain a modified solution B;
(2) Mixing macroporous pseudo-boehmite, an extrusion aid, a modified solution A and a modified solution B, uniformly stirring, rolling to be plastic, extruding strips for molding, and sequentially performing first drying and first roasting treatment to obtain a catalyst carrier;
(3) Mixing nickel salt, ammonium heptamolybdate and/or molybdenum oxide, phosphoric acid and water, stirring and heating to obtain an impregnating solution;
(4) Impregnating the catalyst carrier in the step (2) with the impregnating solution in the step (3), and sequentially carrying out health preserving, second drying and second roasting treatment to obtain the hydrodesulfurization catalyst;
The metal active components of the hydrodesulfurization catalyst comprise Mo and Ni, and the acidic auxiliary agent is P; the hydrodesulfurization catalyst comprises 23-26% of MoO 3, 4.0-6.0% of NiO and 2.5-3.5% of P by mass percent;
The pore-expanding agent comprises carbon black and/or silicon dioxide;
The ratio of the water in the modified solution A to the water in the modified solution B is 1 (0.35-0.42): 0.03-0.04): 0.01 (0.05-0.07): 0.02-0.04): 0.20-0.25): 0.75-0.85;
The wetting agent in the step (1) comprises any one or a combination of at least two of ammonia fluoride, potassium fluoride, ammonium acetate, diethanolamine or polyethylene glycol.
2. The method of claim 1, wherein the small pore pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate process and/or pseudo-boehmite produced by an aluminum alkoxide process.
3. The method according to claim 1, wherein the specific surface area of the small pore pseudo-boehmite is Kong Rong 0.45.45 mL/g and is less than or equal to 250m 2/g.
4. The method of claim 1, wherein the pore-expanding agent is silica.
5. The method of claim 1, wherein the peptizing agent comprises any one or a combination of at least two of nitric acid, citric acid, or acetic acid.
6. The method of claim 5, wherein the peptizing agent is nitric acid.
7. The method of claim 1, wherein the mixing sequence of the pore pseudo-boehmite, the pore-expanding agent, the peptizing agent and the water is:
firstly adding a pore-expanding agent and water, uniformly stirring, then adding the small-pore pseudo-boehmite, uniformly stirring, and then adding a peptizing agent.
8. The method of claim 1, wherein the macroporous pseudo-boehmite of step (2) comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by a carbonization method.
9. The preparation method according to claim 8, wherein the pore volume of the macroporous pseudo-boehmite is more than or equal to 1.0mL/g, and the specific surface area is more than or equal to 380m 2/g.
10. The method of claim 1, wherein the extrusion aid comprises any one or a combination of at least two of sesbania powder, starch, or methylcellulose.
11. The method of claim 10, wherein the extrusion aid is sesbania powder.
12. The preparation method according to claim 1, wherein the mixing sequence of the macroporous pseudo-boehmite, the extrusion aid, the modifying solution A and the modifying solution B is as follows:
Adding macroporous pseudo-boehmite and an extrusion aid, stirring uniformly, adding the modified solution A, stirring uniformly, and then adding the modified solution B.
13. The method according to claim 1, wherein the temperature of the first drying in the step (2) is 120-150 ℃.
14. The method according to claim 1, wherein the first drying time is 3 to 6 hours.
15. The method according to claim 1, wherein the temperature of the first firing is 550-800 ℃.
16. The method according to claim 1, wherein the first firing time is 2 to 6 hours.
17. The method of preparing according to claim 1, wherein the shape of the catalyst support comprises any one or a combination of at least two of cylindrical shape, clover shape or clover shape.
18. The method of claim 17, wherein the catalyst support has a clover shape.
19. The method of claim 17, wherein the catalyst support has a pore volume of 0.70-0.90 ml/g.
20. The method of claim 17, wherein the specific surface area of the catalyst carrier is 300-350 m 2/g.
21. The method according to claim 17, wherein the side pressure strength of the catalyst carrier is not less than 100N/cm.
22. The method of claim 17, wherein the water absorption of the catalyst carrier is 0.85-0.95 ml/g.
23. The method of claim 1, wherein the nickel salt of step (3) comprises any one or a combination of at least two of nickel nitrate, basic nickel carbonate, or nickel acetate.
24. The method of claim 23, wherein the nickel salt is basic nickel carbonate.
25. The preparation method according to claim 1, wherein the nickel salt is added in an amount of 4-6% in terms of oxide.
26. The preparation method according to claim 1, wherein the ammonium heptamolybdate and/or molybdenum oxide is added in an amount of 23-26% in terms of oxide.
27. The preparation method according to claim 1, wherein the phosphoric acid is added in an amount of 2.5 to 3.5% based on the elemental phosphorus.
28. The method according to claim 1, wherein the heating is stopped after the immersion liquid becomes clear and transparent after the stirring is performed to 101-105 ℃ and maintained for 30-70 min.
29. The method of claim 1, wherein the impregnating in step (4) is performed by an isovolumetric impregnation.
30. The preparation method of claim 1, wherein the time for the health maintenance is 3-6 hours.
31. The method according to claim 1, wherein the second drying temperature is 120-150 ℃.
32. The method according to claim 1, wherein the second drying time is 6 to 10 hours.
33. The method according to claim 1, wherein the second firing temperature is 450-600 ℃.
34. The method according to claim 1, wherein the second firing time is 2 to 6 hours.
35. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing a wetting agent and deionized water with a mass ratio of 0.01 (0.20-0.25), and stirring to obtain a modified solution A; mixing small-pore pseudo-boehmite, a pore-enlarging agent, a peptizing agent and water, and stirring to obtain a modified solution B; the wetting agent comprises any one or a combination of at least two of ammonia fluoride, potassium fluoride, ammonium acetate, diethanolamine or polyethylene glycol;
The small-pore pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by an aluminum alkoxide method; kong Rong 0.45.45 mL/g of the small-pore pseudo-boehmite, and the specific surface area is less than or equal to 250m 2/g; the pore-expanding agent comprises carbon black and/or silicon dioxide; the peptizing agent comprises any one or a combination of at least two of nitric acid, citric acid and acetic acid; the mixing sequence of the pore pseudo-boehmite, the pore-enlarging agent, the peptizing agent and the water is that the pore-enlarging agent and the water are added firstly, the pore-enlarging agent and the water are stirred uniformly, then the pore pseudo-boehmite is added, and the peptizing agent is added after the uniform stirring;
(2) Mixing macroporous pseudo-boehmite, an extrusion aid, a modified solution A and a modified solution B, uniformly stirring, rolling to be plastic, extruding to form strips, and sequentially performing first drying at 120-150 ℃ for 3-6 h and first roasting at 550-800 ℃ for 2-6 h to obtain a catalyst carrier;
The macroporous pseudo-boehmite comprises pseudo-boehmite produced by an aluminum sulfate method and/or pseudo-boehmite produced by a carbonization method; the pore volume of the macroporous pseudo-boehmite is more than or equal to 1.0mL/g, and the specific surface area is more than or equal to 380m 2/g; the extrusion aid comprises any one or a combination of at least two of sesbania powder, starch or methyl cellulose; the ratio of the water in the modified solution A to the water in the modified solution B is 1 (0.35-0.42): 0.03-0.04): 0.01 (0.05-0.07): 0.02-0.04): 0.20-0.25): 0.75-0.85; the mixing sequence of the macroporous pseudo-boehmite, the extrusion aid, the modified solution A and the modified solution B is as follows: firstly adding macroporous pseudo-boehmite and an extrusion aid, uniformly stirring, then adding the modified solution A, uniformly stirring, and then adding the modified solution B;
The shape of the catalyst carrier comprises any one or a combination of at least two of a cylindrical shape, a clover shape or a clover shape; the pore volume of the catalyst carrier is 0.70-0.90 mL/g, the specific surface area is 300-350 m 2/g, the side pressure strength is more than or equal to 100N/cm, and the water absorption rate is 0.85-0.95 mL/g;
(3) Mixing nickel salt, ammonium heptamolybdate and/or molybdenum oxide, phosphoric acid and water, stirring and heating to obtain an impregnating solution; the nickel salt comprises any one or a combination of at least two of nickel nitrate, basic nickel carbonate, nickel carbonate or nickel acetate; the nickel salt is added in an amount of 4-6% in terms of oxide; the addition ratio of the ammonium heptamolybdate and/or the molybdenum oxide is 23-26% in terms of oxide; the phosphoric acid is calculated by phosphorus simple substance, and the adding proportion is 2.5-3.5%; stirring and heating to 101-105 ℃, keeping for 30-70 min, and stopping heating after the impregnating solution becomes clear and transparent;
(4) Soaking the catalyst carrier in the step (2) by using the soaking liquid in the step (3), and sequentially carrying out curing for 3-6 hours, second drying for 6-10 hours at 120-150 ℃ and second roasting for 2-6 hours at 450-600 ℃ to obtain the hydrodesulfurization catalyst; the impregnation mode is equal volume impregnation.
36. A hydrodesulfurization catalyst, characterized in that the hydrodesulfurization catalyst is prepared by the method for preparing a hydrodesulfurization catalyst according to any one of claims 1 to 35; the metal active components of the hydrodesulfurization catalyst comprise Mo and Ni, and the acidic auxiliary agent is P; the hydrodesulfurization catalyst comprises 23-26% of MoO 3, 4.0-6.0% of NiO and 2.5-3.5% of P by mass percent.
37. The hydrodesulfurization catalyst of claim 36, wherein the hydrodesulfurization catalyst has a pore volume of 0.40 to 0.55ml/g.
38. The hydrodesulfurization catalyst of claim 36, wherein the hydrodesulfurization catalyst has a specific surface area of 180-250 m 2/g.
39. The hydrodesulfurization catalyst according to claim 36, characterized in that the side pressure strength of the hydrodesulfurization catalyst is not less than 100N/cm.
40. Use of the hydrodesulfurization catalyst of any of claims 36-39 to treat needle coke feedstock.
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