CN112705220B - Catalyst for skeletal isomerization reaction of carbon tetra-alkane, preparation method and application thereof - Google Patents

Catalyst for skeletal isomerization reaction of carbon tetra-alkane, preparation method and application thereof Download PDF

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CN112705220B
CN112705220B CN201911025457.7A CN201911025457A CN112705220B CN 112705220 B CN112705220 B CN 112705220B CN 201911025457 A CN201911025457 A CN 201911025457A CN 112705220 B CN112705220 B CN 112705220B
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catalyst
salt
zirconium
temperature
copper
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CN112705220A (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

Abstract

The invention relates to a catalyst for skeletal isomerization reaction of tetra-alkane, which comprises the following components in terms of the total weight of the catalyst: 5-10 wt% of zirconium element; 0.2 to 4.5 weight percent of aluminum element; 0.5wt% to 8.0wt% copper element; 0.5wt% to 5wt% of elemental sulfur; and 73wt% to 90wt% 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, and the catalyst is prepared through one-step treatment. The method of the invention does not use precipitants such as ammonia water, etc., greatly shortens the preparation flow of the catalyst and reduces the energy consumption. The invention also provides application of the catalyst in the skeletal isomerization reaction of the carbon tetraalkylalkanes, and the catalyst has higher catalytic activity and stability when being used in the skeletal isomerization reaction of the carbon tetraalkylalkanes.

Description

Catalyst for skeletal isomerization reaction of carbon tetra-alkane, 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 skeletal isomerization reaction of a carbon tetraalkyl alkane, and a preparation method and application thereof.
Background
Industrial n-butane is mainly derived from catalytic cracking units. The liquefied petroleum gas yield of the catalytic cracking byproducts in 2016 China reaches 3504 ten thousand tons, wherein about 35% of resources supply four-carbon deep processing, and n-butane resources are relatively rich. The current alkylate production specification in the four-carbon industry chain is maximum and is used for the second-scale production of MTBE (methyl tertiary butyl ether). With the great popularization of urban natural gas, the consumption of the liquefied gas in the city is greatly reduced, and the price falls back, so that the liquefied gas becomes the motive power for driving the four-carbon deep processing project.
With the increasingly strict environmental protection requirements, china is accelerating the upgrading pace of gasoline quality, and national V standard gasoline is comprehensively supplied from 1 month 1 day 2017. The main content of the upgrading of the gasoline standard in China is to meet the requirements of 'desulfurizing, reducing manganese and reducing olefin' of gasoline under the condition of ensuring the octane number. The octane number of the gasoline is difficult to reach the standard when the olefin and the arene are reduced, so that the development of a clean component with high octane number is very critical for blending the gasoline. The hydrocarbon alkylate 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 alkylate is isobutane, so the development of a catalyst for preparing isobutane by skeletal isomerization of n-butane is significant for producing clean gasoline.
The isomerization catalyst is typically a platinum halide/alumina catalyst, in the form of gamma-Al 2 O 3 As a carrier, a proper amount of chloride auxiliary agent is required to be continuously added into the raw materials in the operation process. The main problem of the technology is that the content of water and sulfur in 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 maintenance cost of the equipment are increased, and the environment is polluted.
The n-butane skeleton isomerization catalyst taking zirconia as a carrier contains no chlorine, has loose requirements on the moisture and sulfur content of raw materials, can be regenerated, and is the development direction of the isomerization catalyst. As is known, the preparation process of the catalyst generally generates 'three wastes' pollution, which not only brings environmental protection pressure, but also increases the cost of the catalyst, so that the simple, efficient and clean preparation of the catalyst is an important proposition for industrial catalysis. The following patents disclose the preparation of zirconium oxide catalysts for the isomerization of alkanes such as n-butane.
Patent CN1660973a discloses a method for isomerizing C5, C6 alkanes, the catalyst preparation process of which comprises: zirconium salt solution and alkali solutionPreparing zirconium hydroxide by reaction; mixing zirconium hydroxide with silica sol and drying; containing SO 4 2- Soaking in the solution and drying; soaking in metal salt solution, drying and roasting.
Patent CN106732676A discloses a catalyst for n-butane isomerization, which is prepared by coprecipitating zirconium salt, gallium salt solution and ammonia water or urea water solution, filtering, washing and drying to obtain a precursor, dipping other component solutions, drying and roasting 2 A catalyst.
Patent CN106140197A, CN106101797B discloses a solid super acid catalyst, a preparation method thereof and an isomerization method of light normal alkane, wherein ammonia water and a metal salt solution are coprecipitated, filtered, washed and dried, then impregnated and dried in steps, and finally baked to obtain the catalyst.
Patent CN107051420a discloses a method for preparing a catalyst for n-butane isomerization, which comprises the following steps: carrying out hydrothermal reaction on ammonia water, zirconium salt and the like to generate hydroxide; filtering, washing and drying the precipitate; containing SO 4 2- Is immersed in the acidic solution and dried; soaking 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 SO 4 2- Solution impregnation, drying, mixing with silica sol for molding, nickel salt solution impregnation, drying, roasting and other complex processes.
Patent CN10807998A discloses a catalyst for C5 and C6 alkane isomerization, preparation and application thereof, and a coprecipitation method for preparing metal doped ZrO 2 The precursor is soaked with oxygen tungstic acid and metal salt in steps, and the catalyst is obtained after drying and roasting.
Patent CN109772287a discloses an alkane isomerization catalyst carrier and a preparation method thereof, the catalyst and a preparation method thereof, and the preparation process involves a plurality of steps such as reaction of zirconium salt and ammonia water, filtration, washing, drying, multiple times of dipping and drying, roasting and the like.
As can be seen from the above-mentioned publication, SO is currently used for isomerization of tetra-alkanes 4 2- /ZrO 2 The catalyst is generally prepared byZirconium salt reacts with ammonia water to generate zirconium hydroxide precipitate, and the zirconium hydroxide precipitate is filtered, washed and dried to obtain a catalyst precursor Zr (OH) 4 Respectively impregnating with SO-containing solution 4 2- And (3) solution and metal salt solution, and finally drying and roasting to obtain the catalyst. The method uses ZrO 2 The catalyst is used as a carrier, more zirconium salt is needed, the catalyst cost is high, the catalyst preparation steps are more, the flow is long, alkaline wastewater containing ammonia and the like is generated, a large amount of water is needed for washing the precipitate to be neutral, the energy consumption for drying for many times is more, and the defects are obvious.
Therefore, the existing problems are that research and development of a novel catalyst for skeletal isomerization of the carbon tetraalkylalkanes and a preparation method and application thereof are urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalyst for skeletal isomerization reaction of tetra-carbon alkane, and a preparation method and application thereof. The method takes silicon dioxide in silica sol as a carrier, and prepares the catalyst from zirconium salt, aluminum salt, copper salt and silica sol by 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, precipitants such as ammonia water and the like are not additionally used, so that the preparation flow 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 skeletal isomerization reaction of the carbon tetraalkylalkane at low temperature.
To solve the above technical problems, the first aspect of the present invention provides a catalyst for skeletal isomerization of a tetra-carbon alkane, which comprises the following components based on the total weight of the catalyst:
5-10 wt% of zirconium element;
0.2 to 4.5 weight percent of aluminum element;
0.5wt% to 8.0wt% copper element;
0.5wt% to 5.0wt% of elemental sulfur; and
50-90 wt% of a silica carrier.
In the above technical scheme, based on the total weight of the catalyst, the catalyst comprises the following components:
6-8 wt% of zirconium element;
1 to 3.5 weight percent of aluminum element;
1-3 wt% of copper element;
2 to 4wt% of elemental sulfur; and
60 to 80wt% of a silica support.
According to a second aspect of the present invention, there is provided a method for preparing a catalyst for skeletal isomerization of a tetra-carbon alkane 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 performing mixing treatment to form a mixture;
s3, carrying out dehydration, grinding and roasting treatment on the mixture to obtain the catalyst for the skeletal isomerization reaction of the carbon tetraalkane.
In the above technical scheme, the silica sol is an ammonium silica sol, and preferably the silica content in the silica sol is 30wt% to 50wt%. The use of an ammonium silica sol according to the invention is based on the fact that it has a low sodium content and on the other hand contains a certain amount of free NH 3 Can complex with metal salts to a certain extent, and can help the dispersion of the metal salts.
In the above technical solution, the zirconium salt is selected from one or more of zirconium nitrate, zirconium oxychloride and hydrates thereof, preferably at least one selected from zirconium nitrate and hydrates thereof. The aluminum salt is selected from at least one of aluminum sulfate and hydrate thereof. The copper salt is selected from one or more of copper sulfate, copper nitrate and hydrate thereof.
In the above technical scheme, the molar ratio n (Al)/n (Zr) of the aluminum salt to the zirconium salt is 0.2-2, preferably 0.3-2, based on the molar amount of the element. According to some specific embodiments of the invention, the molar ratio n (Al)/n (Zr) of the aluminum salt to the zirconium salt is any value within 0.261, 0.3, 0.565, 1.087, 1.652, 2, or any two values therein.
In the above technical scheme, the molar ratio n (Cu)/n (Zr) of the copper salt to the zirconium salt is 0.2-1, preferably 0.3-1, based on 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 any value within 0.260, 0.3, 0.39, 0.523, 0.565, 0.826, 1 or any two values therein.
In the technical scheme, the zirconium salt is used in an amount of 5-20 wt% of the silicon dioxide based on the zirconium oxide. According to some embodiments of the invention, the zirconium salt is present in an amount of 5wt%, 8.86wt%, 10.1wt%, 11.8wt%, 14.2wt%, 15.7wt%, 20wt% or any value in the range of any two values therein calculated as zirconia for silica.
In the above technical solution, in step S1, the water is used in an amount of 2 to 4 times, preferably 2.5 to 3 times, the weight of the zirconium salt.
In the above technical scheme, 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 to 150 ℃; the roasting treatment method comprises the following steps: raising the temperature to the roasting temperature of 600-700 ℃ by adopting the time of 3-10h, and keeping the temperature constant for 3-6h.
In a third aspect the present invention provides the use of a catalyst according to the first aspect of the invention or a catalyst prepared according to the preparation method of the second aspect of the invention for skeletal isomerisation reactions of a tetra-alkane, 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 2-4 hours, and the flow rate of the air flow is 30-60mL/min.
In the technical scheme, the skeletal isomerization reaction of the carbon tetraalkylalkanes is carried out under the condition of hydrogen; the reaction temperature of the reaction is 180-220 ℃, the reaction pressure is 0.5-1.5MPa, and the volume space velocity of the carbon tetra-alkane is 0.2-2h -1 The molar ratio of hydrogen to hydrocarbon 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 adopting zirconium dioxide as a carrier, the method provided by the invention uses silicon dioxide in silica sol as a carrier, prepares the catalyst by zirconium salt, aluminum salt, copper salt and silica sol through a one-step method (each substance is mixed, dried, dehydrated and roasted), can obviously reduce the dosage of the zirconium salt, does not use noble metals such as Pd, pt and the like, and therefore, obviously reduces the cost of the catalyst. Meanwhile, in the preparation process of the catalyst, the method does not additionally use precipitants such as ammonia water and the like, so that the preparation flow 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 skeletal isomerization reaction of the carbon tetraalkylalkane at low temperature.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
The measuring method or the calculating method provided by the invention is as follows:
(1) Elemental content: determined by ICP-AES instrument analysis.
(2) The conversion per pass of n-butane= (molar content of n-butane in the product after 1-reaction) ×100%.
(3) Isobutane selectivity= (molar isobutane content in the product after reaction/single pass conversion of n-butane) ×100%.
Examples
Example 1
10g of Zr (NO) 3 ) 4 ·5H 2 O、4.2g Al 2 (SO 4 ) 3 ·18H 2 O、4.8g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 25mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 12 hr, and steaming to remove most of water. Continuously evaporating water in a 130 ℃ drying oven, fully grinding, placing the dried water in a muffle furnace, and introducing air stripsHeating for 3h to 650 ℃ under the condition of the piece, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the catalyst CASZ@SiO for the n-butane skeleton isomerization reaction 2 -1。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 2
10g of Zr (NO) 3 ) 4 ·5H 2 O、12.6g Al 2 (SO 4 ) 3 ·18H 2 O、1.5g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 30mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 12 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 130 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 650 ℃ for 5 hours under the condition of introducing air, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -2。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 3
10g of Zr (NO) 3 ) 4 ·5H 2 O、8.4g Al 2 (SO 4 ) 3 ·18H 2 O、3.3g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 25mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. Stirring the above solutions rapidlyDrop wise into 45g of ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 12 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 130 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 650 ℃ for 2h under the condition of introducing air, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -3。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 4
10g of Zr (NO) 3 ) 4 ·5H 2 O、2.1g Al 2 (SO 4 ) 3 ·18H 2 O、3.0g Cu(NO 3 ) 2 ·3H 2 O was added to a 100mL beaker, followed by 20mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 85deg.C for 10 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 120 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 600 ℃ for 3h under the condition of introducing air, keeping the temperature for 5h, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -4。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 5
10g of Zr (NO) 3 ) 4 ·5H 2 O、8.4g Al 2 (SO 4 ) 3 ·18H 2 O、3.3g Cu(NO 3 ) 2 ·5H 2 O was added to a 100mL beaker, and 35mL deionized water was added, and the mixture was heated to 70℃with stirring to dissolve the solid. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 12 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 140 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 700 ℃ for 5 hours under the condition of introducing air, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -5。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 6
10g of Zr (NO) 3 ) 4 ·5H 2 O、4.2g Al 2 (SO 4 ) 3 ·18H 2 O、0.78g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 25mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 85deg.C for 10 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 140 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 650 ℃ for 4 hours under the condition of introducing air, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -6。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 7
10g of Zr (NO) 3 ) 4 ·5H 2 O、2.1g Al 2 (SO 4 ) 3 ·18H 2 O、0.78g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 30mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 60g of an ammonium silica sol (silica content 40 wt%). Stirring at 75deg.C for 12h, and steaming to remove most of water. Continuously evaporating water in a drying oven at 120 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 700 ℃ for 6h under the condition of introducing air, keeping the temperature for 3h, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -7。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 8
10g of Zr (NO) 3 ) 4 ·5H 2 O、4.2g Al 2 (SO 4 ) 3 ·18H 2 O、2.34g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 30mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 70g of an ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 12 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 120 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 650 ℃ for 5 hours under the condition of introducing air, naturally cooling to room temperature, and obtaining the n-butane skeleton isomerization catalyst CASZ@SiO 2 -8。
The n-butane isomerization reaction is carried out in a fixed bed reactor, and the catalyst (20-40 meshes) is filledFilling 10mL, introducing air (60 mL/h) at 420 ℃ for activation for 4h, reducing the temperature to the reaction temperature, and introducing hydrogen and isobutane, wherein the evaluation condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetraalkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 9
10.0g of Zr (NO) 3 ) 4 ·5H 2 O、4.2g Al 2 (SO 4 ) 3 ·18H 2 O、3.12g CuSO 4 ·5H 2 O was added to a 100mL beaker, followed by 30mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 50g of an ammonium silica sol (silica content 40 wt%). Stirring at 80deg.C for 10 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 120 ℃, fully grinding, placing the dried water in a muffle furnace, heating to 650 ℃ for 5 hours under the condition of introducing air, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -9。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
Example 10
10g of Zr (NO) 3 ) 4 ·5H 2 O、4.2g Al 2 (SO 4 ) 3 ·18H 2 O、3.0g Cu(NO 3 ) 2 ·3H 2 O was added to a 100mL beaker, followed by 25mL deionized water, and the solid was dissolved by stirring with heating at 70 ℃. The above solution was added dropwise, with rapid stirring, to 80g of an ammonium silica sol (silica content 40 wt%). Stirring at 90 deg.C for 8 hr, and steaming to remove most of water. Continuously evaporating water in a drying oven at 140 ℃, fully grinding, placing the dried water in a muffle furnace, and heating under the condition of introducing air5h to 650 ℃, keeping the temperature for 5h, and naturally cooling to room temperature to obtain the n-butane skeleton isomerization catalyst CASZ@SiO 2 -10。
The n-butane isomerization reaction is carried out in a fixed bed reactor, the loading of the catalyst (20-40 meshes) is 10mL, air (60 mL/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 condition is that the reaction temperature is 210 ℃, the reaction pressure is 1.0MPa, and the volume space velocity of the tetra-alkane is 0.3h -1 The molar ratio of hydrogen to hydrocarbon was 1.0. The results of the catalyst performance evaluation are shown in Table 1.
TABLE 1 composition of catalyst and results of Performance test
Figure BDA0002248480580000091
Figure BDA0002248480580000101
As can be seen from the data in Table 1, the catalyst provided by the invention has higher single pass conversion rate of n-butane and isobutane selectivity when being used for n-butane isomerization reaction, namely, the catalyst provided by the invention has higher catalytic activity and stability of skeletal isomerization reaction of the C-tetraalkane, and better effect is obtained.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims (14)

1. A catalyst for skeletal isomerization of a carbon tetraalkane, comprising the following components, based on the total weight of the catalyst:
5-10 wt% of zirconium element;
0.2 to 4.5 weight percent of aluminum element;
0.5wt% to 8.0wt% copper element;
0.5wt% to 5.0wt% of elemental sulfur; and
50-90 wt% of a silica carrier.
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 to 3.5 weight percent of aluminum element;
1-3 wt% of copper element;
2 to 4wt% of elemental sulfur; and
60 to 80wt% of a silica support.
3. A method for preparing the catalyst for skeletal isomerization reaction of tetra-carbon alkane 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 performing mixing treatment to form a mixture;
s3, carrying out dehydration, grinding and roasting treatment on the mixture to obtain the catalyst for the skeletal isomerization reaction of the carbon tetraalkane;
the aluminum salt is selected from at least one of aluminum sulfate and hydrate thereof;
the copper salt is selected from one or more of copper sulfate, copper sulfate hydrate, copper nitrate and copper nitrate hydrate.
4. A method of preparation according to claim 3, wherein the silica sol is an ammonium silica sol, preferably the silica content of the silica sol is from 30wt% to 50wt%.
5. The method according to claim 3 or 4, wherein the zirconium salt is one or more selected from zirconium nitrate, zirconium nitrate hydrate, zirconium oxychloride hydrate.
6. The method according to claim 5, wherein the zirconium salt is at least one selected from the group consisting of zirconium nitrate and hydrates thereof.
7. The method according to claim 3 or 4, 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.
8. The method of claim 3 or 4, wherein the zirconium salt is used in an amount of 5wt% to 20wt% of silica based on zirconia.
9. The method according to claim 3 or 4, 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 to 150 ℃; the roasting treatment method comprises the following steps: raising the temperature to the roasting temperature of 600-700 ℃ by adopting the time of 3-10h, and keeping the temperature constant for 3-6h.
10. Use of a catalyst according to claim 1 or 2 or a catalyst prepared according to the preparation method of any one of claims 3-9 for skeletal isomerization of a tetra-alkane.
11. The use according to claim 10, wherein the use comprises activating the catalyst prior to use.
12. The use according to claim 11, wherein the use of heating in an air stream activates the catalyst.
13. Use according to claim 12, wherein the activation temperature is 380-480 ℃, the activation time is 2-4 hours, and the air flow rate is 30-60mL/min.
14. The use according to claim 10, characterized in that the skeletal isomerization of the tetraalkanes is carried out under hydrogen conditions; the reaction temperature of the reaction is 180-220 ℃, the reaction pressure is 0.5-1.5MPa, and the volume space velocity of the carbon tetra-alkane is 0.2-2h -1 The molar ratio of hydrogen to hydrocarbon is 0.1-1.0.
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