CN109647432B - Isobutane dehydrogenation catalyst and preparation method thereof - Google Patents

Isobutane dehydrogenation catalyst and preparation method thereof Download PDF

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CN109647432B
CN109647432B CN201710946476.8A CN201710946476A CN109647432B CN 109647432 B CN109647432 B CN 109647432B CN 201710946476 A CN201710946476 A CN 201710946476A CN 109647432 B CN109647432 B CN 109647432B
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catalyst
carrier
drying
isobutane
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CN109647432A (en
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姜冬宇
缪长喜
吴文海
樊志贵
曾铁强
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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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals

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Abstract

The invention relates to a catalyst for isobutane dehydrogenation and a preparation method thereof, and mainly solves the problem that the dehydrogenation catalyst prepared in the prior art is low in activity. The invention adopts a composite catalyst, which comprises the following components in parts by weight: a) 0.1-5 parts of Pt or its oxide; b)0.1 to 5 parts of Sn or an oxide thereof; c) 90-99 parts of a composite oxide M1-M2-Al-O carrier, wherein M1 is selected from a mixture of IIA and VIIIB elements, and M2 is selected from at least one of lanthanide elements, so that the problem can be well solved, and the catalyst can be used for industrial production of isobutene prepared by isobutane dehydrogenation.

Description

Isobutane dehydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a catalyst for isobutane dehydrogenation and a preparation method thereof.
Background
Isobutene is generally used as a by-product in refineries and chemical plants. Although MGG and catalytic cracking processes for producing isobutene in a high yield are developed and popularized, the amount of byproducts propylene and isobutene generated from oil refineries and chemical plants cannot meet the market demand, especially MTBE (methyl tert-butyl ether) produced by isobutene etherification as a low-pollution and high-octane gasoline additive becomes a large chemical product which is developed fastest in the world, and the demand for isobutene is increased day by day. Therefore, the process for producing isobutene by utilizing isobutane dehydrogenation is favored in areas with abundant propane and isobutane resources. Commercial dehydrogenation processes in the world are the STAR process from Philips oil, the Catofin process from combined catalysis and rum, the Oleflex process from UOP, and the Snamprogetti fluid bed dehydrogenation process developed by Russian-Laval research institute in conjunction with the engineering of Snamprogetti, Italy. The STAR and Catofin processes employ fixed bed batch regeneration reaction systems; the Oleflex process adopts a moving bed continuous regeneration type reaction system; and the Snamprogetti process adopts a fluidized bed reaction regeneration system. In addition, there are alkane dehydrogenation technologies developed in conjunction with Linde and BASF.
Because of the limitation of thermodynamic factors, isobutane dehydrogenation catalytic reaction is carried out at high temperature, the carbon deposition and inactivation of the catalyst are serious, and the development of a catalyst with high activity, high selectivity and high stability becomes the key of the technology. Catalysts which take platinum as a main active component and are reported by Chinese patent (CN96117222.3) and U.S. patent (US4438288) and catalysts which take chromium as a main active component and are disclosed by Chinese patent (CN200910012450.1, CN200610126812.6) are two important catalysts for direct dehydrogenation catalytic reaction of low-carbon alkane. The direct dehydrogenation process of the low-carbon alkane has already realized industrial application, wherein the Pt catalyst becomes a research hotspot due to the characteristics of high activity, low pollution, low wear rate and the like. The catalyst K-Ce-Pt-Sn/gamma-Al disclosed in the Chinese patent (CN200910209534.4)2O3After 6h of reaction, the conversion of propane was 38%, the selectivity to propylene was 98%, and the amount of coke deposited was small. Wan et al in Industrial&"fluorescence of LanthanumAdditionon Catalytic Properties of PtSnK/Al" published in Engineering chemistry research 2011,50:4280-2O3Catalyst for IsobutananeeDehydrogenation "(addition of La to PtSnK/Al)2O3The influence of the catalytic performance of isobutane dehydrogenation) is shown in the characterization of the article, the addition of a proper amount of La can reduce the carbon deposition amount of the catalyst and improve the dispersion degree of Pt, and the effects of Sn and a carrier are also enhanced, so that Sn exists in an oxidation state, and the stability of the catalyst is improved. The preferred content of La is 0.9%, at which point the initial conversion can reach 49% and the selectivity is greater than 95%.
Isobutane dehydrogenation catalysts have made great progress so far, but there is room for improvement in catalyst activity. The invention adopts M1-M2-Al-O as the carrier to load the Pt-Sn catalyst, improves the performance of the catalyst, has better application prospect, and has no related report at present.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the activity of the isobutane dehydrogenation catalyst in the prior art is low, and the catalyst for preparing isobutene by isobutane dehydrogenation is high in activity. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing isobutene by isobutane dehydrogenation comprises the following components in parts by weight:
a) 0.1-5 parts of Pt or its oxide;
b)0.1 to 5 parts of Sn or an oxide thereof;
c) 90-99 parts of a composite oxide M1-M2-Al-O carrier, wherein M1 is selected from a mixture of IIA and VIIIB elements, and M2 is selected from at least one of lanthanide elements.
In the technical scheme, the catalyst for isobutane dehydrogenation is characterized in that the catalyst is prepared from 0.1-2.0 parts of Pt or oxides thereof and 0.1-2.0 parts of Sn or oxides thereof by weight of a low-carbon alkane catalyst;
in the above technical solution, the preferred technical solution is that VIIIB element in M1 in the composite oxide M1-M2-Al-O carrier is selected from Fe or Co, and the preferred technical solution is Fe.
In the technical scheme, the IIA element in M1 in the composite oxide M1-M2-Al-O carrier is selected from at least one of Be, Mg, Ca, Sr and Ba.
Preferably, the IIA element in M1 in the carrier is selected from at least one of Mg, Ca and Sr.
More preferably, the IIA element in M1 in the carrier is selected from Mg and Ca.
In the technical scheme, the preferable technical scheme is that the composite oxide M1-M2-Al-O carrier, M1 is selected from Fe, Mg and Ca in IIA and VIIIB elements.
M2 in the composite oxide M1-M2-Al-O carrier is selected from at least one of La or Ce.
The preferable technical scheme is that M2 in the composite oxide M1-M2-Al-O carrier is selected from La and Ce.
In the technical scheme, IIA and VIIIB elements selected for M1 in the composite oxide M1-M2-Al-O carrier and lanthanide elements of M2 are used together, so that a synergistic effect is achieved on isobutene selectivity.
In the technical scheme, in the composite oxide M1-M2-Al-O carrier, the molar ratio of Al to M1 is (1-1.99): 1, preferably (1.75-1.95): 1, the molar ratio of IIA to VIIIB in M1 is (1-4); m2 is (1-199): 1, preferably (7-39): 1.
to solve the second technical problem, the invention adopts the following technical scheme: a catalyst for isobutane dehydrogenation and a preparation method thereof comprise the following steps:
a) weighing soluble salts of M1, M2 and Al with required contents, dissolving the soluble salts in a proper amount of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, and adjusting the pH value to 7-10; aging, filtering, drying and roasting the product to obtain an M1-M2-Al-O carrier;
b) dissolving a required amount of soluble salt of Sn in a proper amount of hydrochloric acid solution, adding the soluble salt into the carrier obtained in the step a under stirring, uniformly mixing, carrying out ultrasonic-assisted impregnation, drying and roasting to obtain a catalyst precursor I;
c) dissolving a required amount of soluble Pt salt in a proper amount of water, adding the catalyst precursor I obtained in the step b under stirring, uniformly mixing, ultrasonically assisting for impregnation, drying, and roasting to obtain the isobutane dehydrogenation catalyst.
In the technical scheme, the dipping temperature in the dipping process is 10-80 ℃, the dipping time is 1-24 hours, the drying temperature is 80-150 ℃, the drying time is 6-24 hours, the roasting temperature is 450-650 ℃, and the roasting time is 6-24 hours. The soluble salt of M1, M2 or the oxide thereof can be one of chloride, nitrate or acetate; the soluble salt of Pt is preferably chloroplatinic acid; the soluble salt of tin is selected from stannous chloride or stannic chloride.
The catalyst prepared by the method is subjected to activity evaluation in an isothermal fixed bed reactor, and for the evaluation of a system for preparing low-carbon olefin by dehydrogenating isobutane, the process is briefly described as follows:
the flow of isobutane gas is regulated through a mass flow meter, the isobutane gas enters a preheating zone to be mixed, then the isobutane gas enters a reaction zone, the preheating zone and the reaction zone of the reactor are heated by electric heating wires to reach a preset temperature, and the inner diameter of the reactor is a stainless steel sleeve with phi 9 mm-phi 6mm, and the length of the stainless steel sleeve is about 400 mm. After the reacted gas passes through a condensing tankAnd then the composition is analyzed by gas chromatography. The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: filling about 0.5 g of catalyst into an isothermal reactor with the inner diameter of phi 9mm to phi 6mm (the height of a catalyst bed layer is about 17mm), wherein the volume ratio of water vapor to isobutane is (10-1): 1, the reaction temperature is 400-600 ℃, the reaction pressure is 0-1 MPa, and the mass space velocity of alkane is 3.0-8.0 h-1And the reaction raw material is in contact reaction with the catalyst to obtain isobutene.
In the case of isobutane dehydrogenation catalysts, many side reactions also occur at the acid centers on the surface of the carrier, such as cracking and isomerization of alkanes, cracking, isomerization and polymerization of olefins, and the like, and a single Al2O3Is not favorable for the selectivity and stability of the catalytic reaction.
The method provided by the invention selects a composite oxide M1-M2-Al-O as a carrier, M1 is selected from a mixture of IIA and VIIIB elements, and M2 is selected from at least one of lanthanide series elements. The prepared catalyst is used for isobutane dehydrogenation reaction, the initial conversion rate of isobutane reaches over 56 percent, and the selectivity of isobutane is higher than 97 percent; and a better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Weighing 47.96g of beryllium chloride, 64.88g of ferric chloride, 24.52g of lanthanum chloride and 253.34g of aluminum chloride soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the Be0.6Fe0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.295g of stannic chloride, dissolving the stannic chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 chloroplatinic acid, dissolving in 10mL water, adding into I under stirring, mixing well, soaking at 30 deg.C for 12 hr, and drying at 100 deg.CDrying for 16 hours, and roasting for 20 hours in a muffle furnace at 600 ℃ to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were as follows: 0.5 g of catalyst is loaded into the isothermal fixed bed reactor (the height of a catalyst bed layer is 17mm), the reaction is carried out under normal pressure and at the temperature of 550 ℃; the volume ratio of water vapor to isobutane was 2: 1; the mass space velocity of isobutane is 4.0h-1The results are shown in Table 1.
[ example 2 ]
153.84g of magnesium nitrate, 161.60g of ferric nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Fe0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 3 ]
132.13g of calcium acetate, 69.57g of iron acetate, 31.60g of lanthanum acetate and 307.96g of basic aluminum acetate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ca0.56Fe0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain the productThe catalyst precursor is obtained, denoted as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 4 ]
128.83g of strontium acetate, 69.57g of iron acetate, 31.60g of lanthanum acetate and 307.96g of basic aluminum acetate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Sr0.6Fe0.4La0.1Al1.9An Ox carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1. [ example 5 ]
Weighing 146.56g of barium chloride, 64.88g of ferric chloride, 24.52g of lanthanum chloride and 253.34g of aluminum chloride soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a muffle furnace at 600 ℃ for 20 hours to obtain Ba0.6Fe0.4La0.1Al1.9OXAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Chloroplatinic acid 0.133 was weighed into 10mL of water, added to I with stirring, and mixedAnd (3) uniformly soaking for 12 hours at 30 ℃, drying for 16 hours at 100 ℃, and roasting for 20 hours in a muffle furnace at 600 ℃ to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 6 ]
153.84g of magnesium nitrate, 202.0g of ferric nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.5Fe0.5gLa0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 7 ]
205.13g of magnesium nitrate, 80.80g of ferric nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.8Fe0.2gLa0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 chloroplatinic acid, dissolving in 10mL water, adding into I under stirring, mixing well, soaking at 30 deg.C for 12 hr, drying at 100 deg.C for 16 hr, and standing at 6 deg.CRoasting the mixture for 20 hours in a muffle furnace at the temperature of 00 ℃ to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 8 ]
Weighing 79.92g of beryllium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the Be0.6Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 9 ]
153.84g of magnesium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 chloroplatinic acid, dissolving in 10mL water, adding into I under stirring, mixing well, soaking at 30 deg.C for 12 hr, drying at 100 deg.C for 16 hr, and calcining in 600 deg.C muffle furnace for 20 hr to obtain isobutane dehydrogenation catalystAnd (3) preparing. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 10 ]
141.69g of calcium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ca0.6Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 11 ]
Weighing 126.98g of strontium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Sr0.6Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1. [ example 12 ]
156.80g of barium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, a product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ba0.6Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 13 ]
153.84g of magnesium nitrate, 161.60g of ferric nitrate, 54.82g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Fe0.4Ce0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 14 ]
153.84g of magnesium nitrate, 161.60g of ferric nitrate, 16.25g of lanthanum nitrate, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, a product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Fe0.4La0.05Ce0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 15 ]
153.84g of magnesium nitrate, 161.60g of ferric nitrate, 81.25g of lanthanum nitrate and 656.48g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Fe0.4La0.25Al1.75OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 16 ]
Weighing 153Dissolving 84g of magnesium nitrate, 161.60g of ferric nitrate, 16.25g of lanthanum nitrate and 731.50g of aluminum nitrate soluble salt in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a muffle furnace at 600 ℃ for 20 hours to obtain Mg0.6Fe0.4La0.05Al1.95OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 17 ]
Weighing 96.15g of magnesium nitrate, 88.56g of calcium nitrate, 161.60g of ferric nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing by using 4L of water to obtain a filter cake, drying the filter cake for 16 hours at 100 ℃, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.3Ca0.3Fe0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 18 ]
96.15g of magnesium nitrate and 88g of magnesium nitrate were weighed.Dissolving 56g of calcium nitrate, 116.41g of cobalt nitrate, 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.3Ca0.3Co0.4La0.1Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 19 ]
Weighing 96.15g of magnesium nitrate, 88.56g of calcium nitrate, 80.80g of ferric nitrate, 16.25g of lanthanum nitrate, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, carrying out suction filtration and washing by using 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.3Ca0.3Fe0.4La0.05Ce0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 20 ]
64.10g of magnesium nitrate, 59.03g of calcium nitrate, 202.0g of ferric nitrate, 16.25g of lanthanum nitrate, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried at 100 ℃ for 16 hours and then is roasted in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.0.25Ca0.25Fe0.5Ce0.05La0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 21 ]
102.56g of magnesium nitrate, 94.46g of calcium nitrate, 80.80g of ferric nitrate, 16.25g of lanthanum nitrate, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried at 100 ℃ for 16 hours and then is roasted in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.4Ca0.4Fe0.2Ce0.05La0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. Catalyst and process for preparing sameThe evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 1
Weighing 32.49g of lanthanum nitrate and 712.75g of aluminum nitrate soluble salt, dissolving in 1L of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, adjusting the pH value to 8.2, aging the product for 2 hours, performing suction filtration washing with 4L of water to obtain a filter cake, drying the filter cake at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the La0.1Al1.9O3And (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 2
153.84g of magnesium nitrate, 161.60g of ferric nitrate and 750.26g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in the mixture under continuous stirring, the pH value is adjusted to be 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.6Fe0.4Al2O4And (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 3
256.41g of magnesium nitrate and 16.25g of nitric acid were weighedLanthanum, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in the mixture under continuous stirring, the pH value is adjusted to be 8.2, the product is aged for 2 hours, 4L of water is used for filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then the filter cake is roasted for 20 hours in a 600 ℃ muffle furnace to obtain MgLa0.05Ce0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 4
404.00g of ferric nitrate, 16.25g of lanthanum nitrate, 27.41g of ceric ammonium nitrate and 712.75g of aluminum nitrate soluble salt are weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped under continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried for 16 hours at 100 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain FeLa0.05Ce0.05Al1.9OxAnd (3) a carrier. Weighing 9.85g of carrier, putting the carrier into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, and then drying at 100 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1. Comparative example 5
712.75g of aluminum nitrate soluble salt is weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in the mixture under continuous stirring, the pH value is adjusted to 8.2, and the product is obtainedAging for 2 hr, washing with 4L water to obtain filter cake, drying the filter cake at 100 deg.C for 16 hr, and calcining in a muffle furnace at 580 deg.C for 20 hr to obtain carrier Al2O3. Pouring the mixture into 500ml mixed solution containing 256.41 magnesium nitrate and 32.49g lanthanum nitrate, dipping the mixture for 12 hours at 30 ℃, then drying the mixture for 16 hours at 100 ℃, and roasting the dried mixture for 20 hours in a muffle furnace at 580 ℃ to obtain MgLa0.1Ox/Al1.9OxWeighing 9.85g of the catalyst precursor, putting the weighed mass into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier into the solution under stirring, uniformly mixing the mixture, soaking the mixture for 12 hours at 30 ℃, and then drying the mixture for 16 hours at 100 ℃ to obtain the catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a muffle furnace at 580 ℃ for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
Comparative example 6
712.75g of aluminum nitrate soluble salt is weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in under the condition of continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried at 100 ℃ for 16 hours and then is roasted in a muffle furnace at 580 ℃ for 20 hours to obtain a carrier Al2O3. Pouring the mixture into 500ml mixed solution containing 153.84g magnesium nitrate, 161.60g ferric nitrate, 16.25g lanthanum nitrate and 27.41g ceric ammonium nitrate, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting at 580 ℃ in a muffle furnace for 20 hours to obtain Mg0.6Fe0.4La0.05Ce0.05Al1.9OxWeighing 9.85g of the catalyst precursor, putting the weighed mass into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier into the solution under stirring, uniformly mixing the mixture, soaking the mixture for 12 hours at 30 ℃, and then drying the mixture for 16 hours at 100 ℃ to obtain the catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a muffle furnace at 580 ℃ for 20 hours to obtain the isobutane dehydrogenation catalyst. CatalysisThe evaluation conditions of the agent were the same as in example 1, and the results are shown in Table 1.
Comparative example 7
712.75g of aluminum nitrate soluble salt is weighed and dissolved in 1L of deionized water, the mixture is uniformly mixed, ammonia water is slowly dripped in under the condition of continuous stirring, the pH value is adjusted to 8.2, the product is aged for 2 hours, 4L of water is used for suction filtration and washing to obtain a filter cake, the filter cake is dried at 100 ℃ for 16 hours and then is roasted in a muffle furnace at 580 ℃ for 20 hours to obtain a carrier Al2O3. Pouring the mixture into 500ml mixed solution containing 404.00g of ferric nitrate and 32.49g of lanthanum nitrate, dipping the mixture for 12 hours at 30 ℃, then drying the mixture for 16 hours at 100 ℃, and roasting the dried mixture for 20 hours in a muffle furnace at 580 ℃ to obtain FeLa0.1Ox/Al1.9OxWeighing 9.85g of the catalyst precursor, putting the weighed mass into a beaker, then weighing 0.190g of stannous chloride, dissolving the stannous chloride in 10mL of hydrochloric acid solution, adding the carrier into the solution under stirring, uniformly mixing the mixture, soaking the mixture for 12 hours at 30 ℃, and then drying the mixture for 16 hours at 100 ℃ to obtain the catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the I while stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 100 ℃ for 16 hours, and roasting in a muffle furnace at 580 ℃ for 20 hours to obtain the isobutane dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
The catalyst composition for preparing isobutene by isobutane dehydrogenation is fixed as Pt: 0.5 part, Sn: 1.0 part, and the balance of carrier 98.5 parts. The above example and comparative supports were prepared in 1mol numbers and the composition and mole fraction of the support and the corresponding catalyst performance are listed in table 1.
TABLE 1
Figure BDA0001431814120000151
Figure BDA0001431814120000161
Figure BDA0001431814120000171

Claims (6)

1. The catalyst for isobutane dehydrogenation comprises the following components in parts by weight:
a) 0.1-5 parts of Pt or its oxide;
b)0.1 to 5 parts of Sn or an oxide thereof;
c) 90-99 parts of a composite oxide M1-M2-Al-O carrier, wherein M1 is selected from at least one of IIA elements and a mixture of Fe or Co in VIIIB elements, M2 is selected from at least one of lanthanide elements,
the preparation method of the isobutane dehydrogenation catalyst comprises the following steps:
1) weighing soluble salts of M1, M2 and Al with required contents, dissolving the soluble salts in a proper amount of deionized water, uniformly mixing, slowly dripping ammonia water under continuous stirring, and adjusting the pH value to 7-10; aging, filtering, drying and roasting the product to obtain an M1-M2-Al-O carrier;
2) dissolving a required amount of soluble salt of Sn in a proper amount of hydrochloric acid solution, adding the soluble salt into the carrier obtained in the step a under stirring, uniformly mixing, carrying out ultrasonic-assisted impregnation, drying and roasting to obtain a catalyst precursor I;
3) dissolving a required amount of soluble Pt salt in a proper amount of water, adding the catalyst precursor I obtained in the step b under stirring, uniformly mixing, ultrasonically assisting for impregnation, drying, and roasting to obtain the isobutane dehydrogenation catalyst;
in the composite oxide M1-M2-Al-O carrier, IIA element in M1 is selected from at least one of Be, Mg, Ca, Sr and Ba;
m2 in the composite oxide M1-M2-Al-O carrier is selected from at least one of La or Ce.
2. The catalyst for dehydrogenating isobutane according to claim 1, wherein the part of Pt or an oxide thereof is 0.1-2.5 parts, and the part of Sn or an oxide thereof is 0.1-2.5 parts, based on the weight of the catalyst for dehydrogenating isobutane to prepare isobutene.
3. The catalyst for dehydrogenating isobutane according to claim 1, wherein the molar ratio of Al to M1 is (1-1.99): 1, the molar ratio of IIA to VIIIB in M1 is (1-4).
4. An isobutane dehydrogenation catalyst according to claim 1, wherein the molar ratio of the Al to the M2 is (1-199): 1.
5. the isobutane dehydrogenation catalyst according to claim 1, wherein the impregnation temperature in the step 2) and the step 3) is 10-80 ℃, the impregnation time is 1-24 hours, the drying temperature is 80-150 ℃, the drying time is 6-24 hours, the roasting temperature is 450-650 ℃, and the roasting time is 6-24 hours.
6. The catalyst of any one of claims 1 to 5 is used for dehydrogenation of isobutane, the reaction raw material is isobutane, and the reaction conditions are as follows: the volume ratio of the water vapor to the isobutane is (10-1): 1, the reaction temperature is 400-600 ℃, the reaction pressure is 0-1 MPa, and the mass space velocity of the alkane is 3.0-8.0 h-1And the reaction raw material is in contact reaction with the catalyst to obtain isobutene.
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