CN112337506B - Catalyst for Fischer-Tropsch wax hydrogenation conversion and preparation method and application thereof - Google Patents

Catalyst for Fischer-Tropsch wax hydrogenation conversion and preparation method and application thereof Download PDF

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CN112337506B
CN112337506B CN202011263489.3A CN202011263489A CN112337506B CN 112337506 B CN112337506 B CN 112337506B CN 202011263489 A CN202011263489 A CN 202011263489A CN 112337506 B CN112337506 B CN 112337506B
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catalyst
drying
molecular sieve
fischer
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CN112337506A (en
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韩磊
黄传峰
刘树伟
程秋香
张健
张小琴
刘晓花
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Shaanxi Yanchang Petroleum Group Co Ltd
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates (SAPO compounds)
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products

Abstract

The invention provides a catalyst for Fischer-Tropsch synthesis wax hydroconversion and a preparation method and application thereof, wherein the catalyst comprises Ni and W hydrogenation metals, a Y-type molecular sieve, an isomerization molecular sieve and alumina; the preparation method of the catalyst comprises the following steps: firstly, mixing and pulping aluminum oxide and water, and then sequentially adding a USY molecular sieve and a Ni metal compound to form a mixture; secondly, placing the mixture in a closed reaction kettle for dynamic hydrothermal treatment; thirdly, adding an isomerization molecular sieve after the treatment is finished, fully stirring, filtering, drying, adding dilute nitric acid, extruding into strips, forming and roasting; finally, impregnating the W metal compound by adopting an isometric impregnation method, drying and roasting to obtain a hydrocracking catalyst; the hydrocracking catalyst prepared by the method has proper acid property, pore channel property and metal dispersibility, can effectively reduce the secondary cracking performance in the hydrocracking process of Fischer-Tropsch synthetic wax, and improves the yield and product property of light fuel oil.

Description

Catalyst for Fischer-Tropsch wax hydrogenation conversion and preparation method and application thereof
Technical Field
The invention relates to the technical field of hydrocracking of low-temperature Fischer-Tropsch synthetic wax, in particular to a catalyst for Fischer-Tropsch synthetic wax hydroconversion and a preparation method and application thereof.
Background
The structural characteristics of energy in China are that the coal content is rich, and the petroleum and natural gas resources are limited, so that the coal becomes one of the energy mainly utilized in China. However, in the process of insufficient combustion of coal, carbon monoxide and black smoke are easily generated, and the ecological environment is polluted. Accelerating the development of clean development and utilization technology of coal, and becoming one of the important ways of easing the energy safety environment in China and solving the increasingly prominent ecological environment problem in China. Based on the technical requirements of cleanness, high efficiency, scale and the like in the coal utilization process, the coal-to-liquid synthetic oil becomes the mainstream approach of clean utilization of coal at home and abroad at present, and especially has the advantages of cleanness, environmental protection, excellent combustion performance and the like of coal indirect liquefaction synthetic oil, so that the coal-to-liquid synthetic oil becomes the development hotspot of the current clean coal technology.
At present, fischer-Tropsch wax is an ideal raw material for preparing oil products such as clean diesel oil, aviation kerosene, high-grade lubricating oil base oil and the like, paraffin products of different grades, alpha olefin and other chemicals, and has the characteristics of no sulfur, no nitrogen and low aromatic hydrocarbon content. However, the market demand of high value-added products such as lubricating oil, special wax, alpha olefin, aviation kerosene and the like is limited, so that the production can be carried out only in a small scale, and the Fischer-Tropsch wax product in a large scale cannot be consumed. Therefore, the hydrocracking technology for producing high-quality fuel oil is a main way for processing Fischer-Tropsch wax on a large scale.
Chinese patent 103878017A discloses a non-noble metal isomerization catalyst and a preparation method and application thereof. The catalyst consists of a ten-membered ring molecular sieve and a transition metal oxide loaded with Raney nickel, wherein the weight composition ratio of the ten-membered ring molecular sieve to the transition metal oxide loaded with Raney nickel is 0.2-5. The invention has the advantages of low cost, good activity and high isomerization selectivity when being used for preparing the lubricating oil base oil by Fischer-Tropsch wax isomerization.
Catalyst for mild hydrocracking of fischer-tropsch wax in chinese patent 201410007377.X, consisting essentially of, in mass percent: 0.1 to 1 percent of catalytic active component, 30 to 65 percent of carrier and the balance of metal fiber structured material. Also provided is a rectification reaction apparatus for mild hydrocracking of Fischer-Tropsch wax, a reaction section in which the catalyst of the first aspect of the invention is placed, and a process for mild hydrocracking of Fischer-Tropsch wax, wherein the catalyst used is the catalyst of the first aspect of the invention. The catalyst prepared by the method has the advantages of unique three-dimensional structure, high mass transfer efficiency, high heat transfer efficiency and random shape design. The novel Fischer-Tropsch wax mild hydrocracking method has higher activity and selectivity, but the yield of cracked gas is about 10%.
Chinese patent CN200910272467.0 provides a noble metal catalyst for hydrocracking and isomerization of Fischer-Tropsch wax and a preparation method thereof, wherein catalyst carrier components comprise 70-85 wt% of amorphous silica-alumina and 15-30 wt% of alumina binder, active components are selected from noble metal Pt and Pd elements, the Pt/Pd molar ratio is 0.1-0.6, and the noble metal active components are 0.1-1 wt% of the carrier; the specific surface area of the catalyst is 150-400 m 2 (g), pore volume of 0.3-1.4 ml/g, NH 3 The total acidity of TPD is 0.5-1.5 mmol/g, and the pore distribution of 4-15 nm accounts for 60-90% of the total pore volume. The preparation method comprises the following steps: 1) Adding amorphous silica-alumina with required weight into alumina adhesive, adding 1-5 wt% of pore-forming agent CMC and 1-3 wt% of extrusion aid nitrile powder of amorphous silica-alumina, kneading, rolling into clusters, extruding into strips on a strip extruder, drying, and roasting to obtain a carrier; 2) And loading noble metal elements of Pt and Pd as active components by a conventional impregnation method, drying in vacuum, and roasting to obtain the catalyst.
Chinese patent CN1593757 discloses a catalyst for hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon suspension bed, which is prepared by uniformly mixing iron/copper/potassium/calcium/magnesium/manganese/lanthanum metal salt solutions in a certain mass ratio, adding a precipitator to form precipitation slurry, washing, filtering, adding a water-soluble silicon-containing material into a filter cake, adding potassium nitrate into the filter cake to carry out pulping, spraying, drying and roasting. The catalyst has low cost, and especially, the catalyst can obtain a conversion per pass of more than 80% by applying hydrocracking of a Fischer-Tropsch synthesized heavy hydrocarbon suspension bed, and the yield of the middle distillate oil can reach more than 75%.
The Fischer-Tropsch wax hydrocracking catalysts researched above all take a fixed bed as a main component, but low-carbon hydrocarbons are easy to crack secondarily in the fixed bed catalyst, so that the defects of high yield of cracked gas, easy inactivation of the catalyst, low gasoline octane number, high diesel condensation point and the like still exist during Fischer-Tropsch wax processing, and the overall economy of the coal indirect liquefaction technology is reduced.
Disclosure of Invention
The invention aims to provide a catalyst for Fischer-Tropsch wax hydrogenation conversion, a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a catalyst for Fischer-Tropsch synthesis wax hydroconversion comprises the following components in percentage by mass: 5-9% of Ni metal compound, 21-25% of W metal compound, 5-25% of Y-type molecular sieve, 0-30% of isomerized molecular sieve and Al 2 O 3 20 to 65 percent.
Further, the isomerization molecular sieve is one or a mixture of two of SAPO-11 molecular sieve, ZSM-22 molecular sieve, ZSM-5 molecular sieve and beta molecular sieve.
Furthermore, the specific surface area of the catalyst is 185-300 m 2 Per g, the mesoporous volume is 0.35-0.55 cm 3 The average pore diameter of the mesopores is 32-70 nm;
NH of the catalyst 3 The proportion of the medium and strong acid and weak acid with the temperature of less than 350 ℃ in the determination result of-TPD acidity accounts for 80-95% of the total acid.
A preparation method of a catalyst for Fischer-Tropsch wax hydroconversion comprises the following steps;
a) Mixing, pulping and uniformly stirring alumina and water, adding a Y-type molecular sieve, adjusting the pH to 9-12 with ammonia water, fully stirring, adding a Ni metal compound, continuously stirring uniformly, and standing for 8-24 hours to obtain a mixture;
b) Placing the mixture obtained in the step a) in a closed reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 60-200 ℃, the pressure is 0.1-2.0 MPa, the stirring speed is 100-1000 r/min, and the time is 8-36 h;
c) Stirring the hydrothermal treatment product in the step b), adding an isomerization molecular sieve after cooling to room temperature, stirring for 1-2 h, and then filtering, washing, drying and crushing to obtain powder;
d) Adding dilute nitric acid and sesbania powder into the powder obtained in the step c), extruding strips, drying, heating to 500-550 ℃ at the speed of 1.5-2.5 ℃/min, and roasting for 3-6 h to obtain a catalyst precursor; the addition amount of the sesbania powder is 1-3% of the powder mass, and the dilute nitric acid is obtained by diluting 1-2% of the powder mass of concentrated nitric acid and water according to the proportion of 1 (60-90);
e) Soaking the catalyst precursor obtained in the step d) for 12-24 h by adopting a W metal compound solution prepared by an isometric soaking method, drying, heating to 550-600 ℃ at 1.0-2.0 ℃/min, and roasting for 3-6 h to obtain the Fischer-Tropsch wax hydroconversion catalyst.
Further, the mesoporous specific surface area of the alumina in the step a) is 250-380 m 2 The pore volume of the mesopores is 0.75-0.95 mL/g, and the average pore diameter of the mesopores is 65-80 nm;
the Ni metal compound in the step a) is one or a mixture of nickel nitrate, nickel chloride and nickel acetate.
Further, the drying process in the step c is drying for 1-6 hours at 60-90 ℃, and then drying for 8-24 hours at 100-135 ℃.
Further, the drying process in the step d) comprises the steps of drying at 60-120 ℃ for 12-24 h, and then drying at 150-250 ℃ for 8-24 h.
Further, the W metal compound in the step e) is one or a mixture of ammonium metatungstate, ammonium tungstate and tungsten hexachloride;
the drying process in the step e) comprises the steps of drying at a constant temperature of 60-90 ℃ for 1-6 h, and then drying at a constant temperature of 100-150 ℃ for 8-24 h.
Further, the three times of stirring in the step a) are all 1-4 h.
An application of a catalyst for Fischer-Tropsch synthetic wax hydrogenation conversion in preparing a clean fuel oil product by Fischer-Tropsch synthetic wax oil hydrocracking.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the preparation mode and the material proportioning mode of the existing catalyst are improved, the characteristics of the competitive action of Ni and W metal compounds and a catalyst precursor are utilized, firstly, the Ni metal compounds, a Y molecular sieve and alumina are mixed and subjected to hydrothermal treatment, the dispersibility of Ni species in a catalyst pore channel is improved, the number of catalyst L acid centers is reduced, the distance between the catalyst acid active center and the metal active center is shortened, the secondary cracking of low-carbon hydrocarbons in the catalyst is effectively reduced, and the utilization rate of metals is improved; secondly, according to the characteristic that W species are easy to migrate in the catalyst pore canal and easy to interact with the strong acid sites of the molecular sieve, the strong acid amount of the catalyst is reduced, the acid site density of the catalyst B is improved, more high-activity hydrogenation central phases are formed, the secondary cracking of low-carbon hydrocarbon is reduced, and the overall isomerization activity of the catalyst is improved; then, adding an isomerization molecular sieve to further improve the isomerization activity of the catalyst and the product property; finally, the blockage of mesoporous channels caused by the aggregation of metal crystal phases is reduced by improving the dispersibility of the catalyst supported metal, so that the diffusion resistance of reaction species in the channels is reduced.
The catalyst prepared by the method mainly comprises weak acid and medium-strong acid, has high content of B acid, has the pore canal property mainly comprising mesopores and macropores, has uniform metal distribution and good dispersibility, is beneficial to the diffusion of long-chain hydrocarbons in the catalyst, and can effectively reduce the diffusion resistance of the catalyst; when the catalyst is used for the hydrocracking process of Fischer-Tropsch synthetic wax or long-chain wax oil, the yield of light fuel oil can be greatly improved, the yield of pyrolysis gas is reduced, and the economic benefit is obvious.
The Fischer-Tropsch synthetic wax prepared by the invention can be applied to the process of preparing a clean fuel oil product by hydrocracking Fischer-Tropsch synthetic wax oil with a catalyst, and can also be applied to the following projects:
1) Improving the conversion rate of hydrocarbons with carbon number of more than 22 in the hydrocracking raw material of the Fischer-Tropsch synthetic wax;
2) The selectivity of hydrocarbon products with carbon number of more than 5 in Fischer-Tropsch synthetic wax hydrocracking products is improved;
3) The selectivity of C1-C4 gas products in Fischer-Tropsch synthetic wax hydrocracking products is reduced;
4) The selectivity of hydrocarbon products with 5-12 carbon atoms in Fischer-Tropsch synthetic wax hydrocracking products is improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
714g of Al type A were weighed 2 O 3 Mixing with water, pulping, quickly stirring for 4h, adding 150g of Y molecular sieve, adjusting the pH to 9 with ammonia water, fully stirring for 2h, adding 272.55g of nickel nitrate pentahydrate, continuously stirring for 2h, and standing for 24h to obtain a mixture.
Placing the mixture in a closed reaction kettle for hydrothermal treatment at 105 ℃ and 1.4MPa, wherein the stirring speed is 300 r/min; cooling after the hydrothermal treatment is finished, adding 50g of SAPO-11 molecular sieve after cooling, filtering and washing after stirring for 1h, drying at 70 ℃ for 4h, then drying at 120 ℃ for 12h, and then crushing into powder; adding 1% sesbania powder and dilute nitric acid diluted by concentrated nitric acid and water according to the proportion of 1 to 70 into the powder, extruding the powder into strips, drying the strips at 80 ℃ for 12h, then drying the strips at 130 ℃ for 6h, and then roasting the strips at 500 ℃ for 4h at the heating rate of 1.5 ℃/min to obtain the catalyst precursor.
Adopting an equal-volume impregnation method to prepare a solution containing 330g of ammonium metatungstate for impregnation, standing for 16h, drying at 80 ℃ for 4h, then drying at 135 ℃ for 12h, and then roasting at 600 ℃ for 4h to obtain the catalyst Cat-1.
Example 2:
714g of Al type A are weighed 2 O 3 Mixing with water, pulping, rapidly stirring for 4h, adding 150g of Y molecular sieve, adding 50g of SAPO-11 molecular sieve, and stirring at 300 r/min; stirring for 1h, filtering, washing, drying at 70 deg.C for 4h, drying at 120 deg.C for 12h, and crushing into powder; adding 1% sesbania powder and dilute nitric acid diluted by concentrated nitric acid and water according to the proportion of 1 to 70 into the powder, extruding the powder into strips, drying the strips at 80 ℃ for 12h, then drying the strips at 130 ℃ for 6h, and then roasting the strips at 500 ℃ for 4h at the heating rate of 1.5 ℃/min to obtain the catalyst precursor.
Preparing a solution containing 330g of ammonium metatungstate and 272.55g of nickel nitrate pentahydrate by an isometric impregnation method for impregnation, standing for 16h, drying at 80 ℃ for 4h, drying at 135 ℃ for 12h, and roasting at 600 ℃ for 4h to obtain the catalyst Cat-2.
Example 3:
under the condition that the preparation conditions are not changed according to the embodiment 1, after the hydrothermal treatment is finished and the cooling is finished, 50g of ZSM-22 molecular sieve is added to obtain a catalyst Cat-3.
Example 4:
714g of Al type A are weighed 2 O 3 Mixing with water, pulping, quickly stirring for 4h, adding 150g of Y molecular sieve and 50g of ZSM-5 molecular sieve, adjusting the pH value to 9 with ammonia water, fully stirring for 2h, adding 272.55g of nickel nitrate pentahydrate, stirring the mixture at the speed of 300 r/min, filtering and washing after stirring for 1h, drying at 70 ℃ for 4h, drying at 120 ℃ for 12h, and crushing into powder; adding 1% sesbania powder and dilute nitric acid diluted by concentrated nitric acid and water according to the proportion of 1 to 70 into the powder, extruding the powder into strips, drying the strips at 80 ℃ for 12 hours, drying the strips at 130 ℃ for 6 hours, and roasting the strips at 500 ℃ for 4 hours at a heating rate of 1.5 ℃/min to obtain a catalyst precursor; preparing a solution containing 330g of ammonium metatungstate by an isometric impregnation method for impregnation, standing for 16h, drying at 80 ℃ for 4h, drying at 135 ℃ for 12h, and then roasting at 600 ℃ for 4h to obtain the catalyst Cat-4.
Example 5:
weighing A type 714g Al 2 O 3 And is andmixing water, pulping, quickly stirring for 4h, adding 150g of Y molecular sieve, and adjusting the pH value to 9 with ammonia water to obtain a mixture; placing the mixture in a closed reaction kettle to carry out hydrothermal treatment at 105 ℃ and 1.4MPa, wherein the stirring speed is 300 r/min; after the hydrothermal treatment is finished and cooled, 50g of SAPO-11 molecular sieve is added, after stirring for 1h, filtration and washing are carried out, drying is carried out for 4h at 70 ℃, then drying is carried out for 12h at 120 ℃, and then crushing is carried out to obtain powder; adding 1% sesbania powder and dilute nitric acid diluted by concentrated nitric acid and water according to the proportion of 1 to 70 into the powder, extruding the powder into strips, drying the strips at 80 ℃ for 12 hours, drying the strips at 130 ℃ for 6 hours, and roasting the strips at 500 ℃ for 4 hours at a heating rate of 1.5 ℃/min to obtain a catalyst precursor; preparing a solution containing 330g of ammonium metatungstate and 272.55g of nickel nitrate pentahydrate by an isometric impregnation method for impregnation, standing for 16h, drying at 80 ℃ for 4h, drying at 135 ℃ for 12h, and roasting at 600 ℃ for 4h to obtain the catalyst Cat-5.
Comparative example 1:
714g of Al type A are weighed 2 O 3 Mixing with water, pulping, quickly stirring for 4h, adding 200g of Y molecular sieve, continuously stirring for 2h, and standing for 24h; filtering, washing, drying at 70 deg.C for 4 hr, drying at 120 deg.C for 12 hr, and pulverizing into powder; adding 1% sesbania powder and 1% dilute nitric acid diluted by 1% concentrated nitric acid and water according to the proportion of 1; preparing a nickel nitrate pentahydrate solution containing 330g of ammonium metatungstate and 272.55g of ammonium metatungstate by an isometric impregnation method, impregnating, drying at 135 ℃ for 12 hours after impregnation, and roasting at 600 ℃ for 4 hours to obtain a comparative catalyst Cat-6.
The catalyst evaluation results of examples 1 to 5 and comparative example 1 are shown in table 1.
Figure BDA0002775385950000081
As can be seen from Table 1, under the same process conditions, C of the catalyst of the invention 22+ Single conversion, light fuel oil (C) 5 ～C 12 、C 12 ～C 22 ) The selectivity activity was superior to that of comparative example 1.
Example 6
a) Mixing 714g of alumina with water, pulping, stirring for 1h, adding 892.5g of a Y-type molecular sieve and ammonia water to adjust the pH to 9, stirring fully for 4h, adding 556g of nickel nitrate, stirring for 3h, standing for 12h to obtain a mixture; the mesoporous specific surface area of the obtained alumina is 250-380 m 2 The pore volume of the mesopores is 0.75-0.95 mL/g, and the average pore diameter of the mesopores is 65-80 nm;
b) Placing the mixture obtained in the step a) in a closed reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 100 ℃, the pressure is 1.0MPa, the stirring speed is 100r/min, and the time is 15h;
c) Stirring the hydrothermal treatment product in the step b), cooling to room temperature, and adding 892.5g of a beta molecular sieve. Stirring for 1h, filtering, washing, drying and crushing to obtain powder;
d) Adding dilute nitric acid and sesbania powder into the powder obtained in the step c), extruding strips, drying, heating to 500 ℃ at the speed of 2.0 ℃/min, and roasting for 6 hours to obtain a catalyst precursor; the adding amount of the sesbania powder is 3% of the mass of the powder, and the dilute nitric acid is diluted by 1% of the mass of the powder of concentrated nitric acid and water according to the proportion of 1;
e) Weighing 1203.1g of ammonium tungstate according to the W oxide content, soaking the catalyst precursor obtained in the step d) for 12 hours by adopting a W metal compound solution prepared by an isometric soaking method, then drying at a constant temperature of 70 ℃ for 5 hours, finally drying at a constant temperature of 100 ℃ for 10 hours, heating to 550 ℃ at a speed of 2.0 ℃/min after drying, and roasting for 6 hours to obtain the Fischer-Tropsch wax hydroconversion catalyst. The specific surface area of the prepared catalyst is 185-300 m 2 Per g, the mesoporous volume is 0.35-0.55 cm 3 The average pore diameter of mesopores is 32-70 nm; NH of the catalyst 3 The proportion of the medium and strong acid and weak acid with the temperature of less than 350 ℃ in the TPD acidity determination result accounts for 80 to 95 percent of the total acid.
Example 7
a) Mixing 714g of alumina with water, pulping, stirring for 4h uniformly, adding 102g of Y-type molecular sieve, adjusting the pH to 10 with ammonia water, stirring fully for 1h, adding 405.3g of nickel chloride, stirring continuously for 4h uniformly, and standing for 8h to obtain a mixture;
b) Placing the mixture obtained in the step a) in a closed reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 60 ℃, the pressure is 2.0MPa, the stirring speed is 1000r/min, and the time is 8h;
c) Stirring the hydrothermal treatment product in the step b), cooling to room temperature, adding 612g of ZSM-5 molecular sieve, stirring for 2 hours, filtering, washing, drying and crushing to obtain powder;
d) Adding dilute nitric acid and sesbania powder into the powder obtained in the step c), extruding strips, drying, heating to 550 ℃ at the speed of 2.5 ℃/min, and roasting for 5 hours to obtain a catalyst precursor; the adding amount of the sesbania powder is 13 percent of the mass of the powder, and the dilute nitric acid is diluted by 1.5 percent of concentrated nitric acid and water according to the proportion of 1;
e) Weighing 924.16g of tungsten hexachloride according to the content of W oxide, soaking the catalyst precursor obtained in the step d) by adopting a W metal compound solution prepared by an isometric soaking method for 20 hours, then drying at a constant temperature of 60 ℃ for 4 hours, finally drying at a constant temperature of 150 ℃ for 8 hours, heating to 600 ℃ at a speed of 1.0 ℃/min after drying, and roasting for 3 hours to obtain the Fischer-Tropsch wax hydroconversion catalyst.
Example 8
a) Mixing 714g of alumina with water, pulping, stirring for 2h uniformly, adding 66g of Y-type molecular sieve, adjusting the pH value to 12 with ammonia water, stirring fully for 3h, adding 198.5g of nickel acetate, stirring continuously for 1h uniformly, and standing for 24h to obtain a mixture;
b) Placing the mixture obtained in the step a) in a closed reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 200 ℃, the pressure is 0.1MPa, the stirring speed is 500r/min, and the time is 36h;
c) Stirring, washing, drying and crushing the hydrothermal treatment product in the step b) to obtain powder;
d) Adding dilute nitric acid and sesbania powder into the powder obtained in the step c), extruding strips, drying, heating to 530 ℃ at the speed of 1.5 ℃/min, and roasting for 6 hours to obtain a catalyst precursor; the adding amount of the sesbania powder is 2 percent of the mass of the powder, and the dilute nitric acid is obtained by diluting concentrated nitric acid accounting for 2 percent of the mass of the powder with water according to the proportion of 1;
e) Taking 340.6g of ammonium metatungstate according to the content of W oxide, soaking the catalyst precursor obtained in the step d) for 24 hours by adopting a W metal compound solution prepared by an isometric soaking method, then drying at a constant temperature of 90 ℃ for 1 hour, finally drying at a constant temperature of 130 ℃ for 24 hours, heating to 580 ℃ at a speed of 1.8 ℃/min after drying, and roasting for 4 hours to obtain the Fischer-Tropsch wax hydroconversion catalyst.
The present invention is described in detail with reference to the above embodiments, and those skilled in the art will understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.

Claims (9)

1. A preparation method of a catalyst for Fischer-Tropsch wax hydroconversion is characterized by comprising the following steps:
the catalyst for Fischer-Tropsch synthesis wax hydroconversion comprises the following components in percentage by mass: 5 to 9 percent of Ni metal compound calculated by oxide, 21 to 25 percent of W metal compound calculated by oxide, 5 to 25 percent of Y-shaped molecular sieve, 0 to 30 percent of isomerization molecular sieve and Al 2 O 3 20 to 65 percent;
the preparation method comprises the following steps;
a) Mixing alumina and water, pulping, stirring uniformly, adding a Y-type molecular sieve, adjusting the pH to 9 to 12 with ammonia water, stirring fully, adding a Ni metal compound, stirring uniformly, and standing for 8 to 24h to obtain a mixture;
b) Placing the mixture obtained in the step a) in a closed reaction kettle for hydrothermal treatment, wherein the hydrothermal treatment temperature is 60-200 ℃, the pressure is 0.1-2.0 MPa, the stirring speed is 100-1000r/min, and the time is 8-36h;
c) Stirring the hydrothermal treatment product in the step b), cooling to room temperature, adding an isomerization molecular sieve, stirring for 1-2h, filtering, washing, drying and crushing to obtain powder;
d) Adding dilute nitric acid and sesbania powder into the powder obtained in the step c), extruding, drying, heating to 500-550 ℃ at the speed of 1.5-2.5 ℃/min, and roasting for 3-6 h to obtain a catalyst precursor; the addition amount of the sesbania powder is 1 to 3 percent of the mass of the powder, and the dilute nitric acid is obtained by diluting 1 to 2 percent of the mass of the powder with water according to the proportion of 1 (60 to 90); the drying process comprises the steps of drying at 60 to 120 ℃ for 12 to 24h, and then drying at 150 to 250 ℃ for 8 to 24h;
e) Soaking the catalyst precursor obtained in the step d) for 12 to 24h by using a W metal compound solution prepared by an isometric soaking method, drying, heating to 550 to 600 ℃ at the speed of 1.0 to 2.0 ℃/min, and roasting for 3 to 6h to obtain the Fischer-Tropsch wax hydroconversion catalyst.
2. The process for the preparation of a catalyst for the hydroconversion of fischer-tropsch wax as claimed in claim 1, wherein: the specific surface area of the alumina mesopores in the step a) is 250 to 380m 2 The pore volume of the mesopores is 0.75 to 0.95mL/g, and the average pore diameter of the mesopores is 65 to 80nm;
the Ni metal compound in the step a) is one or a mixture of nickel nitrate, nickel chloride and nickel acetate.
3. The method of claim 1, wherein the catalyst comprises: and c, drying at 60-90 ℃ for 1-6 h, and then drying at 100-135 ℃ for 8-24h.
4. The method of claim 1, wherein the catalyst comprises: the W metal compound in the step e) is one or a mixture of ammonium metatungstate, ammonium tungstate and tungsten hexachloride;
the drying process in the step e) comprises the steps of drying at a constant temperature of 60-90 ℃ for 1-6 h, and then drying at a constant temperature of 100-150 ℃ for 8-24h.
5. The process for the preparation of a catalyst for the hydroconversion of fischer-tropsch wax as claimed in claim 1, wherein: the three stirring times in the step a) are all 1 to 4 hours.
6. A catalyst for the hydroconversion of fischer-tropsch wax prepared according to the preparation process of claim 1, wherein: comprises the following components in percentage by mass: 5 to 9 percent of Ni metal compound calculated by oxide, 21 to 25 percent of W metal compound calculated by oxide, 5 to 25 percent of Y-shaped molecular sieve, 0 to 30 percent of isomerization molecular sieve and Al 2 O 3 The content is 20 to 65 percent.
7. A catalyst for the hydroconversion of Fischer-Tropsch wax according to claim 6, characterised in that: the isomerization molecular sieve is one or a mixture of two of SAPO-11 molecular sieve, ZSM-22 molecular sieve, ZSM-5 molecular sieve and beta molecular sieve.
8. A catalyst for the hydroconversion of Fischer-Tropsch wax according to claim 6 or claim 7, characterised in that: the specific surface area of the catalyst is 185 to 300m 2 The mesoporous volume is 0.35 to 0.55cm 3 The average pore diameter of the mesopores is 32 to 70nm;
NH of the catalyst 3 The proportion of medium and strong acid and weak acid with the temperature of less than 350 ℃ in the TPD acidity measurement result accounts for 80 to 95 percent of the total acid.
9. Use of a catalyst according to claim 6 for the hydroconversion of fischer-tropsch wax for the preparation of a clean fuel oil product by hydrocracking fischer-tropsch wax.
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