CN109651046B - Method for propane/isobutane mixed dehydrogenation - Google Patents

Method for propane/isobutane mixed dehydrogenation Download PDF

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CN109651046B
CN109651046B CN201710946350.0A CN201710946350A CN109651046B CN 109651046 B CN109651046 B CN 109651046B CN 201710946350 A CN201710946350 A CN 201710946350A CN 109651046 B CN109651046 B CN 109651046B
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propane
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CN109651046A (en
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姜冬宇
缪长喜
吴文海
吴省
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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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    • 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
    • C07C5/32—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
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—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
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a method for propane/isobutane mixed dehydrogenation, which mainly solves the problem that a dehydrogenation catalyst prepared in the prior art is low in activity. The invention adopts a propane/isobutane mixed dehydrogenation method, wherein the reaction raw material is propane/isobutane, and the reaction conditions are as follows: the volume ratio of the water vapor to the alkane 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‑1When the catalyst is used, the reaction raw material is in contact reaction with the catalyst to obtain propylene/isobutene; the catalyst comprises the following components in parts by weight: 0.1-5 parts of Pt or its oxide; 0.1 to 5 parts of Sn or an oxide thereof; 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 method can be used for industrial production of propylene/isobutene prepared by mixed alkane dehydrogenation.

Description

Method for propane/isobutane mixed dehydrogenation
Technical Field
The invention relates to a method for propane/isobutane mixed dehydrogenation.
Background
Propylene and isobutene among the low-carbon olefins are one of the most widely used organic raw materials in the field of petrochemical industry, and are generally obtained as byproducts from oil refinery plants and chemical plants. Although mgg (maximum Gas Plus gasoline) catalytic cracking process for producing more propylene and isobutylene has been developed and popularized, the amount of propylene and isobutylene still cannot meet the market demand, especially as the amount of PP (polypropylene) is increased and isobutylene is etherified to produce MTBE as a low pollution and high octane gasoline additive, the demand is increasing day by day. The process for producing propylene and isobutene by dehydrogenating propane and isobutane is favored in areas rich in low-carbon alkane 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 intermittent 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.
Due to the limitation of thermodynamic factors, the propane/isobutane dehydrogenation catalytic reaction is carried out at high temperature, the carbon deposition and inactivation of the catalyst are serious, and the development of the 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 (CN 96117222.3) 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 Lanthanum Addition on Catalytic Properties of PtSnK/Al" published in Engineering Chemistry Research 2011,50:4280-2O3Catalyst for Isobutane Dehydrogenation "(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 La content is 0.9%, where the initial conversion can reach 49% and the selectivity is greater than 95%.
Isobutane and propane dehydrogenation catalysts have made greater progress at present, 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, is applied to propane/iso-butane mixed dehydrogenation, 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 in the prior art, the activity of the propane/isobutane mixed dehydrogenation catalyst is low, and a method for propane/isobutane mixed dehydrogenation is provided. The method has the characteristic of high activity of the propane/isobutane mixed dehydrogenation catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for propane/isobutane mixed dehydrogenation is characterized in that a reaction raw material is propane/isobutane, and the reaction conditions are as follows: the volume ratio of the water vapor to the alkane 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-1When the catalyst is used, the reaction raw material is in contact reaction with the catalyst to obtain propylene/isobutene; the catalyst comprises the following components in parts by weight: 0.1-5 parts of Pt or its oxide; 0.1 to 5 parts of Sn or an oxide thereof; 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 propane/isobutane mixed dehydrogenation catalyst is characterized in that the weight parts of Pt or oxides thereof are 0.1-2.0 parts, and the weight parts of Sn or oxides thereof are 0.1-2.0 parts;
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.
the preparation method of the propane/isobutane mixed dehydrogenation catalyst comprises 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 propane/isobutane mixed 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 propane/isobutane mixed dehydrogenation method specifically comprises the following steps: firstly, preprocessing: filling a catalyst in a reaction tube, inserting the reaction tube into an electric heating multi-stage furnace, introducing nitrogen into the reaction tube, and heating to 450-580 ℃, preferably 510-570 ℃ under the condition that the nitrogen flow is 10 mL/min. Introducing hydrogen instead, and keeping the hydrogen flow for 2 hours under the condition of 30 mL/min; II, dehydrogenation reaction: preheating and mixing alkane gas and steam, and then entering a reaction zone for carrying out catalytic dehydrogenation reaction on mixed alkane; the space velocity of the alkane is 3.0-8.0 h-1Preferably 3.5 to 6.5 hours-1(ii) a The volume ratio of the water vapor to the alkane is (8-1): 1, preferably (6-2): 1; controlling the reading of the gas pressure gauge to be 0-1 MPa, preferably 0.01-0.5 MPa; thirdly, detection: after the reacted gas passes through a condensing tank, the gas after the alkane dehydrogenation reaction is continuously monitored on line by using a gas chromatograph, so that the conversion rate of mixed alkane on the catalyst and the selectivity of diene in the whole reaction process are measured and calculated.
In the case of alkane 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, with 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 propane/isobutane dehydrogenation reaction, the dehydrogenation conversion rate of mixed alkane is more than 49%, the selectivity of diene is higher than 96%, and a good technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
47.96g of beryllium chloride, 64.88g of ferric chloride, 24.52g of lanthanum chloride and 253.34g of chlorine were weighed outDissolving soluble salt of aluminum oxide in 1L of deionized water, mixing uniformly, slowly dripping ammonia water under continuous stirring, adjusting pH value to 8.2, aging the product for 2 hours, leaching 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 of chloroplatinic acid, dissolving in 10mL of water, adding into the catalyst 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 propane/isobutane mixed 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 560 ℃; the volume ratio of the water vapor to the mixed alkane is 2: 1; the mass space velocity of the alkane is 4.0h-1Propane/isobutane was 1: 1, the 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 propane/isobutane mixed dehydrogenation catalyst. Evaluation of catalystThe 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 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 propane/isobutane mixed 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 catalyst 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 propane/isobutane mixed dehydrogenation catalyst. Catalyst evaluation conditions were carried out in the same manner asExample 1, 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. 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 propane/isobutane mixed 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 propane/isobutane mixed dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown inTable 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 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 propane/isobutane mixed 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 propane/isobutane mixed 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 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 propane/isobutane mixed dehydrogenation catalyst. 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 propane/isobutane mixed 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 catalyst 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 propane/isobutane mixed 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 propane/isobutane mixed 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 propane/isobutane mixed 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 and placing the carrier into a beaker, then weighing 0.190g of stannous chloride and 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 catalyst precursor, which is marked as I. Weighing 0.133 of chloroplatinic acid, dissolving in 10mL of water, adding into the catalyst 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 propane/isobutane mixed 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 propane/isobutane mixed dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 16 ]
153.84g of magnesium nitrate, 161.60g of ferric nitrate, 16.25g of lanthanum nitrate and 731.50g 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 Mg0.6Fe0.4La0.05Al1.95OxAnd (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 propane/isobutane mixed 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 catalyst 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 propane/isobutane mixed dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 18 ]
Weighing 96.15g of magnesium nitrate, 88.56g of calcium 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 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 Mg0.3Ca0.3Co0.4La0.1Al1.9OxAnd (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 catalyst 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 propane/isobutane mixed dehydrogenation catalyst. Evaluation of catalystThe 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 ammonium ceric 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 baking in a 600 ℃ muffle furnace for 20 hours to obtain the propane/isobutane mixed 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 ammonium ceric 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 chloroplatinic acid in 10mL water, adding to I with stirring, mixingMixing evenly, dipping 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 propane/isobutane mixed 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 baking in a 600 ℃ muffle furnace for 20 hours to obtain the propane/isobutane mixed dehydrogenation catalyst. The catalyst evaluation conditions were the same as in example 1, and the results are shown in Table 1.
[ example 22 ]
Using the catalyst of example 14, the evaluation conditions were: normal pressure and temperature of 450 ℃; the volume ratio of the water vapor to the alkane is 2: 1; the mass space velocity of the alkane is 4.0h-1. The results are shown in Table 1.
[ example 23 ]
Using the catalyst of example 14, the evaluation conditions were: normal pressure and 510 ℃; the volume ratio of the water vapor to the alkane is 2: 1; the mass space velocity of the alkane is 4.0h-1. The results are shown in Table 1.
[ example 24 ]
Using the catalyst of example 14, the evaluation conditions were: normal pressure and temperature of 580 ℃; the volume ratio of the water vapor to the alkane is 2: 1; the mass space velocity of the alkane is 4.0h-1. 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 catalyst 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 propane/isobutane mixed 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, 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 the filter cake 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 mixture I under 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 propane/isobutane mixed 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 were weighedDissolving 16.25g of lanthanum nitrate, 27.41g of ceric ammonium 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 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 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 propane/isobutane mixed 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 catalyst 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 propane/isobutane mixed 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 are weighed out and dissolved in 1L of deionized waterMixing the above materials, slowly adding ammonia water under stirring, adjusting pH to 8.2, aging 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 Al carrier2O3. 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 catalyst 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 propane/isobutane mixed dehydrogenation catalyst. The evaluation conditions of the catalyst 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 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 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 chloroplatinic acid, dissolving in 10mL water, adding to I under stirring, mixing wellDipping for 12 hours at 30 ℃, drying for 16 hours at 100 ℃, and roasting for 20 hours in a muffle furnace at 580 ℃ to obtain the propane/isobutane mixed dehydrogenation catalyst. The catalyst evaluation conditions 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 catalyst 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 propane/isobutane mixed dehydrogenation catalyst. The evaluation conditions of the catalyst were the same as in example 1, and the results are shown in Table 1.
For the catalyst composition for propane/isobutane mixed dehydrogenation, the fixed ratio was Pt: 0.5 part, Sn: 1.0 part, and the balance of carrier is 98.5 parts. The above example and comparative supports were prepared in 1mol number, and the composition and parts by mol of the support and the corresponding catalyst properties are listed in table 1.
TABLE 1
Figure RE-GDA0001522541710000151
Figure BDA0001431791350000161
Figure BDA0001431791350000171

Claims (5)

1. A method for propane/isobutane mixed dehydrogenation is characterized in that a reaction raw material is propane/isobutane, and the reaction conditions are as follows: the volume ratio of the water vapor to the alkane 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-1When the catalyst is used, the reaction raw material is in contact reaction with the catalyst to obtain propylene/isobutene; the catalyst comprises the following components in parts by weight: 0.1-5 parts of Pt or its oxide; 0.1 to 5 parts of Sn or an oxide thereof; 90-99 parts of a composite oxide M1-M2-Al-O carrier, wherein M1 is selected from a mixture of IIA and Fe elements, the IIA element in M1 is selected from Be and/or Sr, M2 is La, and Al: M1 is (1-1.99) in molar ratio: 1, the molar ratio of IIA to Fe in M1 is (1-4), and Al: M2 is (1-19): 1.
2. the method for propane/isobutane mixed dehydrogenation according to claim 1, characterized in that the part of Pt or its oxide is 0.1-2.5 parts, and the part of Sn or its oxide is 0.1-2.5 parts, calculated by weight.
3. The method for propane/isobutane mixed dehydrogenation according to claim 1, characterized in that the preparation method of propane/isobutane mixed dehydrogenation catalyst comprises 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 propane/isobutane mixed dehydrogenation catalyst.
4. The method for preparing the catalyst for the propane/isobutane mixed dehydrogenation method according to claim 3, wherein the impregnation temperature in the step b) and the step c) is 10-80 ℃, the drying temperature is 80-150 ℃, and the roasting temperature is 450-650 ℃.
5. The method for preparing the catalyst for the propane/isobutane mixed dehydrogenation method according to claim 4, wherein the dipping time in the step b) and the step c) is 1-24 hours, the drying time is 6-24 hours, and the roasting time is 6-24 hours.
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