CN110560043B - Method for producing propylene by propane dehydrogenation - Google Patents

Method for producing propylene by propane dehydrogenation Download PDF

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CN110560043B
CN110560043B CN201810566730.6A CN201810566730A CN110560043B CN 110560043 B CN110560043 B CN 110560043B CN 201810566730 A CN201810566730 A CN 201810566730A CN 110560043 B CN110560043 B CN 110560043B
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propane
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CN110560043A (en
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吴省
缪长喜
洪学思
樊志贵
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Sinopec Shanghai Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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
    • B01J23/002—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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • 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
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/30—Tungsten

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  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to a method for producing propylene by propane dehydrogenation, which mainly solves the problem of low selectivity of a Cr-series dehydrogenation catalyst prepared by the prior art. The method adopts the direct contact reaction of a propane raw material and a catalyst to obtain the propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 520-660 ℃, and the mass space velocity is 0.2-10 h‑1(ii) a The catalyst comprises the following components in parts by weight: a) 1-25 parts of Cr and/or W element or oxide thereof; b)0 to 5 parts of at least one element of group IA or an oxide thereof; c) 0.01-5 parts of at least one element selected from IVB group of the periodic table or its oxide; d) 69-96 parts of alumina carrier, the problem is solved well, and the method can be used for industrial application of propane dehydrogenation.

Description

Method for producing propylene by propane dehydrogenation
Technical Field
The invention relates to a method for producing propylene by propane dehydrogenation.
Background
Propylene is one of the most widely used olefins in the petrochemical field, and is mainly used for producing polypropylene, acrylonitrile, propylene oxide, acrylic acid, isopropanol and the like. The traditional method for preparing propylene by adopting ethylene co-production and light oil (naphtha and light diesel oil) cracking process is one of the most promising methods, but the propylene is limited by raw material sources and is difficult to increase in a large scale, so that new routes for preparing low-carbon olefins such as propylene and the like are vigorously developed in various countries in the world, including routes for preparing olefins from methanol, for preparing propylene by disproportionation of ethylene and butylene, for double decomposition, for dehydrogenating alkanes and the like, but the method for preparing propylene by dehydrogenation reaction by using propane with rich sources and low price as a raw material is one of the most promising methods.
The industrial propane dehydrogenation technology mainly comprises a Pt catalyst and a Cr catalyst, and comprises an Oleflex process of UOP, a Catofin process of Lummus, a STAR process of Uhde, a PDH process of Linde, an FBD process developed by Snamprogetti-Yarsintez cooperation and the like, wherein the industrial devices are mostly the Oleflex technology and the Catofin technology, and the catalysts applied to the Oleflex technology and the Catofin technology are respectively the Pt catalyst and the Cr catalyst. The Pt catalyst is used for dehydrogenation of low-carbon alkane, has the advantages of environmental friendliness, high activity and the like, and has high price, complex preparation and high requirement on purity of reaction raw materials. The Cr catalyst has low price, relatively high activity and low requirement on the purity of raw materials, but has certain influence on the environment, frequent regeneration is needed in the reaction process, and the performance requirement on all aspects of the Cr catalyst is higher.
Chinese patent CN 105727930 reports a catalyst for preparing propylene by direct dehydrogenation of propane, which takes regular mesoporous alumina-zirconia or alumina-ceria composite oxide as a carrier, chromium oxide as an active component and an alkali metal additive, and the catalyst has higher propane conversion rate and propylene selectivity. Chinese patent CN103769156 uses ammonia treated alumina as carrier, Cr as active component, potassium, manganese, cobalt, iron, nickel and the like as auxiliary agent, and prepares dehydrogenation catalyst by co-impregnation method, the Cr content is 2-6%, the auxiliary agent content is 0.1-5%, the catalyst has better selectivity, but the activity is relatively low. Patent CN101940922B reports a low-carbon alkane dehydrogenation catalyst and a preparation method thereof, wherein chromium is used as an active metal component, chromium-containing alumina is used as a carrier, the weight content of chromium oxide in the carrier is 2.0-15.0%, and the activity of the catalyst is improved. Chinese patent CN101940922A reports a low-carbon alkane dehydrogenation catalyst, which takes Cr as an active component and alkali metal as an auxiliary agent, and the reaction temperature is 645 ℃ and the liquid hourly space velocity is 600 hours-1The conversion of propane at normal pressure for 30 minutes of the reaction was 47%, and the selectivity to propylene was about 89%.
The propane dehydrogenation catalyst generally adopts alumina with stronger surface acidity as a carrier, and side reactions such as cracking and the like are easy to occur, so that the problem of lower catalyst selectivity and the like is caused. W has more applications in the petrochemical field, and can enable a catalyst to have better catalytic activity and selectivity through the synergistic effect with Cr, and at present, no patent exists in the aspect of improving the propane dehydrogenation performance by using Cr and W together.
Disclosure of Invention
The invention aims to solve the technical problem that a propane dehydrogenation catalyst in the prior art is low in selectivity, and provides a catalyst for preparing propylene by propane dehydrogenation. 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: the catalyst for producing propylene by propane dehydrogenation comprises the following components in parts by weight:
a) 1-25 parts of Cr and/or W element or oxide thereof;
b)0 to 5 parts of at least one element of group IA or an oxide thereof;
c) 0.01-5 parts of at least one element selected from IVB group of the periodic table or its oxide;
d) 69-96 parts of Al2O3And (3) a carrier.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 5-20 parts by weight of the propane catalyst.
In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 10-18 parts by weight of the propane catalyst.
In the above technical solution, it is more preferable that the alloy simultaneously includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W element is: (0.2-8): 1. in this case, the use of both Cr and W has an unexpected synergistic effect in improving the catalyst selectivity of the propane dehydrogenation catalyst.
In the above technical solution, preferably, the alloy simultaneously includes Cr and W elements or oxides thereof, wherein the weight ratio of Cr to W elements is: (0.25-4): 1.
in the technical scheme, the part of the element selected from the IA group of the periodic table or the oxide thereof is 0.01-3 parts by weight of the propane catalyst, wherein the element of the IA group is at least one selected from Li, Na, K, Rb and Cs.
In the technical scheme, the part of the element selected from IVB group of the periodic table or the oxide thereof is 0.01-3 parts by weight of the propane catalyst, wherein the element of IVB group is selected from at least one of Ti and Zr.
In the above technical solution, more preferably, the range of group ivb element or oxide thereof in the periodic table of elements is 0.3 to 3 parts, and the group ivb element or oxide thereof is selected from Ti and Zr, Ti: the weight ratio of Zr is (0.25-3): 1, and the mixture of Ti and Zr has unexpected synergistic effect on the aspect of improving the catalyst selectivity of the propane dehydrogenation catalyst.
The Cr element and the W element are used together and cooperate with the IA group element and the IVB group element, so that the catalyst has unexpected synergistic effect on the aspect of improving the selectivity of the propane dehydrogenation catalyst.
In the technical scheme, the specific surface of the adopted alumina carrier is 50-500 m2(g) the pore diameter is 5-40 nm.
In the technical scheme, more preferably, the specific surface range of the alumina carrier is 117-350 m2The pore diameter is 8-25 nm.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a catalyst for producing propylene by propane dehydrogenation comprises the following steps:
a) pressing and screening the alumina with certain specific surface area and aperture, selecting 20-40 meshes for screening, and roasting at 400-600 ℃ for 0.5-12 hours to obtain a pretreated carrier I;
b) mixing a carrier I with a soluble salt solution containing Cr and/or W and a soluble solution in the IA group and the IVB group of the periodic table to obtain a mixture I, and adjusting the pH value of the mixture I to 1-7 by using an inorganic ammonia or inorganic ammonium salt solution at the temperature of 10-80 ℃ to obtain a mixture II;
c) and (3) soaking the mixture II for 0.5-8 hours at the temperature of 10-100 ℃, filtering, drying, and roasting at 300-800 ℃ for 0.5-12 hours to obtain the required propane dehydrogenation catalyst.
The soluble salt of Cr can be selected from one of nitrate, acetate or oxalate; the W soluble salt is selected from tungstate, metatungstate or acetate. Li, Na, K, Rb and Cs are selected from one of nitrate, carbonate or acetate and other soluble salts; ti and Zr are selected from one of nitrate, acetate and other soluble salts.
In the technical scheme, the preferable scheme of the inorganic ammonia or inorganic ammonium salt is selected from ammonia water, ammonium carbonate or ammonium bicarbonate, and the preferable range of the pH value of the solution is 1-7, and the more preferable range is 1-3; the preferable range of the dipping temperature is 50-80 ℃, the preferable range of the dipping time is 1-3 hours, the preferable range of the roasting temperature of the catalyst is 400-600 ℃, and the preferable range of the roasting time is 4-8 hours.
In the reaction section, fresh propane raw material and propane recycle material are used as the feed raw material of the reactor, the feed raw material is heated and gasified by steam and a heat exchanger, the heating source of the heat exchanger is the processing material of the compression and recovery section, and the heated gasification material is heated to the reaction temperature and then sent to the reactor. The hot discharge material of the reactor is cooled after heat exchange with the raw material of the reactor, and is sent to the compression section of the device. The hydrocarbon is maintained at a certain negative pressure in the reactor, while the system is still under vacuum conditions, the reactor is thoroughly purged with steam, thereby sweeping the catalyst and residual hydrocarbon from the reactor and entering the recovery section. The regeneration air, in addition to serving to burn the catalyst to remove coke, is also used to restore the bed temperature to the initial operating conditions. When the regeneration is completed, the reactor is pumped to vacuum again, and the next operation cycle is entered. The technical scheme adopted in the laboratory is as follows: the reaction raw material is propane, and the reaction conditions are as follows: the reaction pressure is 0.01-1 MPa, the temperature is 520-660 ℃, and the mass space velocity is 0.2-10 h-1(ii) a The reaction raw material and the catalyst are contacted and reacted to obtain the propylene. The method specifically comprises the following steps:
the flow rate of propane gas is adjusted through a mass flow meter, the propane gas enters a preheating zone to be preheated, then the propane gas enters a reaction zone, a heating section and a reaction section of a reactor are heated by electric heating wires to reach a preset temperature, and the length of a reaction tube of the reactor is about 400-580 mm, wherein the inner diameter of the reaction tube is phi 9 mm-phi 6 mm. The reacted gas was passed through a condensing pot and then analyzed for composition by gas chromatography. Conversion of propane Using post-reaction propaneThe alkane content accounts for the sum of all gas-phase product contents and is multiplied by 100 percent to obtain the product; selectivity of olefin as a percentage of propylene content in other gas components than propane after reaction, i.e. propylene content divided by C1、C2、C4And the percentage of the sum of the propylene contents.
The propane dehydrogenation catalyst generally adopts alumina with stronger surface acidity as a carrier, and side reactions such as cracking and the like are easy to occur, so that the problem of lower catalyst selectivity and the like is caused. W has more applications in the petrochemical industry, and can enable the catalyst to have better catalytic activity and selectivity through the synergistic effect with Cr. The invention takes Cr and/or W as the active components of the catalyst, and the IA group and the IVB group of the periodic table of elements are added in the preparation process, and the result shows that the propane dehydrogenation catalyst prepared by the method has higher selectivity. When the catalyst obtained by adopting the preparation conditions is used for propane dehydrogenation reaction, the propylene selectivity reaches 93.1%, the propane conversion rate is 44%, and a good technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 15nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst.
The flow of propane gas is regulated by a mass flow meter, the propane gas enters a preheating zone for preheating, and then enters a reaction zone, a heating section and a reaction section of the reactor are heated by electric heating wires to reach a preset temperature, and the reactor is a quartz tube with the inner diameter of phi 6mm and the length of 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: 0.5 g of the above catalyst was addedLoading into the isothermal fixed bed reactor, the reaction pressure is normal pressure, and the gas mass space velocity is 1.0 hour-1And the reaction temperature is 580 ℃. The results are shown in Table 1.
[ example 2 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of a solution having a specific surface area of 340m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 9nm, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 3 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of 173m in specific surface area was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 12nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 4 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 45m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the aperture of 28nm per gram, then soaking the alumina carrier in a water bath with the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven with the temperature of 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast the sample for 4 hours at the temperature of 550 ℃ to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 5 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate and 10.44 g of niobium zirconium oxalate nitrate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 6 ]
Ammonium tungstate 10.94 g, potassium nitrate 2.15 g and sodium titanate 3.78 g were weighed into 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 7 ]
Ammonium tungstate 10.94 g, potassium nitrate 2.15 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 8 ]
Ammonium tungstate 10.94 g, lithium nitrate 4.16 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2G, pore diameter 15And (2) adjusting the pH value of the solution of the nm alumina carrier to 3.5 by using 2.5% ammonia water, then soaking the solution in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in a drying oven at the temperature of 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 9 ]
Ammonium tungstate 10.94 g, sodium nitrate 2.74 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 10 ]
Ammonium tungstate 10.94 g, rubidium nitrate 1.05 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 11 ]
Ammonium tungstate 10.94 g, cesium nitrate 1.38 g and zirconium nitrate 10.44 g were weighed into 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with the pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at the temperature of 120 ℃ for 8 hours, putting the sample into a muffle furnace, and drying in the oven at the temperature of 5℃ for 8 hoursRoasting for 4 hours at the temperature of 50 ℃ to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 12 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.22 g of niobium zirconium nitrate oxalate were weighed and added to 100 ml of deionized water, and 86 g of 117m in specific surface area was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 13 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate, 0.76 g of sodium titanate and 8.35 g of zirconium nitrate were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 14 ]
52.66 g of chromium nitrate, 2.15 g of potassium nitrate, 2.84 g of sodium titanate and 2.61 g of zirconium nitrate were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane feed and the catalyst were reacted under the same reaction conditions as in example 1The reaction was carried out, and the results are shown in Table 1.
[ example 15 ]
Ammonium tungstate 10.94 g, potassium nitrate 2.15 g, sodium titanate 1.89 g and zirconium nitrate 5.22 g were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 7 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 16 ]
Ammonium tungstate 10.94 g, potassium nitrate 2.15 g, sodium titanate 0.76 g and zirconium nitrate 8.35 g were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 7 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 17 ]
Ammonium tungstate 10.94 g, potassium nitrate 2.15 g, sodium titanate 2.84 g, and zirconium nitrate 2.61 g were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 7 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 18 ]
31.44 g of chromium oxalate were weighed, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate and 3.70 g of titanium nitrate are added into 100 ml of deionized water, and 86 g of specific surface area 117m is added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 5 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 19 ]
13.17 g of chromium nitrate, 2.73 g of ammonium tungstate, 2.15 g of potassium nitrate and 3.70 g of titanium nitrate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 20 ]
52.66 g of chromium nitrate, 10.93 g of ammonium tungstate, 2.15 g of potassium nitrate and 3.70 g of titanium nitrate were weighed, and the weighed materials were added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 21 ]
21.07 g of chromium nitrate, 4.36 g of ammonium tungstate, 2.15 g of potassium nitrate and 3.70 g of titanium nitrate were weighed, and the weighed materials were added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2G, pore diameter 1Adjusting the pH value of a 5nm alumina carrier solution to 3.5 by using 2.5% ammonia water, then soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in a 120 ℃ oven for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 22 ]
47.4 g of chromium nitrate, 9.81 g of ammonium tungstate, 2.15 g of potassium nitrate and 3.70 g of titanium nitrate were weighed, and the weighed materials were added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 23 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate and 7.98 g of zirconium acetate were weighed, and the weighed materials were added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 5 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 24 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The alumina carrier with the aperture of 15nm is used for regulating the pH value of the solution to 3 by using 2.5 percent ammonia water, and then the solution is soaked in a water bath at the temperature of 80 ℃ for 1 hour, and a sample is taken out to be put inFiltering, drying in a 120 ℃ oven for 8 hours, and then putting the sample into a muffle furnace to be roasted for 4 hours at 550 ℃ to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 25 ]
42.13 g of chromium nitrate, 2.67 g of tungsten acetate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 26 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 27 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 0.76 g of sodium titanate and 8.35 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with the aperture of 15nm to 3 by using 2.5% ammonia water, immersing the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in a 120 ℃ oven for 8 hours, putting the sample into a muffle furnace, and heating the sample at the temperature of 550 DEG CCalcining for 4 hours under the condition to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 28 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 2.15 g of potassium nitrate, 0.76 g of sodium titanate and 8.35 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 29 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 2.15 g of potassium nitrate, 0.76 g of sodium titanate and 8.35 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 30 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 2.84 g of sodium titanate and 2.61 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. Propane feedstock with the above catalystThe reagents were reacted under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 31 ]
42.13 g of chromium nitrate, 2.19 g of ammonium tungstate, 2.15 g of potassium nitrate, 2.84 g of sodium titanate and 2.61 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 32 ]
10.53 g of chromium nitrate, 8.75 g of ammonium tungstate, 2.15 g of potassium nitrate, 2.84 g of sodium titanate and 2.61 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 33 ]
52.66 g of chromium nitrate, 0.22 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 15nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 34 ]
52.66 g of chromium nitrate, 4.3 g of potassium nitrate and 3.78 g of sodium titanate were weighed and added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2Adjusting the pH value of the solution to 3.5 by using 2.5% ammonia water for the alumina carrier with the pore diameter of 15nm per gram, soaking the alumina carrier in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering the sample, drying the sample in an oven at the temperature of 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
[ example 35 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 520 ℃ of temperature; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 36 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 660 ℃ temperature; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 37 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 650 ℃ of temperature; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 38 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: the pressure is 1MPa, and the temperature is 620 ℃; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 39 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: the pressure is 0.05MPa, and the temperature is 620 ℃; the mass space velocity of the propane is 1.0h-1. The results are shown in Table 2.
[ example 40 ]
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 0.2h-1. The results are shown in Table 2.
[ example 41 ] to provide a pharmaceutical composition
26.33 g of chromium nitrate, 5.47 g of ammonium tungstate, 2.15 g of potassium nitrate, 1.89 g of sodium titanate and 5.32 g of zirconium nitrate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3 by using 2.5% ammonia water, then soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to be roasted at 550 ℃ for 4 hours to obtain the required catalyst. The propane raw material reacts with the catalyst under the following reaction conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 10h-1. The results are shown in Table 2.
Comparative example 1
42.13 g of chromium nitrate and 2.19 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 2
10.94 g of ammonium tungstate was weighed, added to 100 ml of deionized water, and added with 86 g of a specific surface area of 117m2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 3
Ammonium tungstate 10.94 g and potassium nitrate 2.15 g were weighed into 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 4
52.66 g of chromium nitrate, 0.68 g of sodium carbonate and 3.03 g of ferric nitrate were weighed and added to 100 ml of deionized water, and 86 g of specific surface area 117m was added2The preparation method comprises the following steps of (1)/g, adjusting the pH value of an alumina carrier with a pore diameter of 15nm to 3.5 by using 2.5% ammonia water, soaking in a water bath at 50 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
Comparative example 5
10.53 g of chromium nitrate and 8.75 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 86 g of a specific surface area of 117m was added2Alumina carrier with 15nm pore diameter, regulating the pH value of the solution to 3.5 by using 2.5 percent ammonia water, then soaking in a water bath at 50 ℃ for 1 hour,and taking out the sample, filtering, drying in an oven at 120 ℃ for 8 hours, and roasting the sample in a muffle furnace at 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above-mentioned catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.
TABLE 1
Figure BDA0001684723390000171
Figure BDA0001684723390000181
[ examples 35 to 41 ]
The catalyst prepared in example 20 was used for propane dehydrogenation, and the reaction conditions and evaluation results are shown in Table 2.
TABLE 2
Figure BDA0001684723390000182
Figure BDA0001684723390000191

Claims (9)

1. The method for producing propylene by propane dehydrogenation comprises the step of directly contacting and reacting a propane raw material with a catalyst to obtain propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 520-660 ℃, and the mass space velocity is 0.2-10 h-1(ii) a The catalyst comprises the following components in parts by weight:
a) 1-25 parts of oxides of two elements of Cr and W;
b)0 to 5 parts but not 0 part of an oxide of at least one element of the IA group;
c) 0.01-5 parts of a mixture of oxides of two elements of Ti and Zr in the IVB group of the periodic table;
d) 69-96 parts of Al2O3And (3) a carrier.
2. The method for producing propylene by propane dehydrogenation according to claim 1, wherein the amount of the oxide of each of the elements Cr and W is 5 to 20 parts by weight based on the weight of the catalyst.
3. The method for producing propylene by propane dehydrogenation according to claim 2, wherein the weight ratio of the Cr to W elements in the catalyst is: (0.2-8): 1.
4. the method for producing propylene by dehydrogenation of propane according to claim 1, wherein the amount of the oxide of at least one element selected from the group IA of the periodic table of elements is 0.01 to 3 parts by weight based on the weight of the catalyst, wherein the element of the group IA is at least one element selected from the group consisting of Li, Na, K, Rb and Cs.
5. The method for producing propylene by dehydrogenation of propane according to claim 1, wherein the amount of the mixture of oxides of two elements of Ti and Zr in group IVB of the periodic Table is 0.01 to 3 parts by weight based on the weight of the catalyst.
6. The method for producing propylene by propane dehydrogenation according to claim 5, wherein the amount of the mixture of oxides of two elements of Ti and Zr in group IVB of the periodic Table is 0.3 to 3 parts by weight based on the weight part of the catalyst, and the ratio of Ti: the weight ratio of Zr is (0.25-3): 1.
7. The method for producing propylene by dehydrogenation of propane according to claim 1, wherein Al is2O3The specific surface area of the carrier is 50-500 m2The pore diameter is 5-40 nm.
8. The method for producing propylene by dehydrogenation of propane according to claim 7, wherein Al is present2O3The specific surface area of the carrier is 117-350 m2The pore diameter is 8-25 nm.
9. The method for producing propylene by dehydrogenation of propane according to any of claims 1 to 8, wherein the method for preparing the catalyst comprises the following steps:
a) al with a certain specific surface area and aperture2O3Tabletting and screening the carrier, selecting 20-40 meshes for screening, and roasting at 400-600 ℃ for 0.5-12 hours to obtain a pretreated carrier I;
b) mixing a carrier I with a soluble solution containing Cr and W and soluble solutions in the IA group and the IVB group of the periodic table of elements in required amounts to obtain a mixture I, and adjusting the pH value of the mixture I to be 1-7 by using an inorganic ammonia or inorganic ammonium salt solution at the temperature of 10-80 ℃ to obtain a mixture II;
c) and (3) soaking the mixture II for 0.5-8 hours at the temperature of 10-100 ℃, filtering, drying, and roasting at 300-800 ℃ for 0.5-12 hours to obtain the required catalyst.
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