阅读说明：本技术 用于丙烷脱氢的方法 (Process for the dehydrogenation of propane ) 是由 吴省 缪长喜 吴文海 张新玉 于 2018-06-05 设计创作，主要内容包括：本发明涉及一种用于丙烷脱氢的方法,主要解决现有技术制备的Cr系脱氢催化剂活性较低的问题。本发明采用丙烷原料与催化剂直接接触反应得到丙烯,其特征在于反应压力为0.01～1MPa、温度为530～660℃、质量空速为0.3～8h<Sup>-1</Sup>；催化剂重量份数计,包括以下组分：a)1～28份Cr和/或W元素或其氧化物；b)0～5份选自元素周期表第ⅠB族中的至少一种元素或其氧化物；c)69～96份氧化铝载体,较好地解决了该问题,可用于丙烷脱氢的工业化应用。(The invention relates to a method for propane dehydrogenation, which mainly solves the problem of low activity of Cr-series dehydrogenation catalysts prepared in the prior art. The method adopts the direct contact reaction of a propane raw material and a catalyst to obtain propylene, and is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 530-660 ℃, and the mass space velocity is 0.3-8 h ‑1 (ii) a The catalyst comprises the following components in parts by weight: a)1 to 28 parts of Cr and/or W element or oxide thereof; b)0 to 5 parts of at least one element selected from group IB of the periodic table of elements or an oxide thereof; c) 69-96 parts of alumina carrier, the problem is solved well, and the method can be used for industrial application of propane dehydrogenation.)

1. a method for propane dehydrogenation is characterized in that a propane raw material is in direct contact reaction with a catalyst to obtain propylene, and the method is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 530-660 ℃, and the mass space velocity is 0.3-8 h^-1(ii) a The catalyst comprises the following components in parts by weight:

a) 1-28 parts of Cr and/or W element or oxide thereof;

b)0 to 5 parts of at least one element selected from group IB of the periodic table of elements or an oxide thereof;

c) 69-96 parts of Al₂O₃And (3) a carrier.

2. The method for propane dehydrogenation according to claim 1, characterized in that the parts of the elements Cr and/or W or their oxides are 3 to 25 parts by weight based on the parts by weight of the propane catalyst.

3. The process according to claim 2, characterized in that the elements are selected from the group consisting of Cr and W in the weight ratio of Cr to W, based on the parts by weight of the propane catalyst: (0.1-10): 1.

4. The method according to claim 1, wherein the amount of the group IB element or the oxide thereof is 0.01-3 parts by weight based on the weight of the propane catalyst, wherein the group IB element is at least one selected from Cu, Ag and Au.

5. Process for the dehydrogenation of propane according to claim 4, characterized in that the elements of group IB of the periodic Table of the elements or their oxides are Cu and Ag.

6. Process for the dehydrogenation of propane according to claim 4, characterized in that the elements of group IB of the periodic Table of the elements or their oxides are Cu and Au.

7. the method for propane dehydrogenation according to claim 1, characterized in that the specific surface of the alumina support is between 50 and 500m²(g) the pore diameter is 5-40 nm.

8. A process for the dehydrogenation of propane according to claim 7, characterized in that the specific surface of the alumina support ranges from 117 to 350m²the pore diameter is 8-25 nm.

9. A method for preparing a catalyst for propane dehydrogenation according to any of claims 1 to 8, characterized by comprising the steps of:

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 required amount of soluble solution containing Cr and/or W and soluble solution in the IB group of the periodic table of elements to obtain a mixture I, and adjusting the pH value of the mixture I to be 1-7 by using 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.

Technical Field

The present invention relates to a process for the dehydrogenation of propane.

Background

With the popularization of civil natural gas and the mature utilization of shale gas development technology, the utilization of low-carbon alkane contained in the natural gas, especially propane, is widely concerned by people. 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 propane dehydrogenation technology is currently industrialized, catalyst systems of the technology are Pt catalysts and Cr catalysts, main dehydrogenation technologies include 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, most industrialized devices are the Oleflex technology and the Catofin technology, and catalysts applied to the Oleflex technology and the Catofin technology are Pt catalysts and Cr catalysts respectively. The Pt dehydrogenation catalyst is used for propane dehydrogenation, has the advantages of environmental friendliness, high activity and the like, but has high price, complex preparation and high requirement on the purity of reaction raw materials. The Cr series catalyst has low price, relatively high activity and low requirement on the purity of raw materials, but has certain influence on the environment, and the reaction process needs frequent regeneration. The low-carbon alkane dehydrogenation process is characterized in that propane is converted into propylene by contacting with a catalyst in a reaction section. Typically, the fresh propane feed is combined with propane recycle from the bottoms of the product separation column and the de-oiling column overhead as feed to the reactor. The raw material is heated and gasified by a heat exchanger, and the gasified raw material is heated again after heat exchange in the heat exchanger. The heated gasification mass is heated in a feed heating furnace to a reaction temperature and then fed to a reactor. The hot discharged 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 for separation and recovery.

Chinese patent CN 104148070 discloses a low-carbon alkane dehydrogenation catalyst containing framework silver, which adopts aluminum oxide containing silver as a carrier, chromium oxide as an active component, and sodium, potassium, calcium, copper, zirconium, silver and the like as auxiliaries, and can improve the stability and the carbon deposition resistance of the catalyst. Patent CN 103769156 discloses a dehydrogenation catalyst and a preparation method thereof, wherein ammonia-treated alumina is used as a carrier, chromium is used as an active component, potassium, manganese, cobalt, iron, nickel, copper and the like are used as auxiliaries, and the dehydrogenation catalyst has the advantages of low chromium oxide content, high activity, good propylene selectivity and the like. Patent CN 102019178A reports a catalyst for preparing propylene by propane dehydrogenation, and preparation and application thereof, wherein the content of chromium oxide is 10-20%, the reaction temperature is 590 ℃, the absolute pressure is 0.105MPa, and the space velocity is 900 hours^-1Under the condition, the conversion rate of propane is 40% and the selectivity of propylene is 85% when the reaction is carried out for 5 min. 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 alkali metal and the metal assistant in the above patent can improve the activity, selectivity or anti-carbon deposition ability of the catalyst to some extent, but the activity of the catalyst still needs to be further improved. W has more applications in the petrochemical industry, and can effectively improve the activity of the catalyst by the synergistic effect with Cr and the addition of a proper transition metal element as an auxiliary agent.

disclosure of Invention

One of the technical problems to be solved by the invention is the problem of low activity of the propane dehydrogenation catalyst in the prior art, and provides a method 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: a method for propane dehydrogenation is characterized in that a propane raw material is in direct contact reaction with a catalyst to obtain propylene, and the method is characterized in that the reaction pressure is 0.01-1 MPa, the temperature is 530-660 ℃, and the mass space velocity is 0.1-10 h^-1(ii) a The catalyst comprises the following components in parts by weight:

a) 1-28 parts of Cr and/or W element or oxide thereof;

b)0 to 5 parts of at least one element selected from group IB of the periodic table of elements or an oxide thereof;

c) 69-96 parts of Al₂O₃And (3) a carrier.

In the technical scheme, the parts of Cr and/or W elements or oxides thereof are 3-25 parts by weight of the propane catalyst.

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 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: (0.1-10): 1. in this case, the use of both Cr and W has an unexpected synergistic effect in improving the catalytic activity 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 IB group of the periodic table of elements or the oxide thereof is 0.01-3 parts by weight of the propane catalyst, wherein the IB group element is selected from at least one of Cu, Ag and Au.

In the above technical solution, more preferably, the group ib element of the periodic table or the oxide thereof is Cu or Ag.

In the above technical solution, more preferably, the group ib element of the periodic table or an oxide thereof is Cu or Au.

In the above technical scheme, the preferred range of the part of group IB element or oxide thereof in the periodic table is 0.3-3 parts by weight of the propane catalyst.

In the above technical solution, as the most preferable technical solution, the group ib element or its oxide is a mixture of Cu, Ag and Au. In this case, the combination of group ib elements or their oxides Cu, Ag and Au in the catalyst has an unexpected synergistic effect in improving the catalyst activity of the propane dehydrogenation catalyst.

The Cr element and the W element are used together and cooperate with the IB element, so that the catalyst has unexpected synergistic effect on the aspect of improving the catalyst activity 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 method of preparing a catalyst for propane dehydrogenation comprising the steps of:

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 required amount of soluble salt solution containing Cr and/or W and soluble solution in the IB group of the periodic table of elements to obtain a mixture I, and adjusting the pH value of the mixture I to be 1-7 by using 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. Cu, Ag and Au 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 530-660 ℃, and the mass space velocity is 0.3-8 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. The conversion rate of the propane is obtained by multiplying the content of the propane which accounts for the sum of the contents of all gas-phase products after the reaction by 100 percent; 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 Cr-series catalyst used for propane dehydrogenation is easy to deposit carbon so that the deactivation speed is accelerated, and the reaction process is complicated due to frequent regeneration. The W element of VIB group has several variable valence states, and Cr and/or W are added simultaneously, so that it can effectively change the acid-base distribution and surface characteristics of catalyst surface, and can make the catalyst possess higher activity. When the catalyst obtained by adopting the preparation conditions is used for propane dehydrogenation reaction, the propane conversion rate is 46 percent, the propylene selectivity is 92.3 percent, and a better technical effect is achieved.

The invention is further illustrated by the following examples.

Detailed Description

[ example 1 ]

47.4 g of chromium nitrate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 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 catalyst is loaded 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 ]

47.4 g of chromium nitrate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 g of a mixture having a specific surface area of 340m was added²per g, poreadjusting the pH value of an alumina carrier with the diameter of 9nm to 3.5 by using 2.5 percent ammonia water, then soaking in a water bath at the temperature of 80 ℃ for 1 hour, taking out a sample, filtering, drying in a drying oven at the temperature of 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast at the temperature of 550 ℃ for 4 hours to obtain the required catalyst. The propane starting material was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 3 ]

47.4 g of chromium nitrate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 g of a specific surface area 173m 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 4 ]

47.4 g of chromium nitrate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 g of a mixture having 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 5 ]

47.4 g of chromium nitrate and 4.4 g of silver nitrate were weighed into 100 ml of deionized water, and 88 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. ProparaffinThe reaction of the above catalyst was carried out under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 6 ]

47.4 g of chromium nitrate and 5.6 g of sodium chloroaurate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 7 ]

Ammonium tungstate 9.8 g and copper nitrate 9.1 g were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 8 ]

Ammonium tungstate 9.8 g and silver acetate 4.3 g were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 9 ]

Weighing 9.8 g of ammonium tungstate and 3.9 g of potassium dicyanoaurate, adding the materials into 100 ml of deionized water, and then addingAdding 88 g of specific surface area 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 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 10 ]

47.4 g of chromium nitrate, 3.77 g of copper acetate and 2.2 g of silver nitrate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 11 ]

47.4 g of chromium nitrate, 3.54 g of copper nitrate and 1.95 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 12 ]

9.8 g of ammonium tungstate, 3.77 g of copper acetate and 2.2 g of silver nitrate were weighed into 100 ml of deionized water, and 88 g of a specific surface area of 117m was added²The preparation method comprises the 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, soaking in a water bath at 80 ℃ for 1 hour, taking out a sample, filtering, drying in an oven at 120 ℃ for 8 hoursThen, the sample is put into a muffle furnace to be roasted for 4 hours at the temperature of 550 ℃, and the required catalyst is obtained. The propane starting material was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 13 ]

9.8 g of ammonium tungstate, 3.54 g of copper nitrate and 1.95 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 g of specific surface area 117m was added²The preparation method comprises the following steps of regulating the pH value of an alumina carrier with the aperture of 15nm to 1 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, 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 14 ]

47.4 g of chromium oxalate, 2.36 g of copper nitrate, 1.47 g of silver nitrate and 1.3 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 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 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 prepared catalyst was charged into a fixed bed reactor, and activity evaluation was performed at 550 ℃ and the results are shown in table 1.

[ example 15 ]

9.8 g of ammonium tungstate, 2.36 g of copper nitrate, 1.47 g of silver nitrate and 1.3 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 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 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 reaction conditions of the propane feedstock and the above-described catalyst were the same as in example 1The reaction was carried out under the conditions shown in Table 1.

[ example 16 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 17 ]

13.17 g of chromium nitrate, 2.73 g of ammonium tungstate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 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 18 ]

65.83 g of chromium nitrate, 13.63 g of ammonium tungstate and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 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 19 ]

7.90 g of chromium nitrate, 1.64 g of ammonium tungstate and 9.1 g of copper nitrate were weighed and added to 100 mlThen 88 g of deionized water with a specific surface area of 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 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 and 9.1 g of copper nitrate were weighed, added to 100 ml of deionized water, and 88 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 ]

23.7 g of chromium nitrate, 4.9 g of ammonium tungstate and 4.4 g of silver nitrate were weighed and added to 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 22 ]

23.7 g of chromium nitrate, 4.9 g of ammonium tungstate and 3.9 g of potassium dicyanoaurate are weighed, added into 100 ml of deionized water, and 88 g of specific surface area 117m is added²alumina carrier with pore diameter of 15nm, adjusting pH value of the solution to 3.5 with 2.5% ammonia water, soaking in 50 deg.C water bath for 1 hr, taking out sample, and processingfiltering, 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 23 ]

23.7 g of chromium nitrate, 4.9 g of ammonium tungstate, 3.77 g of copper acetate and 2.2 g of silver nitrate were weighed and added to 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 24 ]

37.9 g of chromium nitrate, 1.97 g of ammonium tungstate, 3.77 g of copper acetate and 2.2 g of silver nitrate were weighed and added to 100 ml of deionized water, and 88 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 25 ]

9.5 g of chromium nitrate, 7.87 g of ammonium tungstate, 3.77 g of copper acetate and 2.2 g of silver nitrate were weighed into 100 ml of deionized water, and 88 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 26 ]

23.7 g of chromium nitrate, 4.9 g of ammonium tungstate, 3.54 g of copper nitrate and 1.95 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 27 ]

37.9 g of chromium nitrate, 1.97 g of ammonium tungstate, 3.54 g of copper nitrate and 1.95 g of potassium dicyanoaurate are weighed into 100 ml of deionized water, and 88 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 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 28 ]

9.5 g of chromium nitrate, 7.87 g of ammonium tungstate, 3.54 g of copper nitrate and 1.95 g of potassium dicyanoaurate were weighed into 100 ml of deionized water, and 88 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 29 ]

23.7 g of chromium nitrate, 4.9 g of ammonium tungstate, 2.36 g of copper nitrate, 1.47 g of silver nitrate and 1.3 g of potassium dicyanoaurate are weighed, added to 100 ml of deionized water, and 88 g of specific surface area 117m is added²(ii) g, pore size 15nm, using 25% ammonia water to adjust the pH value of the solution to 3.5, then soaking in a water bath at 50 ℃ for 1 hour, taking out the sample, filtering, drying in an oven at 120 ℃ for 8 hours, and then putting the sample into a muffle furnace to roast for 4 hours at 550 ℃ to obtain the required catalyst. The propane starting material was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

[ example 30 ]

37.9 g of chromium nitrate, 1.97 g of ammonium tungstate, 2.36 g of copper nitrate, 1.47 g of silver nitrate and 1.3 g of potassium dicyanoaurate are weighed, added to 100 ml of deionized water, and 88 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 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 31 ]

9.5 g of chromium nitrate, 7.87 g of ammonium tungstate, 2.36 g of copper nitrate, 1.47 g of silver nitrate and 1.3 g of potassium dicyanoaurate were weighed, added to 100 ml of deionized water, and 88 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 evaluation conditions were the same as in example 1, and the results are shown in Table 1.

[ example 32 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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. Propane feedstock and processThe catalyst reacts under the following conditions: normal pressure and 530 ℃; the mass space velocity of the propane is 1.0h^-1. The results are shown in Table 2.

[ example 33 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 1.0h^-1. The results are shown in Table 2.

[ example 34 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following 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 35 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following conditions: the pressure is 1MPa, and the temperature is 620 ℃; the mass space velocity of the propane is 1.0h^-1. As a result thereofSee table 2.

[ example 36 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following 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 37 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 0.3h^-1. The results are shown in Table 2.

[ example 38 ]

23.7 g of chromium nitrate, 2.4 g of tungsten acetate and 9.1 g of copper nitrate were weighed into 100 ml of deionized water, and 88 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 raw material reacts with the catalyst under the following conditions: normal pressure and 620 ℃ of temperature; the mass space velocity of the propane is 8h^-1. The results are shown in Table 2.

Comparative example 1

Weigh 37.9 gChromium nitrate, 1.97 g ammonium tungstate, was added to 100 ml deionized water, followed by 88 g of specific surface area 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

Comparative example 2

9.8 g of ammonium tungstate was weighed, added to 100 ml of deionized water, and 88 g of ammonium tungstate having 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

Comparative example 3

47.4 g of chromium nitrate, 0.68 g of sodium carbonate and 3.03 g of iron nitrate were weighed into 100 ml of deionized water, and 88 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 catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

Comparative example 4

9.5 g of chromium nitrate and 7.87 g of ammonium tungstate were weighed, added to 100 ml of deionized water, and 88 g of a specific surface area of 117m was added²The alumina carrier with the pore diameter of 15nm is used for regulating the pH value of the solution to 3.5 by using 2.5 percent ammonia water, then the solution is soaked in a water bath at the temperature of 50 ℃ for 1 hour, a sample is taken out for filtration, and the sample is dried in a baking oven at the temperature of 120 DEG CAnd drying for 8 hours, and then putting the sample into a muffle furnace to be roasted for 4 hours at the temperature of 550 ℃ to obtain the required catalyst. The propane starting material was reacted with the above catalyst under the same reaction conditions as in example 1, and the results are shown in Table 1.

TABLE 1

[ examples 32 to 38 ]

The catalyst prepared in example 16 was used for propane dehydrogenation, and the reaction conditions and evaluation results are shown in Table 2.

TABLE 2