CN107213909B - Dehydrogenation catalyst and preparation method and application thereof - Google Patents
Dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN107213909B CN107213909B CN201610166407.0A CN201610166407A CN107213909B CN 107213909 B CN107213909 B CN 107213909B CN 201610166407 A CN201610166407 A CN 201610166407A CN 107213909 B CN107213909 B CN 107213909B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
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Abstract
The invention relates to the field of catalysts, and particularly discloses a dehydrogenation catalyst, a preparation method and an application thereof, wherein the dehydrogenation catalyst contains a carrier, an auxiliary agent, a modifier and a dehydrogenation active component, the carrier contains alumina, part of the auxiliary agent and part of the modifier, the auxiliary agent is an IVA group element and an alkali metal element, and the modifier is a halogen group element, wherein the IVA group element is at least one selected from germanium, tin and lead, and the alkali metal element is at least one selected from lithium and potassium; the active component contains a noble metal element selected from at least one of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium. The catalyst has high strength, and when the dehydrogenation catalyst is used for dehydrogenation reaction, particularly for the reaction of preparing isobutene by isobutane dehydrogenation, the selectivity and the yield of the isobutene can be higher.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a dehydrogenation catalyst and a preparation method and application thereof.
Background
In recent years, due to the introduction of various environmental protection policies and the popularization and use of unleaded gasoline, the demand of high-octane additives such as MTBE (methyl tert-butyl ether) and ETBE (ethylene-tetra-ethyl ether) is rapidly increasing globally, and the demand of isobutene as a raw material for producing methyl tert-butyl ether is also increased dramatically. In addition, the development and utilization of downstream products of isobutene enable isobutene produced by traditional petroleum catalytic cracking to be far from meeting the current requirements, so that the sources of isobutene are expanded, the yield of isobutene is increased, and the development of the current petrochemical industry is urgent. In China, isobutane in catalytic cracking petroleum gas is mainly used as a cheap fuel to be burnt, so that the resource is greatly wasted. Therefore, a large amount of cheap isobutane is subjected to dehydrogenation reaction to prepare isobutene with high added value, and the method has important economic, social and environmental benefits.
However, the catalyst used in the dehydrogenation process plays a crucial role in the dehydrogenation, and the physical parameters of the carrier of the catalyst have a great relationship with the performance of the catalyst, so that how to prepare a more efficient dehydrogenation catalyst falls on how to develop a more efficient carrier.
Currently, a lot of researchers at home and abroad have been devoted to the improvement of a catalyst carrier, for example, the improvement of a specific surface area, a pore volume, a pore diameter and the like of a catalyst carrier containing alumina is aimed at obtaining a catalyst with higher catalytic activity, selectivity and the like. However, although the prior art respectively adopts methods of adding alkaline earth metal compounds or fluorides to alumina raw materials to improve alumina carriers, the requirements on the performance of the alumina carriers are continuously increased along with the large-scale industrial application of high-selectivity dehydrogenation catalysts, and how to develop a carrier of a dehydrogenation catalyst, which can further improve the catalytic activity of the catalyst, becomes an important research direction.
For example, patent application publication No. CN101862669A discloses a catalyst for preparing isobutene by isobutane dehydrogenation and a preparation method thereof, and specifically discloses a catalyst using a mesoporous alumina molecular sieve containing tin in the framework as a carrier, but the preparation method of the framework containing tin disclosed in the prior art is complex and high in cost, and when the catalyst containing the framework containing tin is used for catalyzing the isobutane dehydrogenation reaction, the conversion rate of isobutane, the selectivity of isobutene and the yield cannot be particularly and powerfully improved under the high-cost preparation condition.
In addition, the physicochemical properties of the catalyst also have a crucial influence on the process benefit of preparing isobutene by isobutane dehydrogenation, for example, the catalyst for preparing isobutene by isobutane dehydrogenation disclosed in CN102000593A can ensure higher isobutane conversion rate and isobutene yield, but the strength of the catalyst for preparing isobutene by isobutane dehydrogenation disclosed in the CN102000593A is not high, so that the economic benefit of preparing isobutene by isobutane dehydrogenation is greatly influenced, and the catalyst used in the process can be replaced in a shorter period.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a dehydrogenation catalyst and a preparation method and application thereof.
In order to achieve the above object, in a first aspect, the present invention provides a dehydrogenation catalyst comprising a carrier, an auxiliary, a modifier and a dehydrogenation active component, wherein the carrier comprises alumina, a part of the auxiliary and a part of the modifier, the auxiliary is a group IVA element and an alkali metal element, and the modifier is a halogen element, wherein the group IVA element is at least one selected from germanium, tin and lead, and the alkali metal element is at least one selected from lithium and potassium; the active component contains a noble metal element selected from at least one of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium.
In a second aspect, the present invention also provides a process for the preparation of a dehydrogenation catalyst:
(1) preparing a carrier: in the solution state containing halogen elements, an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound are subjected to first contact and coprecipitation; then, sequentially drying and roasting the solid obtained after coprecipitation, wherein the group IVA element in the group IVA element-containing compound is at least one selected from germanium, tin and lead; the alkali metal element in the alkali metal-containing compound is at least one selected from lithium and potassium to obtain a carrier;
(2) preparing a catalyst: carrying out second contact on the obtained carrier and an impregnation liquid, and then sequentially drying and roasting the solid obtained after the second contact, wherein the impregnation liquid comprises a compound containing the IVA group element, an alkali metal compound, a dehydrogenation active component containing the noble metal element and a halogen element; the noble metal element is at least one selected from the group consisting of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium.
In a third aspect, the invention further provides the dehydrogenation catalyst and an application of the dehydrogenation catalyst obtained by the method for preparing the dehydrogenation catalyst in the reaction of preparing isobutene through isobutane dehydrogenation.
The external surface of the carrier and the alumina framework in the dehydrogenation catalyst provided by the invention are both provided with the auxiliary agent and the modifier, and the dehydrogenation catalyst provided by the invention is used for the reaction of preparing isobutene by isobutane dehydrogenation, so that the strength of the catalyst is obviously improved while the yield of isobutene is ensured to be higher, and the economic benefit of preparing isobutene by isobutane dehydrogenation is obviously improved, and according to the effect of the test example provided by the invention, the yield can reach more than 34 percent and even can reach 36.7 percent at most; the selectivity of isobutene can reach over 96 percent, even 97.2 percent at most.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the present invention, it should be specifically understood that the terms "first" and "second" are not directly connected in a material relationship, but are described in a distinguishing manner only and should not be construed as limiting words.
In a first aspect, the present invention provides a dehydrogenation catalyst, which comprises a carrier, an auxiliary agent, a modifier and a dehydrogenation active component, wherein the carrier comprises alumina, a part of the auxiliary agent and a part of the modifier, the auxiliary agent is an IVA group element and an alkali metal element, and the modifier is a halogen group element, wherein the IVA group element is at least one selected from germanium, tin and lead, and the alkali metal element is at least one selected from lithium and potassium; the active component contains a noble metal element selected from at least one of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium.
In the present invention, the partial assistant and the partial modifier are respectively a part of the assistant and the modifier in the above-mentioned "the dehydrogenation catalyst contains a carrier, an assistant, a modifier and a dehydrogenation active component".
The dehydrogenation catalyst provided by the invention has the advantages of high strength, can improve the yield of products when used in dehydrogenation reaction, particularly can ensure that the yield of isobutene is higher in the reaction of preparing isobutene by dehydrogenating isobutane, and greatly improves the selectivity of isobutene.
The dehydrogenation catalyst according to the present invention, wherein the partial promoter may be contained in the carrier in an amount of 0.1 to 10 wt% based on the total amount of the carrier.
The dehydrogenation catalyst according to the present invention, wherein the partial modifier is contained in the carrier in an amount of 0.1 to 15% by weight based on the total amount of the carrier.
In the dehydrogenation catalyst of the present invention, in the partial auxiliary agent of the carrier, the weight ratio of the group IVA element to the alkali metal element is 1: 1-2.
Preferably, in the dehydrogenation catalyst of the present invention, in the partial promoter of the carrier, the group IVA element is tin; the alkali metal element is potassium.
In another preferred aspect, in the dehydrogenation catalyst of the present invention, in the partial promoter of the carrier, the group IVA element is tin and lead, and the alkali metal element is potassium.
In another preferred aspect of the present invention, in the partial auxiliary agent of the carrier, the mass ratio of tin to lead may be preferably 1: 0.2-0.6.
In the dehydrogenation catalyst of the present invention, the content of the active component may be 0.1 to 10% by weight based on the total amount of the noble metal element, based on the total amount of the carrier.
Preferably, in the dehydrogenation catalyst of the present invention, the portion of promoter present on the support is present in an amount of from 20 to 80 wt.%, preferably from 45 to 80 wt.%, based on the total promoter content of the catalyst; the proportion of the modifier in the support is from 15 to 85% by weight, preferably from 55 to 85% by weight, based on the total amount of modifier in the catalyst.
In a second aspect, the present invention also provides a process for the preparation of a dehydrogenation catalyst as described below:
(1) preparing a carrier: in the solution state containing halogen elements, an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound are subjected to first contact and coprecipitation; then, sequentially drying and roasting the solid obtained after coprecipitation, wherein the group IVA element in the group IVA element-containing compound is at least one selected from germanium, tin and lead; the alkali metal element in the alkali metal-containing compound is at least one selected from lithium and potassium to obtain a carrier;
(2) preparing a catalyst: carrying out second contact on the obtained carrier and an impregnation liquid, and then sequentially drying and roasting the solid obtained after the second contact, wherein the impregnation liquid comprises a compound containing the IVA group element, an alkali metal compound, a dehydrogenation active component containing the noble metal element and a halogen element; the noble metal element is at least one selected from the group consisting of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium.
In the method of the present invention, it is particularly preferable that the optional species of the group IVA element-containing compound, the alkali metal-containing compound and the halogen element in the step (2) are the same as those of the group IVA element-containing compound, the alkali metal-containing compound and the halogen element in the step (1), respectively.
According to the method for preparing a dehydrogenation catalyst of the present invention, it is preferable that the group IVA element in the group IVA element-containing compound is tin; the alkali metal element in the alkali metal-containing compound is potassium.
According to the method for producing a dehydrogenation catalyst of the present invention, preferably in step (1), that is, in the method for producing a carrier, the group IVA element in the group IVA element-containing compound is tin and lead; the alkali metal element in the alkali metal-containing compound is potassium.
More preferably, in the method of the present invention, the mass ratio of tin to lead in the carrier is 1: 0.2-0.6.
In the method of the present invention, the kind of the solution containing a halogen element is not particularly limited as long as the solution can contain the halogen element, and in the method of the present invention, the halogen element may be provided by at least one of a group IVA element-containing compound and an alkali metal-containing compound. In the present invention, the kind of the halogen element is not particularly limited, but it is preferable that the halogen element is chlorine element in order to reduce production cost. In the present invention, the solution state may be an aqueous solution state.
In the method of the present invention, the aluminum-containing compound includes at least one selected from the group consisting of aluminum sulfate, aluminum chloride and aluminum nitrate and a meta-aluminate.
In the method of the present invention, the type of the alkali metal-containing compound is not particularly limited, but in the present invention, the alkali metal element in the alkali metal-containing compound may be provided by a nitrate of the alkali metal element, and in the present invention, the alkali metal-containing compound is preferably potassium nitrate.
Preferably, according to the process of the present invention, the aluminium-containing compound is aluminium sulphate and a meta-aluminate. In the method of the present invention, the type of the meta-aluminate is not particularly limited, and it is preferable that the meta-aluminate is sodium meta-aluminate.
In the method of the present invention, it is specifically mentioned that: in the invention, the alumina carrier is preferably prepared by a double aluminum method, so that when the alumina carrier is prepared by the double aluminum method, in order to save the production cost and improve the production efficiency, the molar ratio of the aluminum sulfate to the sodium metaaluminate is preferably 1: 6.
in the method of the present invention, it is preferable that the method of first contacting and coprecipitating the aluminum-containing compound, the group IVA element-containing compound, and the alkali metal-containing compound is: first, an aluminum-containing compound, a group IVA element-containing compound, and an alkali metal-containing compound are dissolved in an appropriate amount of solvent to form solutions (the concentration of the solution is not particularly limited in the present invention, as long as the above compounds are completely dissolved, and those skilled in the art can select the solution according to conventional means), and then the solutions are mixed to perform the first contact and coprecipitation. In the invention, the dissolving solutions are preferably mixed, contacted and coprecipitated by a steady flow pump in a dropping manner, and the dropping speed is not particularly limited by the method provided by the invention, as long as the dropping speed of each dissolving solution is enabled to be equal to that of the aluminum sulfate and the sodium metaaluminate which are dropped at the same time after the dropping of each dissolving solution is completed within the same time, and the amount of the aluminum sulfate and the sodium metaaluminate which are dropped at the same time is 1: a molar ratio of 6.
In the method of the present invention, the kind of the group IVA element-containing compound is not particularly limited as long as the group IVA element can be contained in the outer surface and the skeleton of the obtained alumina support when the dehydrogenation catalyst is prepared by using the group IVA element-containing compound. According to a preferred embodiment of the present invention, the group IVA element-containing compound may be at least one of a group IVA element-containing chloride, a group IVA element-containing sulfate, and a group IVA element-containing nitrate.
In the method of the present invention, the conditions for the first contacting and coprecipitating of the aluminum-containing compound, the group IVA element-containing compound, and the alkali metal-containing compound are not particularly limited, but in order to make the dehydrogenation catalyst of the present invention stronger and to obtain a higher yield of isobutene when used in the reaction for producing isobutene by dehydrogenation of isobutane, it is preferable that the conditions for the first contacting and coprecipitating include: the time is 6-15 h.
In the method of the present invention, preferably, the conditions of the first contacting and co-precipitating include: the temperature is 40-80 ℃.
In the method of the present invention, preferably, the conditions of the first contacting and co-precipitating include: the pH value is 8-10.
In the method of the present invention, in the step (1), the conditions of the drying and the firing are not particularly limited. In order to obtain higher yield of isobutene when the dehydrogenation catalyst is used for the reaction of preparing isobutene by dehydrogenating isobutane, the drying temperature in the step (1) is preferably 60-120 ℃, and the drying temperature is more preferably 80-120 ℃.
In order to make the dehydrogenation catalyst of the present invention have higher strength and obtain higher yield of isobutene when used in the reaction of isobutene preparation by isobutane dehydrogenation, the present invention preferably makes the calcination temperature in the step (1) 400-750 ℃, more preferably makes the calcination temperature 450-650 ℃.
In the method of the present invention, the activated alumina carrier obtained after drying and calcining may be further subjected to shaping, the method of the shaping is not particularly limited, and in order to make the dehydrogenation catalyst of the present invention have higher strength and obtain higher yield of isobutene when used in the reaction of isobutene preparation by isobutane dehydrogenation, the preferred method of the shaping of the present invention may be: mixing the calcined activated alumina carrier with a thickening agent such as sesbania powder, adding a peptizing agent such as 2 wt% nitric acid for molding, curing the molded carrier at room temperature for 5-7h, and sequentially drying and calcining to obtain the molded carrier. In the method of the present invention, it is preferable that the shaping is such that the alumina support may have a spherical shape, a clover shape, a butterfly shape, or the like.
In the method of the present invention, it is preferable that the group IVA element compound, the alkali metal-containing compound, and the halogen element in the step (1) and the step (2) are used in amounts such that the content of the active component is 0.1 to 10% by weight based on the total amount of the noble metal element, based on the total amount of the support; the sum of the contents of the group IVA element and the alkali metal in the carrier accounts for 20 to 80 wt% of the sum of the contents of the group IVA element and the alkali metal in the entire catalyst, and the content of the halogen element in the carrier accounts for 15 to 85 wt% of the total content of the halogen element in the catalyst.
In the method of the present invention, it is preferable that the conditions for the second contacting of the carrier with the impregnation liquid in the step (2) include: the time is 10-15h, and the temperature is 0-70 ℃.
In the method of the present invention, it is preferable that the dehydrogenation active component containing a noble metal element may include at least one of a chloride, a nitrate compound, and an oxide of the noble metal element, and for example, the dehydrogenation active component containing a noble metal element may be chloroplatinic acid, nickel nitrate, palladium chloride, cobalt nitrate, and the like, which are exemplified in examples of the present invention. The invention is not limited thereto.
In the method of the present invention, in the step (2), the solvent may be removed from the mixture obtained after the second contacting under reduced pressure, and the obtained solid may be sequentially dried and calcined. In the step (2) of the present invention, there is no particular limitation on the method of sequentially drying and calcining the obtained solid, and the present invention may preferably be dried at 100 ℃ overnight and then calcined at 600 ℃ to obtain the dehydrogenation catalyst of the present invention, but the present invention is not limited thereto.
In a third aspect, the invention further provides the dehydrogenation catalyst and an application of the dehydrogenation catalyst obtained by the method for preparing the dehydrogenation catalyst in the reaction of preparing isobutene through isobutane dehydrogenation.
The present invention will be described in detail below by way of examples. In the following examples, various reagents used were commercially available unless otherwise specified.
Example 1
This example used the process of the present invention to prepare a dehydrogenation catalyst as described herein.
(1) Preparation of the support
491.4g of sodium metaaluminate, 666g of aluminum sulfate trihydrate, 4.48g of stannic chloride and 5.29g of potassium nitrate are respectively dissolved by using a proper amount of deionized water to form dissolved solutions, and then the obtained saturated solution is added into 1L of deionized water to contact and coprecipitate for 10 hours under the conditions that the temperature is 60 ℃ and the pH value is 8. The solid obtained by coprecipitation is then dried at 100 ℃ overnight and then calcined at 600 ℃ to obtain activated alumina.
Mixing 300g of activated alumina with a proper amount of sesbania powder, adding 2 wt% of nitric acid as a peptizer, and extruding and molding on a clover orifice plate. The extruded strands were cured at room temperature (25 ℃) for 6 hours, then dried at 100 ℃ overnight, and calcined at 600 ℃ to give a shaped activated alumina support 1-A.
The alumina carrier 1-A is tested to contain 0.43 weight percent of tin, 0.43 weight percent of potassium and 0.25 weight percent of chlorine.
(2) Preparation of the catalyst
And (2) taking 200g of the alumina carrier 1-A obtained in the step (1) to contact with an impregnation liquid at 40 ℃ for 12h, wherein the impregnation liquid contains 2.65g of chloroplatinic acid, 1.10g of tin chloride, 1.91g of potassium chloride and 376g of water. After the completion of the contact, the solvent was removed under reduced pressure, and the obtained solid was dried at 100 ℃ overnight and calcined at 600 ℃ in this order to obtain the dehydrogenation catalyst 1-B of the present invention.
Example 2
This example used the process of the present invention to prepare a dehydrogenation catalyst as described herein.
(1) Preparation of the support
491.4g of sodium metaaluminate, 666g of aluminum sulfate trihydrate, 8.96g of stannic chloride and 5.29g of potassium nitrate are respectively dissolved by using a proper amount of deionized water to form dissolved solutions, and then the obtained saturated solution is added into 1L of deionized water to contact and coprecipitate for 12 hours under the conditions that the temperature is 50 ℃ and the pH value is 9. The solid obtained by coprecipitation is then dried at 60 ℃ overnight and then calcined at 750 ℃ to obtain activated alumina.
Mixing 300g of activated alumina with a proper amount of sesbania powder, adding 2 wt% of nitric acid as a peptizer, and extruding and molding on a clover orifice plate. The extruded strands were cured at room temperature (25 ℃) for 5h, then dried at 60 ℃ overnight, and calcined at 700 ℃ to give a shaped activated alumina support 2-a.
The test shows that the alumina carrier 2-A contains 0.88 weight percent of tin, 0.41 weight percent of potassium and 0.27 weight percent of chlorine.
(2) Preparation of the catalyst
And (2) taking 200g of the alumina carrier 2-A obtained in the step (1) to contact with an impregnation liquid at 50 ℃ for 10h, wherein the impregnation liquid contains 2.65g of chloroplatinic acid, 1.10g of tin chloride, 1.91g of potassium chloride and 376g of water. And (3) after the contact is finished, removing the solvent under reduced pressure, and drying the obtained solid at 100 ℃ overnight and roasting at 600 ℃ in sequence to obtain the dehydrogenation catalyst 2-B.
Example 3
This example used the process of the present invention to prepare a dehydrogenation catalyst as described herein.
(1) Preparation of the support
491.4g of sodium metaaluminate, 666g of aluminum sulfate trihydrate, 2.24g of stannic chloride and 5.29g of potassium nitrate are respectively dissolved by using a proper amount of deionized water to form dissolved solutions, and then the obtained saturated solution is added into 1L of deionized water to contact and coprecipitate for 8 hours under the conditions that the temperature is 70 ℃ and the pH value is 8. The solid obtained by coprecipitation is then dried at 120 ℃ overnight and then calcined at 500 ℃ to obtain activated alumina.
Mixing 300g of activated alumina with a proper amount of sesbania powder, adding 2 wt% of nitric acid as a peptizer, and extruding and molding on a clover orifice plate. The extruded strands were cured at room temperature (25 ℃) for 7h, then dried at 110 ℃ overnight, and calcined at 450 ℃ to give a shaped activated alumina support 3-A.
The test shows that the alumina carrier 3-A contains 0.21 weight percent of tin, 0.42 weight percent of potassium and 0.14 weight percent of chlorine.
(2) Preparation of the catalyst
And (2) taking 200g of the alumina carrier 3-A obtained in the step (1) to contact with an impregnation liquid at 40 ℃ for 12h, wherein the impregnation liquid contains 2.65g of chloroplatinic acid, 1.10g of tin chloride, 1.91g of potassium chloride and 376g of water. After the completion of the contact, the solvent was removed under reduced pressure, and the obtained solid was dried at 100 ℃ overnight and calcined at 600 ℃ in this order to obtain dehydrogenation catalyst 3-B of the present invention.
Example 4
This example used the process of the present invention to prepare a dehydrogenation catalyst as described herein.
(1) Preparation of the support
491.4g of sodium metaaluminate, 666g of aluminum sulfate trihydrate, 3.20g of stannic chloride, 0.75g of lead chloride and 5.29g of potassium nitrate are respectively dissolved by using a proper amount of deionized water to form dissolved solutions, and then the obtained saturated solution is added into 1L of deionized water at the temperature of 80 ℃ and the pH value of 9 to be contacted and coprecipitated for 15 hours. The solid obtained by coprecipitation is then dried at 80 ℃ overnight and then calcined at 650 ℃ to obtain activated alumina.
Mixing 300g of activated alumina with a proper amount of sesbania powder, adding 2 wt% of nitric acid as a peptizer, and extruding and molding on a clover orifice plate. The extruded strands were cured at room temperature (25 ℃) for 7h, then dried at 100 ℃ overnight, and calcined at 550 ℃ to give a shaped activated alumina support 4-A.
The alumina carrier 4-A is tested to contain 0.31 weight percent of tin, 0.12 weight percent of lead, 0.43 weight percent of potassium and 0.48 weight percent of chlorine.
(2) Preparation of the catalyst
And (2) taking 200g of the alumina carrier 4-A obtained in the step (1) to contact with an impregnation liquid at 40 ℃ for 12h, wherein the impregnation liquid contains 2.65g of chloroplatinic acid, 1.10g of tin chloride, 1.91g of potassium chloride and 376g of water. After the contact is finished, the solvent is removed under reduced pressure, and the obtained solid is dried at 100 ℃ overnight and roasted at 600 ℃ in sequence to obtain the dehydrogenation catalyst 4-B.
Example 5
This example prepared a dehydrogenation catalyst in the same manner as in example 4, except that:
in step (1) of this example, the amounts of tin chloride and lead chloride used in the preparation of the carrier were 2.21g and 1.35g, respectively.
The rest of the procedure was the same as in example 4, to obtain a molded activated alumina carrier 5-A.
The alumina carrier 5-A is tested to contain 0.21 weight percent of tin, 0.21 weight percent of lead, 0.43 weight percent of potassium and 0.20 weight percent of chlorine.
Step (2) of this example was the same as step (2) of example 4, to obtain dehydrogenation catalyst 5-B according to the present invention.
Example 6
This example prepared a dehydrogenation catalyst in the same manner as in example 4, except that:
in step (1) of this example, i.e., preparation of the carrier, the amount of tin chloride used was 3.20g, and lead chloride was not used.
The rest of the procedure was the same as in example 4, to obtain a molded activated alumina carrier 6-A.
The test shows that the alumina carrier 6-A contains 0.31 weight percent of tin, 0.43 weight percent of potassium and 0.18 weight percent of chlorine.
Step (2) of this example was the same as step (2) of example 4, to obtain dehydrogenation catalyst 6-B according to the present invention.
Example 7
This example prepared a dehydrogenation catalyst in the same manner as in example 4, except that:
in step (1) of this example, i.e., preparation of the carrier, the amount of tin chloride used was 4.53g, and lead chloride was not used.
The rest of the procedure was the same as in example 4, to obtain a molded activated alumina support 7-A.
The alumina carrier 7-A was tested to contain 0.43 wt% tin, 0.43 wt% potassium, 0.18 wt% chlorine.
Step (2) of this example was the same as step (2) of example 4, to obtain dehydrogenation catalyst 7-B according to the present invention.
Example 8
This example prepared a dehydrogenation catalyst in the same manner as in example 1, except that:
in step (1) of this example, the amount of potassium nitrate used in the preparation of the carrier was 10.58 g.
The rest of the procedure was the same as in example 1 to obtain a shaped activated alumina carrier 8-A.
The alumina carrier 8-A was tested to contain 0.44 wt% tin, 0.84 wt% potassium, 0.24 wt% chlorine.
Step (2) of this example was the same as step (2) of example 1, to obtain dehydrogenation catalyst 8-B according to the present invention.
Example 9
This example prepared a dehydrogenation catalyst in the same manner as in example 1, except that:
in step (1) of this example, the amount of potassium nitrate used in the preparation of the carrier was 2.65 g.
The rest of the procedure was the same as in example 1 to obtain a molded activated alumina carrier 9-A.
The alumina carrier 9-A was tested to contain 0.44 wt% tin, 0.22 wt% potassium, and 0.27 wt% chlorine.
Step (2) of this example was the same as step (2) of example 1, to obtain dehydrogenation catalyst 9-B according to the present invention.
Comparative example 1
Mesoporous alumina molecular sieve supports 1-D containing tin in the support were prepared using the method disclosed in example 4 of CN 101862669A.
Tests show that the alumina carrier 1-D contains 1.02 wt% of tin, no potassium element and 0.87 wt% of chlorine.
A dehydrogenation catalyst was prepared by the method disclosed in example 4 of CN101862669A and was designated 1-DD.
Test examples 1 to 10
The catalysts obtained in examples 1 to 9 and comparative example 1 were used in the reaction for producing isobutylene by dehydrogenation of isobutane, and the evaluation conditions of the reaction are shown in table 1 below. The results are shown in table 2 below. And the abrasion strengths of the catalysts obtained in examples 1 to 9 and comparative example 1 were measured, and the results are specifically shown in table 2, wherein the abrasion strengths were measured by a spin collision method, specifically: the catalyst abrasion strength data was represented by the amount of fine powder generated per unit mass (1kg) of the catalyst sample, i.e., the abrasion rate (abrasion rate: amount of fine powder/original weight of catalyst × 100%).
Test example 11
The catalyst particles of example 1 of CN102000593A were measured for their attrition strength in the same manner as in test examples 1 to 10 described above, and as a result, their attrition rate was 15.3%.
TABLE 1
| Volume airspeed | Reaction pressure | Reaction temperature | Hydrogen to hydrocarbon molar ratio |
| 1500h-1 | 0.1MPa | 600℃ | 2：1 |
TABLE 2
As can be seen from the results in the above examples, comparative examples, test examples and table 2, the catalyst of the present invention has a low wear rate, i.e., a high strength, and is significantly higher than the strength of the catalyst in the comparative example. Moreover, when the catalyst is used for preparing isobutene by isobutane dehydrogenation, the conversion rate of isobutane, the selectivity of isobutene and the yield of isobutene can be obviously higher than those of the dehydrogenation catalyst obtained by the method in the prior art, and the method for preparing the dehydrogenation catalyst has the advantages of simplicity, low cost and suitability for industrial production.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
1. A dehydrogenation catalyst comprises a carrier, an auxiliary agent, a modifier and a dehydrogenation active component, and is characterized in that the carrier comprises alumina, a part of the auxiliary agent and a part of the modifier, the auxiliary agent is an IVA element and an alkali metal element, the modifier is a halogen element, wherein the IVA element is at least one selected from germanium, tin and lead, and the alkali metal element is at least one selected from lithium and potassium; the active component contains a noble metal element selected from at least one of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium;
wherein the carrier is prepared by the following method: in the solution state containing halogen elements, an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound are subjected to first contact and coprecipitation; then, drying and roasting the solid obtained after coprecipitation in sequence; the aluminum-containing compound comprises at least one selected from aluminum sulfate, aluminum chloride and aluminum nitrate and meta-aluminate;
wherein, in part of the auxiliary agent of the carrier, the weight ratio of the IVA group element to the alkali metal element is 1: 1-2.
2. The catalyst according to claim 1, wherein the partial amount of the auxiliary agent in the carrier is 0.1 to 10% by weight based on the total amount of the carrier; the content of the partial modifier is 0.1 to 15 weight percent.
3. The catalyst according to claim 1 or 2, wherein in the partial promoter of the support, the group IVA element is tin; the alkali metal element is potassium.
4. The catalyst according to claim 1 or 2, wherein in the partial promoter of the carrier, the group IVA elements are tin and lead, and the alkali metal element is potassium.
5. The catalyst according to claim 4, wherein in the partial promoter of the carrier, the mass ratio of tin to lead is 1: 0.2-0.6.
6. The catalyst of claim 1, wherein, based on the total amount of support; the content of the active component is 0.1-10 wt% calculated by the total amount of the noble metal elements, the content of the partial auxiliary agent in the carrier accounts for 20-80 wt% of the total content of the auxiliary agent in the catalyst, and the content of the partial modifier in the carrier accounts for 15-85 wt% of the total content of the modifier in the catalyst.
7. A method for preparing a dehydrogenation catalyst,
(1) preparing a carrier: in the solution state containing halogen elements, an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound are subjected to first contact and coprecipitation; then, sequentially drying and roasting the solid obtained after coprecipitation, wherein the group IVA element in the group IVA element-containing compound is at least one selected from germanium, tin and lead; the alkali metal element in the alkali metal-containing compound is at least one selected from lithium and potassium to obtain a carrier;
wherein the group IVA element-containing compound and the alkali metal-containing compound are used in such amounts that the weight ratio of the group IVA element to the alkali metal element in the carrier is 1: 1-2;
the aluminum-containing compound comprises at least one selected from aluminum sulfate, aluminum chloride and aluminum nitrate and meta-aluminate;
(2) preparing a catalyst: carrying out second contact on the obtained carrier and an impregnation liquid, and then sequentially drying and roasting the solid obtained after the second contact, wherein the impregnation liquid comprises a compound containing the IVA group element, an alkali metal compound, a dehydrogenation active component containing the noble metal element and a halogen element; the noble metal element is at least one selected from the group consisting of platinum, palladium, nickel, cobalt, rhodium, iridium, and ruthenium.
8. The method according to claim 7, wherein in the method for producing the carrier, the group IVA element-containing compound, the alkali metal-containing compound and the group halogen element-containing compound are used in such amounts that the total amount of the group IVA element and the alkali metal element in the carrier is from 0.1 to 10% by weight, based on the total amount of the carrier; the halogen element is 0.1-15 wt%.
9. The method according to claim 7 or 8, wherein, in the method for producing the support, the group IVA element in the group IVA element-containing compound is tin; the alkali metal element in the alkali metal-containing compound is potassium.
10. The method according to claim 7 or 8, wherein in the method for producing the carrier, the group IVA element in the group IVA element-containing compound is tin and lead, and the alkali metal element in the alkali metal-containing compound is potassium.
11. The method of claim 10, wherein the mass ratio of tin to lead in the carrier is 1: 0.2-0.6.
12. The process of claim 7, wherein the aluminum-containing compound is aluminum sulfate and a meta-aluminate.
13. The method of claim 7, wherein the conditions of the first contacting and co-precipitating comprise: the time is 6-15h, the temperature is 40-80 ℃, and the pH value is 8-10.
14. The method according to claim 7, wherein the group IVA element compound, the alkali metal-containing compound and the halogen element in the step (1) and the step (2) are used in such amounts that the active component is contained in an amount of 0.1 to 10% by weight based on the total amount of the noble metal element, based on the total amount of the carrier; the sum of the contents of the group IVA element and the alkali metal in the carrier accounts for 20 to 80 wt% of the sum of the contents of the group IVA element and the alkali metal in the entire catalyst, and the content of the halogen element in the carrier accounts for 15 to 85 wt% of the total content of the halogen element in the catalyst.
15. Use of the catalyst according to any one of claims 1 to 6 or the catalyst prepared by the method according to any one of claims 7 to 14 in the reaction of preparing isobutene by the dehydrogenation of isobutane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862669A (en) * | 2010-06-23 | 2010-10-20 | 东南大学 | Catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN102000593A (en) * | 2010-11-09 | 2011-04-06 | 北京化工大学 | Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof |
| CN103785384A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101862669A (en) * | 2010-06-23 | 2010-10-20 | 东南大学 | Catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof |
| CN102000593A (en) * | 2010-11-09 | 2011-04-06 | 北京化工大学 | Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof |
| CN103785384A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of catalyst for low carbon alkane dehydrogenation to prepare alkene |
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