CN109647396B - Catalyst for preparing isobutene by dehydrogenating isobutane - Google Patents

Catalyst for preparing isobutene by dehydrogenating isobutane Download PDF

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CN109647396B
CN109647396B CN201710946412.8A CN201710946412A CN109647396B CN 109647396 B CN109647396 B CN 109647396B CN 201710946412 A CN201710946412 A CN 201710946412A CN 109647396 B CN109647396 B CN 109647396B
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CN109647396A (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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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6522—Chromium
    • 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
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6525—Molybdenum
    • 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
    • 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

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Abstract

The invention relates to a catalyst for preparing isobutene by isobutane dehydrogenation, which mainly solves the problem that the dehydrogenation catalyst prepared by 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 VIB 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

Catalyst for preparing isobutene by dehydrogenating isobutane
Technical Field
The invention relates to a catalyst for preparing isobutene by dehydrogenating isobutane.
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 of propylene was 98% and the amount of coke formation was small, and this study did not provide stability data. Yu et Al, "Effect of Cr promoter on the performance of Pt-Sn/γ -Al", journal of Fuel Chemistry and Technology 2006,34:209-2O3catalyst for expanding moisture "(addition of Cr to PtSn/gamma-Al)2O3Influence of propane dehydrogenation performance of catalyst) research on the addition of Cr additive to PtSn/gamma-Al2O3The influence of propane dehydrogenation performance shows that the PtSn/gamma-Al can be obviously improved by adding a small amount of Cr2O3The dehydrogenation stability of the catalyst can improve the selectivity of propylene and reduce the carbon deposit on the surface of the catalyst. The method is caused by the synergistic effect between Cr and Pt-Sn, on one hand, Pt promotes the reduction of Cr to generate +3 Cr which can improve the selectivity of propylene; on the other hand, Cr makes Sn difficult to reduce, and maintains the active oxidation state valence state under a strong reducing atmosphere, thereby improving the dehydrogenation stability of the catalyst. "expand dehydrogenation over PtSnNa/La-doped" published by Yu et al in Fuel Processing Technology 2013,111:94-104Al2O3catalyst:Effect of La content”(PtSnNa/La-doped Al2O3Dehydrogenation of propane above: influence of La) was characterized and found that La entered Al2O3The catalyst acidity and carbon deposit amount are reduced with the increase of La content, the Pt dispersion degree is improved, and the effects of Sn and a carrier are enhanced. The preferred La content is 1.0%, at which point the initial conversion can reach 41% and the selectivity is greater than 96%. When La is excessive, Pt aggregates and Sn also becomes a metal, resulting in a decrease in catalyst activity.
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 VIB elements, and M2 is selected from at least one of lanthanide.
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 the VIB element in M1 in the composite oxide M1-M2-Al-O carrier is selected from Cr or Mo, and the preferred technical solution is Cr.
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 Cr, Mg and Ca in IIA and VIB 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 VIB elements selected by 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, the molar ratio of Al to M1 in the composite oxide M1-M2-Al-O carrier is (1-1.99) to 1, preferably (1.75-1.95) to 1, and the molar ratio of IIA to VIB in M1 is (0.25-4); the ratio of Al to M2 is (1-199) to 1, preferably (7-39) to 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. The reacted gas was passed through a condensing pot and then analyzed for composition 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) to 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 VIB 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 39.97g of beryllium chloride, 133.22g of chromium 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the Be0.5Cr0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours 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 the water vapor to the isobutane is 2: 1; the mass space velocity of isobutane is 4.0h-1The results are shown in Table 1.
[ example 2 ]
Weighing 128.2g of magnesium nitrate, 200.08g of chromium 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5La0.1Al1.9OxAnd (3) a carrier. 9.85g of the carrier was weighed into a beaker, then 0.190g of stannous chloride was weighed and dissolved in 10mL of hydrochloric acid solution, and added with stirringThe carrier is evenly mixed, dipped for 12 hours at the temperature of 30 ℃, and then dried for 16 hours at the temperature of 90 ℃ 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 90 ℃ 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 ]
88.09g of calcium acetate, 200.08g of chromium nitrate, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ca0.5Cr0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
107.36g of strontium acetate, 200.08g of chromium nitrate, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Sr0.5Cr0.5La0.1Al1.9An Ox carrier. Weighing 9.85g of carrier, placing into a beaker, then weighing 0.190g of stannous chloride, dissolving in 10mL of hydrochloric acid solution, adding the carrier under stirring, mixing uniformly, soaking at 30 ℃ for 12 hours, then soaking at 90 DEG CDrying for 16 hours gives the catalyst precursor, 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 90 ℃ 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 ]
122.13g of barium chloride, 133.22g of chromium chloride, 24.52g of lanthanum chloride and 253.34g of aluminum chloride 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ba0.5Cr0.5La0.1Al1.9OXAnd (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 90 ℃ 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 90 ℃ 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 6 ]
51.28g of magnesium nitrate, 320.12g of chromium 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.2Cr0.8La0.1Al1.9OxAnd (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 90 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weigh 0.133 of chlorineDissolving platinic acid in 10mL of water, adding the platinic acid into the I under stirring, uniformly mixing, soaking at 30 ℃ for 12 hours, drying at 90 ℃ 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, 80.03g of chromium 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.8Cr0.2La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 8 ]
Weighing 66.6g of beryllium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the Be0.5Mo0.5La0.1Al1.9OxAnd (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 90 ℃ for 16 hours to obtain a catalyst precursor, which is marked as I. Weighing 0.133 chloroplatinic acid in 10mL water, adding to I under stirring, mixing well at 30 deg.CDipping for 12 hours, drying for 16 hours at 90 ℃, 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 9 ]
128.21g of magnesium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.5Mo0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 10 ]
118.08g of calcium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ca0.5Mo0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 deg.C for 16 hr, baking in 600 deg.C muffle furnaceBurning 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 ]
105.82g of strontium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Sr0.5Mo0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
130.67g of barium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Ba0.5Mo0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. Catalyst evaluationThe conditions were the same as in example 1, and the results are shown in Table 1.
[ example 13 ]
Weighing 128.2g of magnesium nitrate, 200.08g of chromium nitrate, 54.82g 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5Ce0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
Weighing 128.2g of magnesium nitrate, 200.08g of chromium 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 8.0, 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 90 ℃, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5La0.05Ce0.05Al1.9OxAnd (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 90 ℃ 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain the isobutane dehydrogenation catalyst. Catalyst evaluation conditions were the same as in example 1The results are shown in Table 1.
[ example 15 ]
Weighing 128.2g of magnesium nitrate, 200.08g of chromium nitrate, 81.25g of lanthanum nitrate and 656.48g 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5La0.25Al1.75OxAnd (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 90 ℃ 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 90 ℃ 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 128.2g of magnesium nitrate, 200.08g of chromium nitrate, 16.25g of lanthanum nitrate and 731.50g 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5La0.05Al1.95OxAnd (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 90 ℃ 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 90 ℃ 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 ]
64.10g of magnesium nitrate, 59.04g of calcium nitrate, 200.08g of chromium 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.25Ca0.25Cr0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
64.10g of magnesium nitrate, 59.04g of calcium nitrate, 136.61g of molybdenum chloride, 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.25Ca0.25Mo0.5La0.1Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
64.10g of magnesium nitrate, 59.04g of calcium nitrate, 200.08g of chromium 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 8.0, 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 90 ℃ for 16 hours and then is roasted in a 600 ℃ muffle furnace for 20 hours, and Mg is obtained0.25Ca0.25Cr0.5La0.05Ce0.05Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 ]
Weighing 25.64g of magnesium nitrate, 23.61g of calcium nitrate, 320.12g of chromium 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 8.0, 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 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.1Ca0.1Cr0.8Ce0.05La0.05Al1.9OxAnd (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 90 ℃ 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 90 deg.C for 16 hr, and calcining in 600 deg.C muffle furnace for 20 hr to obtain isobutaneA 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, 80.03g of chromium 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 8.0, 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 90 ℃ and then is roasted for 20 hours in a 600 ℃ muffle furnace, and Mg is obtained0.4Ca0.4Cr0.2Ce0.05La0.05Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 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 8.0, aging the product for 2 hours, performing suction filtration washing with 4L of water to obtain a filter cake, drying the filter cake at 90 ℃ 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 90 ℃ 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 90 ℃ 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,the results are shown in Table 1.
Comparative example 2
Weighing 128.2g of magnesium nitrate, 200.08g of chromium nitrate and 750.26g 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 8.0, aging the product for 2 hours, leaching and washing with 4L of water to obtain a filter cake, drying the filter cake at 90 ℃ for 16 hours, and roasting in a 600 ℃ muffle furnace for 20 hours to obtain Mg0.5Cr0.5Al2O4And (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 90 ℃ 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 90 ℃ 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, 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 8.0, 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 90 ℃, and then 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 90 ℃ 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 90 ℃ 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
And weighing 400.Dissolving 15g of chromium nitrate, 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 8.0, 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 90 ℃ for 16 hours, and roasting in a muffle furnace at 600 ℃ for 20 hours to obtain the CrLa0.05Ce0.05Al1.9OxAnd (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 90 ℃ 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 90 ℃ 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 under the condition of continuous stirring, the pH value is adjusted to 8.0, 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 90 ℃, and then is roasted for 20 hours in a muffle furnace at 580 ℃, so that a carrier Al is obtained2O3. 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 90 ℃, and roasting the dried mixture for 20 hours in a 600 ℃ muffle furnace 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 90 ℃ 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 90 ℃ 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 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a muffle furnace at 580 ℃, so that a carrier Al is obtained2O3. Pouring the mixture into 500ml of mixed solution containing 128.2g of magnesium nitrate, 200.08g of chromium nitrate, 16.25g of lanthanum nitrate and 27.41g of ceric ammonium nitrate, soaking the mixture for 12 hours at 30 ℃, then drying the mixture for 16 hours at 90 ℃, and roasting the dried mixture for 20 hours in a 600 ℃ muffle furnace to obtain Mg0.5Cr0.5La0.05Ce0.05Al1.9OxWeighing 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 90 ℃ 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 90 ℃ 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 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 8.0, 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 90 ℃, and then is roasted for 20 hours in a muffle furnace at 580 ℃, so that a carrier Al is obtained2O3. Pouring the mixture into 500ml of mixed solution containing 400.15g of chromium nitrate and 32.49g of lanthanum nitrate, soaking the mixture for 12 hours at 30 ℃, then drying the mixture for 16 hours at 90 ℃, and roasting the dried mixture for 20 hours in a 600 ℃ muffle furnace to obtain CrLa0.1Ox/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 90 ℃ to obtain the catalyst precursor, which is marked as I. Weighing 0Dissolving chloroplatinic acid of 133 in 10mL of water, adding the solution into the catalyst I while stirring, uniformly mixing, dipping for 12 hours at 30 ℃, drying for 16 hours at 90 ℃, 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.
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 98.4 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 BDA0001431802870000141
Figure BDA0001431802870000151
Figure BDA0001431802870000161

Claims (7)

1. The 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 a mixture of at least one of VIB elements and Mg and Ca in IIA elements, and M2 is at least one selected from lanthanide;
the VIB element in the M1 is selected from Cr or Mo, and the M2 is selected from at least one of La or Ce;
the preparation method of the 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 isobutane dehydrogenation catalyst.
2. The catalyst for preparing isobutene through isobutane dehydrogenation according to claim 1, wherein the part of Pt or an oxide thereof is 0.1-2.0 parts, and the part of Sn or an oxide thereof is 0.1-2.0 parts, based on the weight of the catalyst for preparing isobutene through isobutane dehydrogenation.
3. The catalyst for preparing isobutene through isobutane dehydrogenation according to claim 1, wherein the molar ratio of Al to M1 is (1-1.99): 1, the molar ratio of IIA to VIB in M1 is (0.25-4).
4. The catalyst for preparing isobutene through isobutane dehydrogenation according to claim 1, wherein the molar ratio of Al to M2 is (1-199): 1.
5. a preparation method of the catalyst for preparing isobutene through isobutane dehydrogenation according to any one of claims 1 to 4, comprising the following steps of:
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.
6. The method for preparing the catalyst for preparing the isobutene through the dehydrogenation of the isobutane according to claim 5, wherein the dipping temperature in the step b) and the step c) 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.
7. The catalyst of any one of claims 1 to 4 or the catalyst prepared by the method of claim 5 or 6 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.
CN201710946412.8A 2017-10-12 2017-10-12 Catalyst for preparing isobutene by dehydrogenating isobutane Active CN109647396B (en)

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