CN107213919B - Alumina carrier, preparation method and application thereof - Google Patents
Alumina carrier, preparation method and application thereof Download PDFInfo
- Publication number
- CN107213919B CN107213919B CN201610165171.9A CN201610165171A CN107213919B CN 107213919 B CN107213919 B CN 107213919B CN 201610165171 A CN201610165171 A CN 201610165171A CN 107213919 B CN107213919 B CN 107213919B
- Authority
- CN
- China
- Prior art keywords
- containing compound
- alkali metal
- alumina carrier
- carrier
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts, and particularly discloses an alumina carrier and an application thereof. The invention also provides a preparation method of the alumina carrier, which comprises the following steps: contacting and coprecipitating an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound in a solution state containing a halogen element; the resulting solid is then dried and calcined in that order. The method for preparing the alumina carrier is simple, has lower cost and is suitable for industrial production, and the catalyst prepared by the alumina carrier has high strength and can improve the yield and selectivity of products and the conversion rate of raw materials when used for dehydrogenation reaction.
Description
Technical Field
The invention relates to the field of catalysts, in particular to an alumina carrier 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 an alumina carrier, a preparation method and application thereof.
In order to achieve the above object, in one aspect, the present invention provides an alumina carrier, which contains alumina, an additive and a modifier, wherein the additive 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.
In another aspect, the present invention also provides a method for preparing an alumina carrier, comprising: contacting and coprecipitating an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound in a solution state containing a halogen element; then, drying and roasting the obtained solid in sequence; 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.
In a third aspect, the invention also provides a carrier of the invention and an application of the alumina carrier obtained by the method for preparing the alumina carrier in preparing a dehydrogenation catalyst.
The external surface and the alumina framework of the carrier obtained by the method for preparing the alumina carrier provided by the invention are both provided with the auxiliary agent and the modifier, when the alumina carrier provided by the invention or the carrier obtained by the method for preparing the alumina carrier provided by the invention is used for preparing the dehydrogenation catalyst, the yield of isobutene is ensured to be higher, and the strength of the catalyst prepared by the alumina carrier is obviously improved, so that the economic benefit of isobutene prepared by isobutane dehydrogenation is obviously improved, and the preparation method of the invention also has the advantages of simplicity, lower cost and suitability for industrial production, in particular, when the dehydrogenation catalyst prepared by the carrier provided by the invention is used for the reaction of isobutene prepared by isobutane dehydrogenation, the yield of isobutene can be higher, and according to the effect of the embodiment of the invention, the yield can reach more than 34.7 percent, even up to 36.7%; and the selectivity of the isobutene can reach over 96.1 percent, even can reach 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 one aspect, the invention provides an alumina carrier, which contains alumina, an auxiliary agent and a modifier, wherein 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.
When the dehydrogenation catalyst containing the alumina carrier with excellent strength provided by the invention is used for preparing isobutene through isobutane dehydrogenation, the yield of isobutene can be high.
According to the alumina carrier, the content of the auxiliary agent in the alumina carrier can be 0.1-10 wt% based on the total weight of the carrier.
The alumina carrier of the invention, wherein, preferably based on the total amount of the carrier, the content of the modifier in the alumina carrier can be 0.1-15 wt%.
According to the alumina carrier of the present invention, preferably, the weight ratio of the group IVA element to the alkali metal element in the alumina carrier may be 1: 1-2.
According to a preferred embodiment of the present invention, the group IVA element in the alumina support is tin, and the alkali metal element is potassium.
According to another preferred embodiment of the present invention, the group IVA element in the alumina support is tin and lead, and the alkali metal element is potassium.
In another preferred embodiment, the mass ratio of tin to lead in the alumina carrier is preferably 1: 0.2-0.6.
The carrier having the aforementioned composition of the present invention can be prepared by various methods as long as it is ensured that the requirements of the aforementioned carrier of the present invention can be satisfied after preparation.
In another aspect, the present invention also provides a method for preparing an alumina carrier, comprising: contacting and coprecipitating an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound in a solution state containing a halogen element; then, drying and roasting the solid obtained after coprecipitation in sequence; 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.
According to the method for preparing the alumina carrier, the amount of the halogen element in the solution and the amount of the compound containing the IVA element and the compound containing the alkali metal in the solution are preferably such that the total amount of the IVA element and the alkali metal element in the alumina carrier is 0.1 to 10 wt% based on the total amount of the carrier; the halogen element in the alumina carrier is 0.1-15 wt%.
Preferably, according to the method for preparing an alumina carrier of the present invention, the compound containing a group IVA element 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 alumina carrier may be 1: 1-2.
Preferably, in the method for preparing an alumina carrier according to the present invention, the group IVA element in the group IVA element-containing compound may be tin; the alkali metal element in the alkali metal-containing compound may be potassium.
According to another preferred embodiment of the present invention, in the method for producing an alumina support according to the present invention, it is preferable that 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.
More preferably, in the above another preferred embodiment of the present invention, the group IVA element-containing compound is used in an amount such that the mass ratio of tin to lead in the alumina 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.
According to the method for preparing an alumina carrier of the present invention, it is preferable that 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.
According to the method for preparing the alumina carrier, the aluminum-containing compound is preferably aluminum sulfate and metaaluminate. 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 for preparing an alumina carrier according to the present invention, preferably, the method of contacting and coprecipitating the aluminum-containing compound, the group IVA element-containing compound, and the alkali metal-containing compound comprises: 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 methods), and then the solutions are mixed to contact and coprecipitate. 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 for producing an alumina carrier according to 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 obtained alumina carrier when the alumina carrier can be produced 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 for preparing an alumina support of the present invention, the conditions for contacting and coprecipitating 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 catalyst comprising the alumina support of the present invention stronger and to obtain a higher yield of isobutene when used in the reaction for preparing isobutene by dehydrogenation of isobutane, it is preferable that the conditions for contacting and coprecipitating include: the time is 6-15 h.
In the method for preparing an alumina carrier according to the present invention, preferably, the conditions of contacting and coprecipitating include: the temperature is 40-80 ℃.
In the method for preparing an alumina carrier according to the present invention, preferably, the conditions of contacting and coprecipitating include: the pH value is 8-10.
In the method for producing an alumina carrier of the present invention, conditions for drying and calcining the solid obtained after the coprecipitation in this order are not particularly limited. In order to ensure that the strength of the catalyst containing the alumina carrier is higher and isobutene with higher yield can be obtained when the catalyst is used for preparing isobutene by isobutane dehydrogenation, the drying temperature is preferably 60-120 ℃, and the drying temperature is more preferably 80-120 ℃.
In order to obtain higher yield of isobutene when the catalyst containing the alumina carrier is used for preparing isobutene by isobutane dehydrogenation, the roasting temperature is preferably 400-750 ℃, and more preferably 450-650 ℃.
In the method for preparing the alumina carrier, the active alumina obtained after drying and roasting can be molded, the molding method is not particularly limited, and in order to enable the catalyst containing the alumina carrier to be used in the reaction of preparing isobutene through isobutane dehydrogenation, the molding method is preferably as follows: mixing the activated alumina obtained after calcination with a thickener 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 a third aspect, the invention also provides the carrier and the application of the alumina carrier obtained by the method for preparing the alumina carrier in the preparation of dehydrogenation catalysts.
In the present invention, a person skilled in the art can use the alumina carrier of the present invention to prepare a dehydrogenation catalyst by various conventional methods, and in order to make the catalyst containing the alumina carrier of the present invention have higher strength and obtain isobutene with higher yield and selectivity when used in the reaction for preparing isobutene by isobutane dehydrogenation, the present invention preferably can obtain the catalyst for the reaction for preparing isobutene by isobutane dehydrogenation by the following methods:
the alumina carrier of the present invention is dipped in a mixture containing chloroplatinic acid, stannic chloride, potassium chloride, etc. for 10-15 hr, and the solvent is removed from the dipped mixture under reduced pressure to obtain solid matter, which is then dried and calcined successively. In the present invention, the method of sequentially drying and calcining the obtained solid is not particularly limited, and the present invention preferably can be dried overnight at 100 ℃ and then calcined at 600 ℃ to obtain a catalyst for the reaction of producing isobutene by dehydrogenation of isobutane.
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
In this example, the alumina carrier of the present invention was prepared by the method of the present invention.
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 was tested to contain 0.43 wt% tin (as measured by using an L5S UV spectrophotometer, infra), 0.43 wt% potassium (as measured by using an FP640 flame spectrophotometer, infra), and 0.25 wt% chlorine (as measured by using a PXS-450 ionizer, infra).
Example 2
In this example, the alumina carrier of the present invention was prepared by the method of the present invention.
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 wt% of tin, 0.41 wt% of potassium and 0.27 wt% of chlorine.
Example 3
In this example, the alumina carrier of the present invention was prepared by the method of the present invention.
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 wt% of tin, 0.42 wt% of potassium and 0.14 wt% of chlorine.
Example 4
In this example, the alumina carrier of the present invention was prepared by the method of the present invention.
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 test shows that the alumina carrier 4-A contains 0.31 wt% of tin, 0.12 wt% of lead, 0.43 wt% of potassium and 0.48 wt% of chlorine.
Example 5
This example used the same method to prepare an alumina support as in example 4, except that:
the amounts of tin chloride and lead chloride used in this example 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 test shows that the alumina carrier 5-A contains 0.21 wt% of tin, 0.21 wt% of lead, 0.43 wt% of potassium and 0.20 wt% of chlorine.
Example 6
This example used the same method to prepare an alumina support as in example 4, except that:
in this example, tin chloride was used in an amount of 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 wt% of tin, 0.43 wt% of potassium and 0.18 wt% of chlorine.
Example 7
This example used the same method to prepare an alumina support as in example 4, except that:
in this example, tin chloride was used in an amount of 4.53g, but 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 test shows that the alumina carrier 7-A contains 0.43 wt% of tin, 0.43 wt% of potassium and 0.18 wt% of chlorine.
Example 8
This example prepared an alumina support in the same manner as example 1, except that:
in this example, the amount of potassium nitrate used 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 test shows that the alumina carrier 8-A contains 0.44 wt% of tin, 0.84 wt% of potassium and 0.24 wt% of chlorine.
Example 9
This example prepared an alumina support in the same manner as example 1, except that:
in this example, the amount of potassium nitrate 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 test shows that the alumina carrier 9-A contains 0.44 wt% of tin, 0.22 wt% of potassium and 0.27 wt% of chlorine.
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.
Test examples 1 to 10
200g of an alumina carrier shown in the following Table 2 was taken and added to an impregnation solution composed of 2.65g of chloroplatinic acid, 1.10g of tin chloride, 1.91g of potassium chloride and 376g of water, the impregnation was carried out for 12 hours, the solvent was removed under reduced pressure, the obtained solid was dried overnight at 100 ℃ and calcined at 600 ℃ in this order to obtain catalysts 1-B to 9-B and 10-D for the reaction for producing isobutene by dehydrogenation of isobutane, the names of the catalysts obtained in the respective test examples and the results of the abrasion strengths expressed by abrasion rates thereof are specifically shown in Table 2, wherein the abrasion strengths were measured by a rotary 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%).
The above catalysts 1-B to 9-B and 10-D were used in the reaction for producing isobutylene by dehydrogenation of isobutane, the evaluation conditions of the reaction are shown in Table 1, and the reaction results are shown in Table 2.
Test example 11
The attrition strength of the catalyst particles in example 1 of CN102000593A was measured in the same manner as in the above test example, and the 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
It can be seen from the results in the above examples, comparative examples, test examples and table 2 that the alumina carrier prepared by the method of the present invention contains the auxiliary agent and the modifier, and the dehydrogenation catalyst containing the above alumina carrier provided by the present invention has a low wear rate, i.e., a high strength, which is significantly higher than that 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 carrier obtained by the method in the prior art.
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.
Claims (13)
1. An alumina carrier is characterized by comprising alumina, an auxiliary agent and a modifier, wherein 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 alumina carrier is prepared by the following method: contacting and coprecipitating an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound in a solution state containing a halogen element; then drying and roasting the obtained solid in sequence, wherein the aluminum-containing compound comprises metaaluminate and at least one of aluminum sulfate, aluminum chloride and aluminum nitrate;
wherein, the weight ratio of the IVA group element and the alkali metal element in the alumina carrier is 1: 1-2.
2. The carrier as claimed in claim 1, wherein the content of the auxiliary agent in the alumina carrier is 0.1-10 wt% based on the total amount of the carrier; the content of the modifier in the alumina carrier is 0.1-15 wt%.
3. The carrier according to claim 1 or 2, wherein the group IVA element is tin; the alkali metal element is potassium.
4. The carrier according to claim 1 or 2, wherein the group IVA element is tin and lead; the alkali metal element is potassium.
5. The carrier according to claim 4, wherein the mass ratio of tin to lead in the alumina carrier is 1: 0.2-0.6 in the carrier.
6. A method for preparing an alumina carrier is characterized by comprising the following steps: contacting and coprecipitating an aluminum-containing compound, a group IVA element-containing compound and an alkali metal-containing compound in a solution state containing a halogen element; then, drying and roasting the obtained solid in sequence; 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;
wherein the compound containing the IVA group element and the compound containing alkali metal are used in such amounts that the weight ratio of the IVA group element to the alkali metal element in the alumina carrier is 1: 1-2;
the aluminum-containing compound includes at least one selected from aluminum sulfate, aluminum chloride and aluminum nitrate and a meta-aluminate.
7. The process according to claim 6, wherein the amount of the halogen element and the amounts of the group IVA element-containing compound and the alkali metal-containing compound in the solution are such that the total amount of the group IVA element and the alkali metal element in the alumina carrier is from 0.1 to 10 wt%, based on the total amount of the carrier; the halogen element in the alumina carrier is 0.1-15 wt%.
8. The method according to claim 6 or 7, wherein 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.
9. The method according to claim 6 or 7, wherein 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.
10. The method as claimed in claim 9, wherein the group IVA element-containing compound is used in an amount such that the mass ratio of tin to lead in the alumina carrier is 1: 0.2-0.6.
11. The process of claim 6, wherein the aluminum-containing compound is aluminum sulfate and metaaluminate.
12. The method of claim 6, wherein the contacting and co-precipitating conditions comprise: the time is 6-15h, the temperature is 40-80 ℃, and the pH value is 8-10.
13. Use of a support according to any one of claims 1 to 5 or prepared by a process according to any one of claims 6 to 12 in the preparation of a dehydrogenation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165171.9A CN107213919B (en) | 2016-03-22 | 2016-03-22 | Alumina carrier, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165171.9A CN107213919B (en) | 2016-03-22 | 2016-03-22 | Alumina carrier, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107213919A CN107213919A (en) | 2017-09-29 |
| CN107213919B true CN107213919B (en) | 2020-05-12 |
Family
ID=59927368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610165171.9A Active CN107213919B (en) | 2016-03-22 | 2016-03-22 | Alumina carrier, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107213919B (en) |
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 |
| 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 |
| CN104549249A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for alkene preparation through dehydrogenation and preparation method of catalyst |
-
2016
- 2016-03-22 CN CN201610165171.9A patent/CN107213919B/en active Active
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 |
| 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 |
| CN104549249A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for alkene preparation through dehydrogenation and preparation method of catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107213919A (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1283519A (en) | Catalyst having two-peak hole radius distribution | |
| CN105642341B (en) | Supported amorphous catalyst of phosphatizing nickel and its preparation and application for light paraffins isomerization | |
| CN109499558B (en) | Alpha-alumina carrier, silver catalyst and olefin epoxidation method | |
| CN105749986B (en) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and the preparation method and application thereof | |
| EP4023329A1 (en) | Dearsenification adsorbent and preparation method therefor | |
| CN101190413B (en) | Petroleum naphtha reforming catalyst and preparation method thereof | |
| CN112439443B (en) | Light olefin skeleton conversion catalyst and preparation method thereof | |
| CN107216230B (en) | Isobutane dehydrogenation method | |
| CN102125839B (en) | Alkyne hydrogenation catalyst and preparation method thereof | |
| WO2021110083A1 (en) | Catalyst suitable for hydrocarbon conversion reaction, preparation method therefor and application thereof | |
| CN107213919B (en) | Alumina carrier, preparation method and application thereof | |
| CN107213909B (en) | Dehydrogenation catalyst and preparation method and application thereof | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN106563440A (en) | Crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and preparation method thereof | |
| CN114433062B (en) | Preparation method of isobutane dehydrogenation catalyst and application of isobutane dehydrogenation catalyst in preparation of isobutene | |
| CN114433217B (en) | Benzene and synthesis gas alkylation catalyst and preparation method and application thereof | |
| CN109529925A (en) | Load Performance of Isomerization Catalysts for Light n-Paraffin, preparation method and its application method of molybdenum boride | |
| CN113546671B (en) | Light gasoline cracking yield-increasing propylene catalyst containing ultra-macroporous silica gel, and preparation method and application thereof | |
| CN109022025A (en) | Full-cut fraction pyrolysis gasoline process for selective hydrogenation | |
| CN106582628B (en) | Selective opening catalyst and preparation method thereof | |
| JPS5910346A (en) | Preparation of hydrocarbon conversion catalyst | |
| CN1047326C (en) | Platinum-rhenium reforming catalyst | |
| CN112439399B (en) | Alpha-alumina carrier, preparation method, silver catalyst and application | |
| CN115501890B (en) | N-butane skeleton isomerization catalyst and its preparation method and application | |
| CN114602442B (en) | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |