CN108421563B - Hydroisomerization catalyst and preparation method thereof - Google Patents

Hydroisomerization catalyst and preparation method thereof Download PDF

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Publication number
CN108421563B
CN108421563B CN201710080814.4A CN201710080814A CN108421563B CN 108421563 B CN108421563 B CN 108421563B CN 201710080814 A CN201710080814 A CN 201710080814A CN 108421563 B CN108421563 B CN 108421563B
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carrier
catalyst
complexing agent
organic
preparation
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CN108421563A (en
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张乐
毕云飞
聂红
李明丰
丁石
刘清河
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • B01J37/024—Multiple impregnation or coating
    • 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
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Abstract

The invention relates to a hydroisomerization catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: (1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst; (2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting; wherein the carrier contains an inorganic refractory oxide and a mesoporous molecular sieve. The hydroisomerization catalyst prepared by the method has higher activity and isomerization selectivity.

Description

Hydroisomerization catalyst and preparation method thereof
Technical Field
The present invention relates to a process for the preparation of a hydroisomerization catalyst and to a hydroisomerization catalyst prepared by this process.
Background
Increasing awareness of environmental concerns and stricter environmental regulations are forcing the oil refining community to focus more on the development of clean fuel production technologies. The future market of vehicle fuel tends to be ultra-low sulfur, and fuel which can not meet the emission standard can not enter the market. Hydrogenation technology is used as an effective desulfurization means and plays an increasingly important role in the production of clean vehicle fuels, wherein a high-efficiency hydrogenation catalyst is a core technology of the hydrogenation technology, and therefore, the development of a novel hydroisomerization catalyst with higher activity and selectivity is one of the most urgent needs of the oil refining industry.
Hydroisomerization catalysts are typically prepared by impregnation, i.e., by impregnating a support with a solution containing the desired active component (e.g., Ni, Mo, Co, W, etc.), followed by drying, calcination, or no calcination.
CN103551162A discloses a diesel oil hydrodesulfurization and denitrification catalyst, which comprises a carrier, an auxiliary agent and active metal; the carrier being Al2O3-ZrO2-TiO2-SiO2A multi-oxide composite support; the auxiliary agent is phosphorus; nickel, cobalt, molybdenum and tungsten are taken as active components; the catalyst comprises the following components in percentage by weight based on the weight of the catalyst: 1-6 wt% of cobalt oxide in terms of oxide; 1-15 wt% of nickel oxide, 2-12 wt% of molybdenum oxide, 12-35 wt% of tungsten oxide and 1.5-5 wt% of auxiliary agent phosphorus pentoxide; the pore volume of the catalyst is not less than 0.2mL/g, and the specific surface area is not less than 140m2(ii)/g, mechanical strength is not less than 15N/mm; the proportion of each component in the composite carrier in the carrier is respectively as follows: 2-15 wt% of titanium oxide, 2-20 wt% of silicon oxide and 5-15 wt% of zirconium oxide; the balance being alumina. The catalyst is prepared by a step impregnation method: the co-immersion liquid was divided into two equal volumes, the carrier was impregnated in two steps, and calcination was performed after completion of each step of impregnation.
CN103657667A discloses a preparation method of a novel heavy oil hydrodemetallization catalyst with a macroporous structure, which is characterized by comprising the following steps: the method specifically comprises the following steps: 1) preparing aluminum sol; 2) mixing asphalt residue powder and alumina sol to prepare a macroporous structure catalyst carrier; 3) impregnating the molded catalyst carrier by adopting an isometric fractional two-step impregnation method; finally, the catalyst is prepared. The two-step impregnation method of the preparation method comprises the following specific steps: the first step is to impregnate Mo, the second step is to impregnate Ni, and the impregnating solution does not contain organic complexing agent.
The two-step impregnation process provided by the prior art results in an increase in activity of the hydroisomerization catalyst, but to a limited extent.
CN100469440C, CN102909027A disclose that Ni-W-Mo ternary metal hydroisomerization catalysts are prepared by introducing organic dispersing agents or complexing agents (such as ethylene glycol, oxalic acid, citric acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, etc.) into the carrier during the preparation process. Compared with the catalyst provided by the existing method, the obtained catalyst has better hydrofining performance. There is still a need to further improve the catalyst activity.
Disclosure of Invention
Aiming at the defect of low activity of the prior art hydroisomerization catalyst, the invention provides a novel preparation method of the hydroisomerization catalyst and the hydroisomerization catalyst prepared by the method, and the hydroisomerization catalyst prepared by the method has high activity and isomerization selectivity.
The inventor of the invention finds that the complexing impregnation technology can weaken the interaction between the active component and the carrier, improve the metal dispersion degree, change the metal vulcanization sequence, form more active phases and improve the number of active centers by introducing the complexing agent in the impregnation process and drying at low temperature. However, because low-temperature drying is adopted in the complex impregnation technology, and a high-temperature roasting process is not carried out, the metal compound still exists on the surface of the carrier in the form of metal salt, and the acting force of the active component and the carrier is weaker, so that metal is continuously aggregated in the reaction process under the conditions of high temperature and high pressure and hydrogenation reaction of a severe raw material, the auxiliary effect is weakened, the number of active centers is reduced, the intrinsic activity is reduced, and the activity and the stability of the catalyst are reduced. The catalyst prepared by the high-temperature roasting method has good stability, but the acting force of the active component and the carrier is strong, the intrinsic activity of the active center is low, and the dispersion and the blocking action of the complexing agent are avoided, so that the active component has large lamella, the number of the active centers is small, and the activity is low.
The inventor of the invention further discovers through research that the catalyst is prepared through a two-step impregnation method, the first step impregnation and the second step impregnation are respectively used for introducing a hydrogenation metal active component and an organic complexing agent, the organic complexing agent is added in the first step impregnation process and is converted into carbon through roasting, the activity of the catalyst can be improved, the high activity of the catalyst can be effectively maintained for a long time, and the service life of the catalyst is greatly prolonged. Presumably, the reason for this is that the organic complexing agent added in the first impregnation step hinders the aggregation of the active metal during the calcination process and makes it more uniformly dispersed; meanwhile, the metal compound can be converted into metal oxide by roasting after the first step of impregnation, and the organic complexing agent is converted into carbon, so that the combination between the active metal and the carrier is firmer, and the activity and the stability of the catalyst are improved. The organic complexing agent added in the second step of dipping process covers the surface of the catalyst, so that the aggregation of active metal in the vulcanization process can be effectively prevented, the metal dispersity is improved, and the formation of a II-type active phase with higher activity and the formation of more active centers are facilitated, so that the activity of the catalyst is further enhanced. Therefore, the technology can effectively overcome the technical defects of the conventional impregnation method and the existing complex impregnation method.
Thus, the present invention also provides a process for the preparation of a hydroisomerization catalyst comprising the steps of:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the carrier contains an inorganic refractory oxide and a mesoporous molecular sieve.
In addition, the method of the invention also provides a hydroisomerization catalyst prepared by the method.
The hydroisomerization catalyst prepared by the method has high catalytic activity, selectivity and activity stability, for example, the conversion rate of the catalyst S3 prepared by the method is 45%, the isomerization selectivity is 64.6%, which is far higher than the 35.4% conversion rate and 52.6% isomerization selectivity of the reference agent D2 prepared by the conventional impregnation method, and the hydroisomerization catalyst prepared by the method has higher hydrogenation activity and isomerization selectivity. And the method provided by the invention is simple to operate, so that the method has a good industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to the present invention, there is provided a process for preparing a hydroisomerization catalyst, comprising the steps of:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the carrier contains an inorganic refractory oxide and a mesoporous molecular sieve.
According to the present invention, it is preferable that the calcination conditions in the step (1) are such that the content of char in the semi-finished catalyst is 0.04 to 0.4% by weight based on the total amount of the semi-finished catalyst.
In the present invention, the above-mentioned carbon content can be obtained by controlling the calcination temperature in the calcination conditions and the amount of introduction of a combustible gas, which may be one or more of various gases having an oxygen content of not less than 20% by volume, such as air, oxygen, and a mixed gas thereof.
The combustible gas is introduced at a rate of not less than 0.2 liter/hour per gram of the carrier. On one hand, the combustible gas is introduced to meet the combustion condition, so that the salt of the active metal component is converted into oxide, and the organic complexing agent is converted into carbon; on the other hand, carbon dioxide and water formed by combustion and other components can be discharged to avoid the deposition on the catalyst to cause vacancy obstruction of the active phase.
Preferably, the combustible gas is introduced at a rate of 0.2 to 20 liters/hour, preferably 0.3 to 10 liters/hour, per gram of the support.
According to the present invention, preferably, the temperature of the calcination in step (1) is 350-. Controlling the roasting temperature within the range can ensure that the organic complexing agent can form carbon on the carrier within the content range to obtain the semi-finished catalyst.
According to the present invention, preferably, the molar ratio of the organic complexing agent to the metal active component in step (1) is 0.03-2: 1, preferably 0.08 to 1.5:1, more preferably 0.1 to 1.4: 1, more preferably 0.5 to 1.3: 1.
according to the present invention, preferably, the molar ratio of the organic complexing agent in the step (1) to the organic complexing agent in the step (2) is 1: 0.25 to 4, preferably 1: 0.5-2.
In the present invention, the organic complexing agents in step (1) and step (2) may be the same or different, and preferably, the organic complexing agents are selected from one or more of oxygen-containing and/or nitrogen-containing organic substances.
The oxygen-containing organic matter is preferably selected from one or more of organic alcohol and organic acid.
The organic alcohol is preferably a dihydric or higher polyhydric alcohol, more preferably a polyhydric alcohol having 2 to 6 carbon atoms or an oligomer or polymer thereof, such as one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, and butanediol. The molecular weight of the polyethylene glycol is preferably 200-1500.
The organic acid is preferably a compound containing one or more COOH groups and C2-C7, and specifically can be one or more of acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid.
The nitrogen-containing organic matter is preferably selected from one or more of organic amine and organic ammonium salt.
The organic amine is preferably a compound containing one or more NH groups and having a carbon number of from 2 to 7, and can be a primary amine, a secondary amine or a tertiary amine, and particularly preferably ethylenediamine.
The organic ammonium salt is preferably EDTA.
In particular, the organic complexing agent is particularly preferably one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is preferably 200-.
Preferably, the organic complexing agent in step (1) is selected from one or more of organic acids, more preferably, the organic complexing agent in step (1) is selected from one or more of fatty acids of C2-C7. By using an organic acid as the organic complexing agent in step (1), a hydroisomerization catalyst having higher activity can be obtained.
In the present invention, the drying conditions are not particularly limited, and may be various drying conditions commonly used in the art, and the drying conditions in the step (1) and the step (2) may be the same or different.
Preferably, the drying temperature in the step (1) is 100-250 ℃, and the time is 1-12 h.
Preferably, the drying temperature in the step (2) is 100-200 ℃, and the time is 1-12 h.
According to the present invention, the hydrogenation metal active component is preferably used in an amount such that the hydrogenation metal active component is contained in an amount of 10 to 60 wt%, preferably 15 to 50 wt%, and more preferably 20 to 40 wt%, in terms of oxide, based on the total amount of the hydroisomerization catalyst.
According to the present invention, it is preferable that the concentration of the water-soluble salt of the hydrogenation metal active component is 0.2 to 8mol/L, preferably 0.2 to 5mol/L, and more preferably 0.2 to 2mol/L, in terms of the metal element. The concentrations herein are the respective concentrations of the water-soluble salts of the various hydrogenation metal active components, not the total concentration.
The water-soluble salt of the hydrogenation metal active component can be various water-soluble compounds with the solubility meeting the loading requirement or capable of forming the hydrogenation metal active component with the solubility meeting the requirement in water in the presence of a cosolvent, and can be one or more of nitrate, chloride, sulfate and carbonate, and is preferably nitrate.
According to the invention, preferably, the hydrogenation metal active component comprises at least one element selected from the group VIB metals and at least one element selected from the group VIII metals.
According to the invention, the group VIB metal element is preferably molybdenum and/or tungsten.
According to the invention, the group VIII metal element is preferably cobalt and/or nickel.
According to the present invention, preferably, the group VIB metal element-containing compound may be selected from one or more of ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide, and tungsten oxide.
The group VIII metal element-containing compound may be one or more selected from the group consisting of group VIII metal nitrates, group VIII metal chlorides, group VIII metal sulfates, group VIII metal formates, group VIII metal acetates, group VIII metal phosphates, group VIII metal citrates, group VIII metal oxalates, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal phosphides, group VIII metal sulfides, group VIII metal aluminates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.
Preferably, the group VIII metal element-containing compound is selected from one or more of group VIII metal oxalates, group VIII metal nitrates, group VIII metal sulfates, group VIII metal acetates, group VIII metal chlorides, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.
The group VIII metal element-containing compound may be selected from, but is not limited to, one or more of nickel nitrate, nickel sulfate, nickel acetate, nickel hydroxycarbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt hydroxycarbonate, cobalt chloride, and nickel chloride.
According to the present invention, the supporting manner of the hydrogenation metal active component is not particularly limited.
According to the present invention, preferably, the loading of the hydrogenation metal active component is to load the hydrogenation metal active component on the carrier by an impregnation method.
According to the present invention, the order of loading the hydrogenation metal active components on the carrier is not particularly limited, and all the hydrogenation metal active components may be loaded on the carrier in common by impregnating the carrier with a solution containing a plurality of water-soluble salts, or the hydrogenation metal active components may be sequentially loaded on the carrier by preparing the water-soluble salt-containing solutions to impregnate the carrier stepwise, respectively. When stepwise impregnation is used, it is preferred to dry and preferably to calcine further after each impregnation. The manner and conditions of drying and firing may be selected with reference to the prior art.
According to the present invention, the supporting method of the organic complexing agent is not particularly limited. The organic complexing agent can be prepared into an impregnation liquid impregnation carrier together with one or more of water-soluble salts of the hydrogenation metal active component, or can be prepared into the impregnation liquid impregnation carrier separately, preferably the former.
According to the present invention, the impregnation method may be an equal volume impregnation or a supersaturation impregnation, the temperature of the impregnation is not particularly limited, and may be various temperatures that can be attained by the impregnation solution, and the time of the impregnation is not particularly limited as long as the required amount of the desired components can be supported, for example: the impregnation temperature may be 15-60 deg.C and the impregnation time may be 0.5-5 hours.
According to the present invention, the support contains an inorganic refractory oxide and a mesoporous molecular sieve. According to the present invention, the term "inorganic refractory oxide" means an inorganic oxygen-containing compound having a decomposition temperature of not less than 300 ℃ under an oxygen or oxygen-containing atmosphere (e.g., a decomposition temperature of 300-1000 ℃).
According to the present invention, the inorganic refractory oxide may be various inorganic refractory oxides commonly used in the art. The inorganic heat-resistant oxide may be selected from, for example, one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
According to a preferred embodiment of the present invention, the inorganic refractory oxide is alumina, and further preferably the support is alumina and a mesoporous molecular sieve (i.e., an alumina-mesoporous molecular sieve).
According to a preferred embodiment of the present invention, the mesoporous molecular sieve is present in the support in an amount of 2 to 75 wt.%, preferably 5 to 60 wt.%, based on the total amount of the support.
According to a preferred embodiment of the invention, the support is an alumina and a mesoporous molecular sieve, the content of the mesoporous molecular sieve in the support being 2-75 wt.%, preferably 5-60 wt.%, and the content of alumina being 25-98 wt.%, preferably 40-95 wt.%, based on the total amount of the support.
In the present invention, the mesoporous molecular sieve refers to a zeolite molecular sieve having a ten-membered ring pore structure, preferably one or more selected from SAPO-11, SAPO-31, SAPO-41, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57. Further preferred is one or more of SAPO-11, ZSM-5, ZSM-22 and the like.
Wherein the alumina is further preferably alumina obtained by calcining a hydrated alumina (aluminum hydroxide) colloidal composite.
A preferred method for preparing the alumina-mesoporous molecular sieve is to mix and calcine alumina and/or alumina precursors and the mesoporous molecular sieve. The carrier can be made into various molding matters which are easy to operate according to different requirements, such as microspheres, spheres, tablets or strips. The molding may be carried out by a conventional method, and for example, it may be a method of mixing the alumina and/or its precursor with the mesoporous molecular sieve, extruding into a rod, and calcining. Wherein, the precursor of the alumina can be selected from one or more of various hydrated alumina and alumina sol. During extrusion molding, a proper amount of extrusion aid and/or adhesive can be added, and then extrusion molding is carried out. The kinds and amounts of the extrusion aid and the peptizing agent are well known to those skilled in the art and are not described herein. The roasting adopts the method and conditions which are commonly used in the field, for example, the roasting temperature can be 350-650 ℃; preferably 400 ℃ and 600 ℃, and the calcination time is 2-6 hours, preferably 3-5 hours.
The catalyst of the present invention is generally used by reducing it to a metallic state in a hydrogen atmosphere, and the reduction method may be a method known to those skilled in the art. Such as: with V (hydrogen): and (3) performing temperature rise reduction on the V (catalyst) at the speed of 1-5 ℃/min and at the temperature of 300-400 ℃ for 3-5 h.
The invention also provides a hydroisomerization catalyst prepared by the preparation method.
Compared with the catalyst prepared by the conventional method, the hydroisomerization catalyst prepared by the method provided by the invention has higher hydrogenation activity and isomerization selectivity, and can be applied to the isomerization reaction of various raw oil containing straight-chain alkane, including but not limited to the following reactions: hydrocracking tail oil isomerization pour point depression, biological aviation kerosene freezing point depression, Fischer-Tropsch synthetic wax pour point depression and the like.
In the present invention, the dry weight means the weight measured by baking a sample at 600 ℃ for 4 hours.
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
In the following examples, the contents of the respective elements in the catalyst were analyzed and measured by a 3271E type X-ray fluorescence spectrometer, manufactured by japan food and electronics industries co. The carbon content in the catalyst semi-finished product was analyzed and measured using an EMIA-320V carbon sulfur analyzer manufactured by HORIBA, Japan. Unless otherwise specified, the alumina used in the examples was RPB-90 from the midpetrochemical ChangLing catalyst division and the silica-alumina carrier was Siral40 from Condea, Germany.
Preparation example 1
Preparing a mesoporous molecular sieve: SAPO-11 molecular sieve was synthesized according to the procedure of example 16 in US 4440871. 230.6g of phosphoric acid (85% by weight) was weighed, 440.0g of distilled water and 144.0g of pseudoboehmite (dry rubber powder produced by catalyst works of Changling refinery, 71% by weight on dry basis) were added thereto, and the mixture was uniformly stirred to obtain a mixture P1. 649.2g of a 40 wt% aqueous solution of hydroxytetran-butylamine and 26.0g of fumed silica (silica content 92.8 wt%, water content 7.2 wt%) were weighed and stirred uniformly to obtain a mixture P2. The mixtures P1 and P2 were mixed and 102.0g of di-n-propylamine were added with stirring to give a reaction mixture. And (3) putting the reaction mixture into a polytetrafluoroethylene sealed reaction kettle, crystallizing for 24 hours at 200 ℃, filtering, washing a solid product to be neutral, and drying at 120 ℃ to obtain the SAPO-11 molecular sieve (net content is 85.0 wt%).
Preparing an alumina-mesoporous molecular sieve carrier: 150 g of SAPO-11 molecular sieve, 850 g of dry-based pseudo-boehmite (trade name SD powder, dry basis 69 wt%) produced by Shandong aluminum works and 30 g of sesbania powder are mixed, extruded into trilobal strips with the circumscribed circle diameter of 1.6 mm, dried at 120 ℃ and roasted at 550 ℃ for 3 hours to prepare a carrier Z1, and the content of the mesoporous molecular sieve in the carrier Z1 is 15.0 wt%.
Preparation example 2
50 g of SAPO-11 molecular sieve, 950 g of dry-based pseudo-boehmite (product name SD powder produced by Shandong aluminum works, dry basis 69 wt%) and 30 g of sesbania powder are mixed, extruded into trilobal strips with the circumscribed circle diameter of 1.6 mm, dried at 120 ℃ and roasted at 550 ℃ for 3 hours to prepare a carrier Z2, and the content of the mesoporous molecular sieve in the carrier Z2 is 5.0 wt%.
Preparation example 3
600 g of SAPO-11 molecular sieve, 400 g of dry-based pseudo-boehmite (trade name SD powder, dry basis 69 wt%) produced by Shandong aluminum works and 30 g of sesbania powder are mixed, extruded into trilobal strips with the circumscribed circle diameter of 1.6 mm, dried at 120 ℃ and roasted at 550 ℃ for 3 hours to prepare a carrier Z3, and the content of the mesoporous molecular sieve in the carrier Z3 is 60.0 wt%.
Example 1
Respectively weighing 54 g of molybdenum trioxide, 19 g of basic cobalt carbonate, 20 g of phosphoric acid and 20 g of citric acid, putting the molybdenum trioxide, 19 g of basic cobalt carbonate, 20 g of phosphoric acid and 20 g of citric acid into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of carrier Z1 by adopting a saturated impregnation method for 2 hours, drying at 120 ℃ for 2 hours, roasting at 400 ℃ for 2 hours in an air flow-in state, wherein the air flow-in speed is 2 liters/hour relative to each gram of carrier to obtain a semi-finished catalyst Z1-S1, wherein the carbon content of Z1-S1 is shown in Table 1; adding 5g of ethanol into 150 g of deionized water, stirring to obtain a clear solution, soaking the Z1-S1 in the solution for 2 hours by adopting a saturated soaking method, and then drying the solution for 3 hours at 110 ℃ to obtain the catalyst S1. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S1 is shown in Table 1.
Comparative example 1
A hydroisomerization catalyst was prepared by the same method as in example 1, except that the hydroisomerization catalyst S1 obtained in example 1 was calcined at 400 ℃ for 3 hours to obtain catalyst D1, and the content of the hydrogenation metal active component in the catalyst D1, in terms of oxide based on the total amount of D1, is shown in Table 1.
Example 2
Respectively weighing 54 g of molybdenum trioxide, 21 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid, putting the molybdenum trioxide, 21 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid into 140 g of deionized water, heating, stirring and dissolving to obtain a clear impregnation solution, impregnating 200 g of carrier Z2 by adopting a saturated impregnation method for 2 hours, then drying at 150 ℃ for 2 hours, roasting the carrier at 360 ℃ for 3 hours in an air flow-in state, wherein the air flow-in speed is 10 liters/hour relative to each gram of carrier to obtain a semi-finished catalyst Z2-S2, wherein the carbon content of Z2-S2 is shown in Table 1; adding 30 g of citric acid into 150 g of deionized water, stirring to obtain a clear solution, soaking Z2-S2 in the solution for 2 hours by adopting a saturated soaking method, and then drying for 3 hours at 150 ℃ to obtain the hydroisomerization catalyst S2. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S2 is shown in Table 1.
Example 3
Respectively weighing 30 g of nickel nitrate, 45 g of ammonium metatungstate (hydrate, molecular weight of 3037, the same below) and 15 g of oxalic acid, putting the nickel nitrate, the ammonium metatungstate and the oxalic acid into 140 g of deionized water, stirring and dissolving to obtain a clear solution, dipping 200 g of carrier Z3 by adopting a saturated dipping method for 2 hours, then drying the carrier Z3 for 2 hours at 120 ℃, then roasting the carrier Z for 4 hours under the condition of introducing air flow, wherein the roasting temperature is 450 ℃, and the air introduction rate is 0.3 liter/hour relative to each gram of carrier to obtain a semi-finished catalyst Z3-S3, wherein the carbon content of Z3-S3 is shown in Table 1; 10 g of diethylene glycol is put into 150 g of deionized water, stirred to obtain a clear solution, and the solution is used for soaking Z3-S3 for 2 hours by adopting a saturated soaking method, and then dried for 6 hours at 120 ℃ to obtain a catalyst S3. The content of the hydrogenation metal active component in terms of oxide based on the total amount of S3 is shown in Table 1.
Comparative example 2
30 g of nickel nitrate, 45 g of ammonium metatungstate, 15 g of oxalic acid and 10 g of diethylene glycol are respectively weighed and put into 140 g of deionized water, stirred and dissolved to obtain a clear solution, 200 g of carrier Z3 is soaked in the solution by adopting a saturated soaking method for 2 hours, and then dried for 2 hours at 120 ℃ to obtain the catalyst D2. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D2, is shown in table 1.
Comparative example 3
A hydroisomerization catalyst was prepared by following the procedure of example 3, except that the support Z3 was replaced by alumina, giving catalyst D3. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D3, is shown in table 1.
Comparative example 4
A hydroisomerization catalyst was prepared by the method of example 3, except that the support Z3 was replaced by the same weight of silica-alumina support, giving catalyst D4. The content of the hydrogenation metal active component, calculated as the oxide, based on the total amount of D4, is shown in table 1.
Example 4
A hydroisomerization catalyst was prepared in the same manner as in example 3, except that the active metal component was impregnated into the carrier, and then calcined at 480 c for 6 hours. The content of carbon in the obtained catalyst semi-finished product is shown in table 1, and the content of the hydrogenation metal active component in the obtained catalyst S4 is shown in table 1 in terms of oxide based on the total amount of S4.
Example 5
A hydroisomerization catalyst was prepared by the same method as in example 3, except that the air feed rate was 1.0 liter/hr per gram of the carrier at the time of calcination, and the content of the hydrogenation metal active component in the catalyst S5 based on the total amount of S5 in terms of oxide was as shown in Table 1.
Example 6
A hydroisomerization catalyst was prepared by the same method as in example 3, except that the ratio of the amount of the organic complexing agent used in step (1) to that used in step (2) was changed from 15 g: 10 g is changed into 5 g: 20 g of the catalyst S6 was obtained, and the content of the hydrogenation metal active component in terms of oxide based on the total amount of S6 was as shown in Table 1.
TABLE 1
Figure BDA0001225831890000141
Figure BDA0001225831890000151
Test example 1
In this test example, the catalytic activity and selectivity of the hydroisomerization catalyst prepared by the method of the present invention and the hydroisomerization catalyst provided in the comparative example were evaluated by the following methods, and the evaluation results are shown in table 2 below.
The evaluation of the catalytic performance of the catalyst was carried out on a high-pressure continuous micro-device. 1.5g of 40-60 mesh catalyst S1(S2 or S3 or S4 or S5 or S6 or D1 or D2 or D3 or D4) is loaded into a constant temperature zone of a fixed bed micro-reactor, hydrogen is introduced, the temperature is raised to 360 ℃, reduction is carried out for 4h, then the temperature is reduced to the reaction temperature, n-decane is started to be added, and the mass space velocity of reaction feeding is 2.0h-1The hydrogen-hydrocarbon molar ratio was 3000. Sampling analysis was started after 1.5h of stabilization.
The product was quantitatively analyzed by a TRACE GC-2000 gas chromatograph from CE. The chromatographic column adopts a capillary column, and the chromatographic conditions are as follows: capillary column (OV-17, nonpolar column), inner diameter 0.32mm, length 25m, split ratio 40:1, temperature programming; FID detector. Conversion and selectivity were calculated from the results of the analysis of the gas and liquid samples. The results of hydroisomerization evaluation of the catalysts prepared in the respective examples and comparative examples are shown in table 2.
TABLE 2
Figure BDA0001225831890000152
Figure BDA0001225831890000161
The results in table 2 show that the catalyst provided by the present invention has significantly better hydrogenation activity and hydroisomerization selectivity than hydroisomerization catalysts prepared by prior methods.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (22)

1. A process for the preparation of a hydroisomerization catalyst comprising the steps of:
(1) loading water-soluble salt of a hydrogenation metal active component and an organic complexing agent on a carrier by adopting an impregnation method, and then drying and roasting to obtain a semi-finished catalyst, wherein the roasting condition is that the carbon content in the semi-finished catalyst is 0.03-0.5 wt% based on the total amount of the semi-finished catalyst;
(2) taking a solution containing an organic complexing agent as an impregnation solution, impregnating the semi-finished catalyst obtained in the step (1), and then drying without roasting;
wherein the carrier contains an inorganic refractory oxide and a mesoporous molecular sieve.
2. The production process according to claim 1, wherein the calcination conditions in the step (1) are such that the amount of the char in the semi-finished catalyst is 0.04 to 0.4% by weight based on the total amount of the semi-finished catalyst.
3. The preparation method as claimed in claim 1, wherein the calcination in step (1) is carried out under the condition of gas introduction, the calcination temperature is 350-500 ℃, and the calcination time is 0.5-8 h; the gas is introduced at a rate of 0.2 to 20 liters per hour per gram of the carrier.
4. The preparation method as claimed in claim 3, wherein the calcination in step (1) is carried out under the condition of gas introduction, the calcination temperature is 360-450 ℃, and the calcination time is 1-6 h; the gas is introduced at a rate of 0.3 to 10 liters per hour per gram of the carrier.
5. The production method according to any one of claims 1 to 4, wherein in the step (1), the molar ratio of the organic complexing agent to the metal active component is from 0.03 to 2: 1.
6. the preparation method according to claim 5, wherein in the step (1), the molar ratio of the organic complexing agent to the metal active component is 0.08-1.5: 1.
7. the preparation method according to any one of claims 1 to 4, wherein the molar ratio of the organic complexing agent in the step (1) to the organic complexing agent in the step (2) is 1: 0.25-4.
8. The preparation method according to any one of claims 1 to 4, wherein the organic complexing agent in step (1) is the same as or different from the organic complexing agent in step (2), and the organic complexing agent in step (1) and step (2) is selected from one or more of oxygen-containing organic substances and/or nitrogen-containing organic substances.
9. The preparation method according to claim 8, wherein the oxygen-containing organic substance is selected from one or more of organic alcohol and organic acid, and the nitrogen-containing organic substance is selected from one or more of organic amine and organic ammonium salt.
10. The preparation method according to claim 8, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms.
11. The preparation method according to claim 9, wherein the organic complexing agent in step (1) is one or more of organic acids with 2-7 carbon atoms.
12. The production process according to any one of claims 1 to 4, wherein the hydrogenation metal active component is used in an amount such that the content of the hydrogenation metal active component is 10 to 60% by weight in terms of oxide based on the total amount of the hydroisomerization catalyst.
13. The production process according to claim 12, wherein the hydrogenation metal active component is used in an amount such that the content of the hydrogenation metal active component is 15 to 50% by weight in terms of oxide based on the total amount of the hydroisomerization catalyst.
14. The preparation method according to any one of claims 1 to 4, wherein the hydrogenation metal active component is at least one selected from group VIB metal elements and at least one selected from group VIII metal elements; the inorganic heat-resistant oxide is selected from one or more of alumina, silica, alumina-silica, titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia.
15. The production method according to claim 14, wherein the group VIB metal element is molybdenum and/or tungsten, and the group VIII metal element is cobalt and/or nickel.
16. The production method according to any one of claims 1 to 4, wherein the content of the mesoporous molecular sieve in the carrier is 2 to 75% by weight based on the total amount of the carrier.
17. The preparation method as claimed in claim 16, wherein the content of the mesoporous molecular sieve in the carrier is 5 to 60 wt% based on the total amount of the carrier.
18. The production method according to any one of claims 1 to 4, wherein the carrier is alumina and a mesoporous molecular sieve, and the content of the mesoporous molecular sieve in the carrier is 2 to 75 wt% and the content of alumina is 25 to 98 wt%, based on the total amount of the carrier.
19. The process according to claim 18, wherein the carrier is alumina and a mesoporous molecular sieve, and the content of the mesoporous molecular sieve in the carrier is 5 to 60% by weight and the content of the alumina is 40 to 95% by weight, based on the total amount of the carrier.
20. The production method according to any one of claims 1 to 4, wherein the medium pore molecular sieve is a zeolite molecular sieve having a ten-membered ring pore structure.
21. The method of claim 20, wherein the mesoporous molecular sieve is selected from one or more of SAPO-11, SAPO-31, SAPO-41, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57.
22. A hydroisomerization catalyst prepared by the process of any of claims 1-21.
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