CN112705220A - Catalyst for carbon-tetra-alkyl hydrocarbon skeleton isomerization reaction and preparation method and application thereof - Google Patents

Catalyst for carbon-tetra-alkyl hydrocarbon skeleton isomerization reaction and preparation method and application thereof Download PDF

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CN112705220A
CN112705220A CN201911025457.7A CN201911025457A CN112705220A CN 112705220 A CN112705220 A CN 112705220A CN 201911025457 A CN201911025457 A CN 201911025457A CN 112705220 A CN112705220 A CN 112705220A
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catalyst
salt
temperature
zirconium
isomerization reaction
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CN112705220B (en
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刘波
吕建刚
邵益
王迪
周海春
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • 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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Abstract

The invention relates to a catalyst for a skeletal isomerization reaction of carbon-tetrahydrocarbon, which comprises the following components based on the total weight of the catalyst: 5-10 wt% of zirconium element; 0.2-4.5 wt% of aluminum element; 0.5-8.0 wt% of copper element; 0.5 wt% to 5 wt% elemental sulfur; and 73 wt% to 90 wt% of a silica support. The invention also provides a preparation method of the catalyst, which takes zirconium salt, aluminum salt and copper salt as raw materials and silicon dioxide as a carrier to prepare the catalyst by one-step treatment. The method does not additionally use ammonia water and other precipitants, greatly shortens the preparation process of the catalyst, and reduces the energy consumption. The invention also provides the application of the catalyst in the skeletal isomerization reaction of the carbon-tetraalkyl hydrocarbon, and the catalyst has higher catalytic activity and stability when being used in the skeletal isomerization reaction of the carbon-tetraalkyl hydrocarbon.

Description

Catalyst for carbon-tetra-alkyl hydrocarbon skeleton isomerization reaction and preparation method and application thereof
Technical Field
The invention belongs to the technical field of heterogeneous catalyst preparation, and particularly relates to a catalyst for a tetraalkyl carbon skeleton isomerization reaction, and a preparation method and application thereof.
Background
Commercial n-butane comes mainly from catalytic cracking units. In 2016, the yield of catalytic cracking by-product liquefied petroleum gas in China reaches 3504 ten thousand tons, about 35 percent of resources supply carbon four for deep processing, and the n-butane resources are rich. The alkylate production scale is largest in the C.sub.C. industry chain, and is used for the second time in the MTBE (methyl tert-butyl ether) production scale. With the vigorous popularization of urban natural gas, the consumption of liquefied gas in cities is greatly reduced, the price falls back, and the liquefied gas becomes a prime power for driving the carbon four deep processing project.
With the increasing strictness of the environmental protection requirement, the upgrading pace of gasoline quality is quickened in China, and the national V-standard gasoline is completely supplied in China from 1 month and 1 day in 2017. The main content of the gasoline standard upgrading in China is to meet the requirements of 'desulfurization, manganese reduction and olefin reduction' of gasoline under the condition of ensuring the octane number. The octane number of the gasoline is difficult to reach the standard by reducing the olefin and the aromatic hydrocarbon, so the development of high-octane number clean components for blending the gasoline is very critical. The hydrocarbon alkylation oil has the advantages of higher octane number, low volatility, no aromatic hydrocarbon and olefin, almost no sulfur and the like, and is very suitable for oil blending. One of the raw materials for producing hydrocarbon alkylation oil is isobutane, so that the development of an isobutane catalyst by skeletal isomerization of n-butane is of great significance for clean gasoline production.
The isomerization catalyst is generally of the platinum halide/alumina type, with gamma-Al2O3As carrier, during the operation, proper amount of chloride is required to be added into the raw materials continuouslyAnd (4) an auxiliary agent. The main problems of the technology are that the content of water and sulfur in the raw materials is strictly required to be less than 0.1ppm, and meanwhile, chlorine-containing substances generated in the reaction process are corrosive to equipment, so that the material cost and the maintenance cost of the equipment are increased, and the environment is polluted.
The n-butane skeletal isomerization catalyst using zirconia as a carrier does not contain chlorine, has loose requirements on the moisture content and the sulfur content of raw materials, can be regenerated, and is the development direction of the isomerization catalyst. As is known to all, the preparation process of the catalyst generally produces 'three wastes' pollution, which not only brings environmental protection pressure, but also increases the cost of the catalyst, therefore, the simple, convenient, efficient and clean preparation of the catalyst is an important proposition of industrial catalysis. The following patents disclose the preparation of zirconium oxide catalysts for isomerization of alkanes such as n-butane.
Patent CN1660973A discloses an isomerization method of C5, C6 alkane, the preparation process of the catalyst comprises: reacting the zirconium salt solution with an alkali solution to prepare zirconium hydroxide; mixing zirconium hydroxide and silica sol, and drying; containing SO4 2-Dipping and drying the solution; dipping in metal salt solution, drying and roasting.
Patent CN106732676A discloses a n-butane isomerization catalyst, which is prepared by coprecipitation of zirconium salt, gallium salt solution and ammonia water or urea aqueous solution, filtration, washing and drying to obtain a precursor, then impregnating other component solutions, drying and roasting to finally obtain ZrO2A catalyst.
Patents CN106140197A and CN106101797B disclose a solid super acidic catalyst, a preparation method thereof, and an isomerization method of light normal paraffin, wherein the catalyst is prepared by coprecipitation of ammonia water and a metal salt solution, filtering, washing, drying, impregnation step by step, drying, and finally roasting.
Patent CN107051420A discloses a preparation method of an n-butane isomerization catalyst, which comprises the following steps: hydrothermal reaction of ammonia water, zirconium salt, etc. to produce hydroxide; filtering, washing and drying the precipitate; containing SO4 2-Dipping and drying the solution; dipping in metal salt solution, drying and roasting.
Patent CN10822184A discloses an alkane isomerization catalyst and a preparation method thereof, comprising the preparation of zirconium hydroxide and SO4 2-Solution dipping, drying, mixing with silica sol for molding, nickel salt solution dipping, drying, roasting and other complex processes.
The patent CN10807998A discloses a catalyst for isomerization of C5 and C6 alkanes, a preparation method and an application thereof, and a coprecipitation method for preparing metal-doped ZrO2And (3) impregnating the precursor with oxygen tungstic acid and metal salt step by step, drying and roasting to obtain the catalyst.
Patent CN109772287A discloses a paraffin isomerization catalyst carrier and a preparation method thereof, and the catalyst and the preparation method thereof, wherein the preparation process involves a plurality of steps of reaction of zirconium salt and ammonia water, filtration, washing, drying, multiple dipping and drying, roasting and the like.
From the above publications, it is known that SO is currently used for the isomerization of tetrakacarbon4 2-/ZrO2The catalyst is prepared through the reaction of zirconium salt and ammonia water to produce zirconium hydroxide precipitate, filtering, washing and drying to obtain catalyst precursor Zr (OH)4Respectively soaking in a solution containing SO4 2-Solution and metal salt solution, and finally drying and roasting to obtain the catalyst. The method uses ZrO2The catalyst is a carrier, more zirconium salt is needed, the catalyst cost is high, the catalyst preparation steps are multiple, the flow is long, alkaline wastewater containing ammonia and the like is generated, a large amount of water is needed for washing precipitates to be neutral, the drying energy consumption is more for multiple times, and the defects are obvious.
Therefore, there is a need to develop a new catalyst for skeletal isomerization of tetraalkyl hydrocarbons, and a preparation method and applications thereof.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a catalyst for a skeletal isomerization reaction of a tetraalkyl hydrocarbon, and a preparation method and an application thereof, aiming at the defects of the prior art. The method takes silicon dioxide in silica sol as a carrier, and prepares the catalyst by zirconium salt, aluminum salt, copper salt and the silica sol through a one-step method, so that the dosage of the zirconium salt is obviously reduced, and the cost of the catalyst is reduced. In addition, in the preparation process of the catalyst, ammonia water and other precipitating agents are not additionally used, so that the preparation process of the catalyst is greatly shortened, and the energy consumption is reduced. The catalyst prepared by the method has higher catalytic activity and stability of the carbon-tetraalkyl hydrocarbon skeleton isomerization reaction at low temperature.
In order to solve the above technical problems, a first aspect of the present invention provides a catalyst for a skeletal isomerization reaction of a tetraalkyl hydrocarbon, comprising the following components, based on the total weight of the catalyst:
5-10 wt% of zirconium element;
0.2-4.5 wt% of aluminum element;
0.5-8.0 wt% of copper element;
0.5 wt% to 5.0 wt% elemental sulfur; and
50 to 90 wt% of a silica support.
In the above technical scheme, the catalyst comprises the following components by total weight of the catalyst:
6-8 wt% of zirconium element;
1-3.5 wt% of aluminum element;
1-3 wt% of copper element;
2-4 wt% of elemental sulfur; and
60 to 80 wt% of a silica support.
In a second aspect, the present invention provides a method for preparing a catalyst for a skeletal isomerization reaction of a tetraalkyl hydrocarbon according to the first aspect of the present invention, comprising the steps of:
s1, dissolving zirconium salt, aluminum salt and copper salt in water to form a solution;
s2, adding the solution into silica sol, and mixing to form a mixture;
s3, dehydrating, grinding and roasting the mixture to obtain the catalyst for the skeletal isomerization reaction of the tetrakacarbon.
In the above technical scheme, the silica sol is an ammonium silica sol, and preferably, the silica sol contains 30 wt% to 50 wt% of silica. In the inventionThe ammonium silica sol is used on the one hand because of its low sodium content and on the other hand because it contains a certain content of free NH3Can be complexed with the metal salt, and can help the dispersion of the metal salt to a certain extent.
In the above technical solution, the zirconium salt is selected from one or more of zirconium nitrate, zirconium oxychloride and a hydrate thereof, and preferably selected from at least one of zirconium nitrate and a hydrate thereof. The aluminum salt is at least one selected from aluminum sulfate and hydrates thereof. The copper salt is selected from one or more of copper sulfate, copper nitrate and hydrates thereof.
In the above-mentioned embodiment, the molar ratio n (Al)/n (Zr) of the aluminum salt to the zirconium salt is 0.2 to 2, preferably 0.3 to 2, in terms of the molar amount of the element. According to some specific embodiments of the invention, the molar ratio of the aluminum salt to the zirconium salt, n (al)/n (zr), is 0.261, 0.3, 0.565, 1.087, 1.652, 2, or any value within the range of any two of these values.
In the above embodiment, the molar ratio n (Cu)/n (Zr) of the copper salt to the zirconium salt is 0.2 to 1, preferably 0.3 to 1, in terms of the molar amount of the element. According to some specific embodiments of the invention, the molar ratio n (cu)/n (zr) of the copper salt to the zirconium salt is 0.260, 0.3, 0.39, 0.523, 0.565, 0.826, 1 or any value in the range consisting of any two of these values.
In the technical scheme, the amount of the zirconium salt is 5-20 wt% of the silica in terms of zirconia. According to some specific embodiments of the invention, the zirconium salt is used in an amount of 5 wt%, 8.86 wt%, 10.1 wt%, 11.8 wt%, 14.2 wt%, 15.7 wt%, 20 wt%, or any value within the range of any two numerical compositions, calculated as zirconia, of the silica.
In the above technical solution, in step S1, the amount of water is 2 to 4 times, preferably 2.5 to 3 times of the weight of the zirconium salt.
In the above technical solution, in step S2, the temperature of the mixing treatment is 70-90 ℃, and the time of the mixing treatment is 5-12 hours. In step S3, the dehydration treatment is performed at a temperature of 100-150 ℃; the roasting treatment method comprises the following steps: the temperature is raised to 600-700 ℃ roasting temperature for 3-10h, and the constant temperature is kept for 3-6 h.
In a third aspect, the present invention provides the use of a catalyst according to the first aspect of the invention or prepared according to the method of preparation of the second aspect of the invention in skeletal isomerization reactions for tetrakaolefins, in particular n-butane. Preferably the application comprises activating the catalyst prior to use. More preferably, the catalyst is activated using heating in an air stream. Further preferably, the temperature of the activation is 380-480 ℃, the time of the activation is 2-4h, and the flow rate of the air flow is 30-60 mL/min.
In the technical scheme, the isomerization reaction of the carbon-tetraalkyl hydrocarbon skeleton is carried out under the hydrogen condition; the reaction temperature is 180-220 ℃, the reaction pressure is 0.5-1.5MPa, and the volume space velocity of the carbon-tetralkyl hydrocarbon is 0.2-2h-1The hydrogen-hydrocarbon molar ratio is 0.1-1.0.
Compared with the prior art, the invention has the following beneficial effects:
compared with the existing method for preparing the catalyst by using zirconium dioxide as a carrier, the method takes silicon dioxide in silica sol as the carrier, and prepares the catalyst by using zirconium salt, aluminum salt, copper salt and silica sol through a one-step method (mixing, drying, dehydrating and roasting the substances), so that the use amount of the zirconium salt can be obviously reduced, and noble metals such as Pd, Pt and the like are not used, thereby obviously reducing the cost of the catalyst. Meanwhile, in the preparation process of the catalyst, no precipitator such as ammonia water is additionally used in the method, so that the preparation process of the catalyst is greatly shortened, and the energy consumption is reduced. The catalyst prepared by the method has higher catalytic activity and stability of the carbon-tetraalkyl hydrocarbon skeleton isomerization reaction at low temperature.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
The measurement method or the calculation method provided by the invention is as follows:
(1) the element content is as follows: determined by analysis with an ICP-AES instrument.
(2) N-butane conversion per pass (1-molar n-butane content in the product after the reaction) × 100%.
(3) The selectivity of isobutane was (molar content of isobutane in the product after the reaction/conversion per pass of n-butane) × 100%.
Examples
Example 1
10g of Zr (NO) are added3)4·5H2O、4.2g Al2(SO4)3·18H2O、4.8g CuSO4·5H2O was added to a 100mL beaker, 25mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 12 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 130 ℃, after fully grinding, placing the mixture in a muffle furnace, heating the mixture for 3h to 650 ℃ under the condition of introducing air, keeping the temperature for 4h, and naturally cooling the mixture to room temperature to obtain the n-butane skeletal isomerization reaction catalyst CASZ @ SiO2-1。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 2
10g of Zr (NO) are added3)4·5H2O、12.6g Al2(SO4)3·18H2O、1.5g CuSO4·5H2O was added to a 100mL beaker, 30mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 12 hr, and evaporating to remove most water. Continuously evaporating to remove water in a drying oven at 130 deg.C, grinding completely, and placing in a muffle furnaceHeating to 650 ℃ under the condition of introducing air, keeping the temperature for 5h, and naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-2。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 3
10g of Zr (NO) are added3)4·5H2O、8.4g Al2(SO4)3·18H2O、3.3g CuSO4·5H2O was added to a 100mL beaker, 25mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 45g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 12 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 130 ℃, after fully grinding, placing the dried product in a muffle furnace, heating the product for 10h to 650 ℃ under the condition of introducing air, keeping the temperature for 2h, and naturally cooling the product to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-3。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 4
10g of Zr (NO) are added3)4·5H2O、2.1g Al2(SO4)3·18H2O、3.0g Cu(NO3)2·3H2O was added to a 100mL beaker, followed by addition of 20mL of deionized water and heating and stirring at 70 ℃ to dissolve the solid. Fast speedThe above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with stirring. Stirring at 85 deg.C for 10 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 120 ℃, after fully grinding, placing the dried product in a muffle furnace, heating to 600 ℃ under the condition of introducing air, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-4。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 5
10g of Zr (NO) are added3)4·5H2O、8.4g Al2(SO4)3·18H2O、3.3g Cu(NO3)2·5H2O was added to a 100mL beaker, followed by addition of 35mL of deionized water, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 12 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 140 ℃, after fully grinding, placing the dried product in a muffle furnace, heating the product for 5h to 700 ℃ under the condition of introducing air, keeping the temperature for 5h, and naturally cooling the product to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-5。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 6
10g of Zr (NO) are added3)4·5H2O、4.2g Al2(SO4)3·18H2O、0.78g CuSO4·5H2O was added to a 100mL beaker, 25mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 85 deg.C for 10 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 140 ℃, fully grinding, placing in a muffle furnace, heating to 650 ℃ under the condition of introducing air, keeping the temperature for 4h, naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-6。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 7
10g of Zr (NO) are added3)4·5H2O、2.1g Al2(SO4)3·18H2O、0.78g CuSO4·5H2O was added to a 100mL beaker, 30mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 60g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 75 deg.C for 12h, and evaporating most of water. Continuously evaporating water in a drying oven at 120 ℃, after fully grinding, placing the dried product in a muffle furnace, heating to 700 ℃ under the condition of introducing air, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-7。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced for activation for 4h at the temperature of 420 ℃, the temperature is reduced to the reaction temperature, hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the tetracarbon hydrocarbon bodyThe volume space velocity is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 8
10g of Zr (NO) are added3)4·5H2O、4.2g Al2(SO4)3·18H2O、2.34g CuSO4·5H2O was added to a 100mL beaker, 30mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 70g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 12 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 120 ℃, after fully grinding, placing the dried product in a muffle furnace, heating to 650 ℃ under the condition of introducing air, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-8。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 9
10.0g of Zr (NO) was added3)4·5H2O、4.2g Al2(SO4)3·18H2O、3.12g CuSO4·5H2O was added to a 100mL beaker, 30mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 50g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 80 deg.C for 10 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 120 ℃, after fully grinding, placing the dried product in a muffle furnace, heating the product for 5h to 650 ℃ under the condition of introducing air, keeping the temperature for 4h, and naturally cooling the product to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-9。
The isomerization reaction of n-butane is carried out in a fixed bed reactor, catalyticallyThe loading of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetracarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 10
10g of Zr (NO) are added3)4·5H2O、4.2g Al2(SO4)3·18H2O、3.0g Cu(NO3)2·3H2O was added to a 100mL beaker, 25mL of deionized water was added, and the mixture was heated and stirred at 70 ℃ to dissolve the solid. The above solution was added dropwise to 80g of ammonium type silica sol (silica content 40 wt%) with rapid stirring. Stirring at 90 deg.C for 8 hr, and evaporating to remove most water. Continuously evaporating water in a drying oven at 140 ℃, fully grinding, placing in a muffle furnace, heating to 650 ℃ under the condition of introducing air, keeping the temperature for 5 hours, naturally cooling to room temperature to obtain the n-butane skeletal isomerization catalyst CASZ @ SiO2-10。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading amount of a catalyst (20-40 meshes) is 10mL, air (60mL/h) is introduced at the temperature of 420 ℃ for activation for 4h, the temperature is reduced to the reaction temperature, and hydrogen and isobutane are introduced, wherein the evaluation conditions are that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the carbon-tetrahydrocarbon is 0.3h-1The hydrogen-hydrocarbon molar ratio was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
TABLE 1 composition of catalyst and Performance test results
Figure BDA0002248480580000091
Figure BDA0002248480580000101
As can be seen from the data in Table 1, the catalyst provided by the invention has higher conversion per pass of n-butane and selectivity of isobutane when used for isomerization reaction of n-butane, namely, the catalyst provided by the invention has higher catalytic activity and stability of skeletal isomerization reaction of carbon-tetracarbon, and achieves better effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A catalyst for a skeletal isomerization reaction of a tetraalkyl carbon, comprising the following components, based on the total weight of the catalyst:
5-10 wt% of zirconium element;
0.2-4.5 wt% of aluminum element;
0.5-8.0 wt% of copper element;
0.5 wt% to 5.0 wt% elemental sulfur; and
50 to 90 wt% of a silica support.
2. The catalyst according to claim 1, characterized in that it comprises the following components, based on the total weight of the catalyst:
6-8 wt% of zirconium element;
1-3.5 wt% of aluminum element;
1-3 wt% of copper element;
2-4 wt% of elemental sulfur; and
60 to 80 wt% of a silica support.
3. A method for preparing the catalyst for a tetraalkyl carbon skeletal isomerization reaction according to claim 1 or 2, comprising the steps of:
s1, dissolving zirconium salt, aluminum salt and copper salt in water to form a solution;
s2, adding the solution into silica sol, and mixing to form a mixture;
s3, dehydrating, grinding and roasting the mixture to obtain the catalyst for the skeletal isomerization reaction of the tetrakacarbon.
4. The method according to claim 3, wherein the silica sol is an ammonium silica sol, and preferably the silica sol has a silica content of 30 wt% to 50 wt%.
5. The production method according to claim 3 or 4, wherein the zirconium salt is selected from one or more of zirconium nitrate, zirconium oxychloride and a hydrate thereof, preferably at least one selected from zirconium nitrate and a hydrate thereof;
the aluminum salt is at least one selected from aluminum sulfate and hydrates thereof;
the copper salt is selected from one or more of copper sulfate, copper nitrate and hydrates thereof.
6. The production method according to any one of claims 3 to 5, wherein the molar ratio n (Al)/n (Zr) of the aluminum salt to the zirconium salt is 0.2 to 2, and the molar ratio n (Cu)/n (Zr) of the copper salt to the zirconium salt is 0.2 to 1, based on the molar amount of the element.
7. A method according to any one of claims 4 to 6, wherein the zirconium salt is used in an amount of 5 to 20 wt.% based on zirconia relative to the silica.
8. The production method according to any one of claims 3 to 7, wherein in step S2, the temperature of the mixing treatment is 70 to 90 ℃, and the time of the mixing treatment is 5 to 12 hours;
in step S3, the dehydration treatment is performed at a temperature of 100-150 ℃; the roasting treatment method comprises the following steps: the temperature is raised to 600-700 ℃ roasting temperature for 3-10h, and the constant temperature is kept for 3-6 h.
9. Use of a catalyst according to claim 1 or 2 or prepared according to the preparation method of any one of claims 3 to 8 for a skeletal isomerization reaction of a tetraalkyl hydrocarbon, preferably the use comprises activating the catalyst before use; more preferably, the catalyst is activated using heating in an air stream; further preferably, the temperature of the activation is 380-480 ℃, the time of the activation is 2-4h, and the flow rate of the air flow is 30-60 mL/min.
10. The use according to claim 9, wherein the tetracarbon skeletal isomerization reaction is carried out under hydrogen conditions; the reaction temperature is 180-220 ℃, the reaction pressure is 0.5-1.5MPa, and the volume space velocity of the carbon-tetralkyl hydrocarbon is 0.2-2h-1The hydrogen-hydrocarbon molar ratio is 0.1-1.0.
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