CN112973661B - Alkane dehydrogenation catalyst and preparation method and application thereof - Google Patents

Alkane dehydrogenation catalyst and preparation method and application thereof Download PDF

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CN112973661B
CN112973661B CN202010227117.9A CN202010227117A CN112973661B CN 112973661 B CN112973661 B CN 112973661B CN 202010227117 A CN202010227117 A CN 202010227117A CN 112973661 B CN112973661 B CN 112973661B
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cerium
source
catalyst
zirconium
oxide
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CN112973661A (en
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许本静
阎子峰
柴永明
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Shanxi Tengmao Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to the field of alkane dehydrogenation. Discloses an alkane dehydrogenation catalyst, a preparation method and application thereof. The alkane dehydrogenation catalyst comprises: a carrier and an active ingredient supported on the carrier; the carrier contains gallium oxide and/or indium oxide, and a binder, wherein the binder is selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide, and the active component contains cerium-zirconium solid solution Ce xZr1‑ xO2, wherein x is less than 1. The catalyst can be applied to a fixed bed or fluidized bed process, and can effectively realize olefin preparation by alkane dehydrogenation.

Description

Alkane dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of alkane dehydrogenation, in particular to an alkane dehydrogenation catalyst and a preparation method and application thereof.
Background
Olefins are important large chemical raw materials for petrochemical production, and have wide application. Olefins are mainly produced by steam cracking of hydrocarbons (such as naphtha steam cracking), catalytic cracking of olefins (such as Superflex technology), catalytic cracking of heavy oils (such as TMP, DCC technology) and catalytic pyrolysis of heavy oils (such as CPP technology), and further catalytic dehydrogenation of alkanes is an important technical route for olefin production.
Catalytic dehydrogenation of alkane can obtain economically acceptable single pass conversion and alkene selectivity under proper temperature conditions, so that the catalytic dehydrogenation method is adopted for preparing alkene by alkane dehydrogenation.
In the prior art, dehydrogenation catalysts for the dehydrogenation of alkanes contain a group VIII metal and a metal compound which is reducible to the metal. These metals are supported on a carrier such as alumina or silica. Catalysts containing group VIII metals can exhibit high dehydrogenation activity and selectivity. However, such catalysts coke faster during the dehydrogenation reaction and sometimes deactivate even within minutes. In the prior art, sn is introduced into a catalyst containing a group VIII metal to improve the activity and life of the catalyst, such as Pt/Sn/ZnAl 2O4 catalyst having high dehydrogenation activity and olefin selectivity to alkane, however, the introduction of Sn cannot be taken out of the trouble that the catalyst needs frequent regeneration. Such catalysts are generally classified into two types, cr-based catalysts and Pt-based catalysts. Both Cr-based and Pt-based catalysts deactivate due to coking within a few hours of continuous feed, and thus the catalyst must be frequently regenerated. Moreover, pt is expensive, the high investment and catalyst use costs limit the application of the dehydrogenation process using Pt catalysts, and the economy of the process is only reasonable in countries or regions where isobutane resources are abundant and the price is low. In addition, with Pt catalysts, the recycle gas must also be deoxygenated, as the catalyst is very sensitive to oxygen, including molecular oxygen, methanol, MTBE, dimethyl ether, and water; for Cr catalysts, the dehydrogenation performance of the supported Cr catalyst has reached near perfect level, for example, the selectivity of olefins is still above 95% in the Catofin process at a conversion rate approaching the thermodynamic equilibrium limit, however, the environmental problem of hexavalent Cr once leaked is not small.
Thus, there is also a need for improved catalysts for alkane dehydrogenation.
Disclosure of Invention
The invention aims to solve the defect that the existing alkane dehydrogenation catalyst uses noble metal, and provides an alkane dehydrogenation catalyst, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides an alkane dehydrogenation catalyst comprising: a carrier and an active ingredient; the carrier contains gallium oxide and/or indium oxide and a binder; the binder is at least one selected from aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2, wherein x is less than 1.
Preferably, the support contains 0.5 to 20% by weight of gallium oxide and/or indium oxide, 80 to 99.5% by weight of the binder, based on the total amount of the support.
Preferably, the carrier is present in an amount of 20 to 80% by weight and the active component is present in an amount of 20 to 80% by weight, based on the total amount of the catalyst.
The second aspect of the present invention provides a process for the preparation of an alkane dehydrogenation catalyst comprising:
(1) Mixing a cerium source and a zirconium source, and preparing a cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2 from the obtained mixture, wherein x is more than 0 and less than 1;
(2) Mixing and pulping the cerium-zirconium solid solution, a gallium source and/or an indium source, an aluminum source and/or a silicon source to obtain carrier slurry; or alternatively
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, the aluminum source and/or the silicon source into composite powder;
(3) And forming the carrier slurry or the composite powder to obtain the alkane dehydrogenation catalyst.
In a third aspect, the present invention provides an alkane dehydrogenation catalyst prepared by the process of the present invention.
The fourth aspect of the invention provides the use of the alkane dehydrogenation catalyst of the invention in the preparation of alkene by alkane dehydrogenation.
Through the technical scheme, the invention provides the alkane dehydrogenation catalyst without noble metals. The catalyst can be applied to a fixed bed or fluidized bed process, and can effectively realize the preparation of olefin by alkane dehydrogenation, such as the preparation of propylene by propane dehydrogenation and the preparation of isobutene by isobutane dehydrogenation, wherein the single pass conversion rate of alkane can reach 40-50wt%, and the olefin selectivity can reach 85-90 wt%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In a first aspect the present invention provides an alkane dehydrogenation catalyst comprising: a carrier and an active ingredient; the carrier contains gallium oxide and/or indium oxide and a binder; the binder is at least one selected from aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2, wherein x is less than 1.
The invention provides an alkane dehydrogenation catalyst without noble metal, which selects a carrier containing gallium oxide and/or indium oxide and cooperatively uses an active component containing cerium-zirconium solid solution Ce xZr1-xO2, so that alkane dehydrogenation, especially propylene preparation by propane dehydrogenation and isobutene preparation by isobutane dehydrogenation can be effectively realized.
In the invention, in the cerium-zirconium solid solution Ce xZr1-xO2 contained in the active ingredient, x is preferably less than or equal to 0.5. Can realize better alkane dehydrogenation effect.
In the present invention, it is further preferable that the carrier contains 0.5 to 20% by weight of gallium oxide and/or indium oxide and 80 to 99.5% by weight of the binder, based on the total amount of the carrier, in the composition of the alkane dehydrogenation catalyst. When gallium oxide and indium oxide are contained in the support at the same time, it is preferable that the weight ratio of gallium oxide to indium oxide is 9 to 19:1.
In the present invention, in the composition of the alkane dehydrogenation catalyst, it is further preferable that the carrier is contained in an amount of 20 to 80% by weight and the active component is contained in an amount of 20 to 80% by weight, based on the total amount of the catalyst; preferably, the carrier is present in an amount of 30 to 70% by weight and the active ingredient is present in an amount of 30 to 70% by weight. The catalyst obtained according to the composition range can better realize the effect of alkane dehydrogenation.
According to the invention, the catalyst composition provided by the invention comprises a Ce xZr1-xO2 component of the cerium-zirconium solid solution as an active component, a diffraction peak of Ce xZr1-xO2 in a spectrogram can be obtained through XRD test, an XRD spectrogram card is marked by contrast, and the specific composition of the cerium-zirconium solid solution can be determined by further combining element analysis. The composition of the resulting cerium-zirconium solid solution may also be calculated from the raw material feed for preparing the cerium-zirconium solid solution. The value of x in the general formula of the obtained cerium-zirconium solid solution representation can be determined according to the analysis result or the feeding amount.
Meanwhile, the gallium oxide and/or indium oxide are/is contained in the carrier of the catalyst, and experiments prove that the catalyst can be cooperated with an active component to provide an effect of alkane dehydrogenation.
The second aspect of the present invention provides a process for the preparation of an alkane dehydrogenation catalyst comprising:
(1) Mixing a cerium source and a zirconium source, and preparing a cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2 from the obtained mixture, wherein x is more than 0 and less than 1;
(2) Mixing and pulping the cerium-zirconium solid solution, a gallium source and/or an indium source, an aluminum source and/or a silicon source to obtain carrier slurry; or alternatively
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, the aluminum source and/or the silicon source into composite powder;
(3) And forming the carrier slurry or the composite powder to obtain the alkane dehydrogenation catalyst.
In the present invention, preferably, x.ltoreq.0.5.
In the present invention, cerium-zirconium solid solution Ce xZr1-xO2 as an active component can be prepared separately. Preferably, in step (1), the cerium-zirconium solid solution is prepared by one of the following methods: coprecipitation, sol-gel, complexation, surfactant templating or solution burning. Preferably, the preparation method of the cerium-zirconium solid solution comprises a coprecipitation method or a sol-gel method.
One embodiment of the present invention may be a coprecipitation method. The cerium source and the zirconium source may be mixed into an aqueous solution containing cerium and zirconium, and then the obtained mixture is brought into contact with a precipitant to perform a precipitation reaction, the reaction product is filtered and washed to obtain a cake of precipitate containing cerium and zirconium, and the cake is dried and baked to obtain a cerium-zirconium solid solution, and the composition structure of the cerium-zirconium solid solution may be determined by XRD and elemental analysis. Wherein the amounts of cerium source and zirconium source satisfy the composition of the obtained cerium zirconium solid solution.
Another embodiment of the present invention may be a sol-gel process. The cerium source and the zirconium source can be mixed into an aqueous solution containing cerium and zirconium, then mixed with an aqueous solution containing acid or alkali, subjected to hydrolysis reaction or polymerization reaction to obtain a gel product, dried and baked to obtain a cerium-zirconium solid solution, and the composition structure of the cerium-zirconium solid solution can be determined by XRD and elemental analysis. Wherein the amounts of cerium source and zirconium source satisfy the composition of the obtained cerium zirconium solid solution.
Some embodiments of the invention provide that the specific implementation may be a solution combustion process. The specific steps may include: soluble salts of zirconium and cerium and urea (or an organic such as ethylene glycol) are dissolved in a small amount of water, and the resulting mixture is heated to burn to form a solid solution powder.
Some embodiments of the invention provide that the specific embodiment may be a surfactant templating method. The specific steps may include: dissolving a zirconium source, a cerium source and a surfactant in water, stirring, then adjusting the pH value by ammonia water, and then carrying out heating reaction; and carrying out suction filtration, washing, drying and roasting treatment on the reaction product to obtain the cerium-zirconium solid solution. The surfactant may be selected from at least one of cationic, nonionic and anionic surfactants. The anionic surfactant may be at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate and potassium laureth phosphate; the nonionic surfactant may be selected from at least one of polyethylene glycol 4000 to polyethylene glycol 10000, tween 20, tween 60, tween 80, P123 (PEO-PPO-PEO, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer); the cationic surfactant may be at least one selected from dodecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, and octadecyl dimethyl benzyl ammonium chloride. The pH value is adjusted to 8-12. The conditions of the heating reaction are as follows: the reaction temperature is 60-90 ℃ and the reaction time is 24-144h.
In the present invention, the cerium source and the zirconium source are substances that can be prepared to be converted into a cerium-zirconium solid solution. Preferably, the cerium source is a precursor of cerium oxide, preferably at least one selected from cerium chloride, cerium nitrate, cerium sulfate and cerium acetate; the zirconium source is a precursor of zirconium oxide, preferably at least one selected from zirconium oxychloride, zirconium chloride, zirconium nitrate, zirconyl nitrate, zirconium sulfate and zirconium acetate.
In the present invention, preferably, the molar ratio of the cerium source to the zirconium element is x: (1-x). The cerium-zirconium solid solution provided by the invention can be obtained. Where x is as defined for x in the general formula shown in the finally prepared cerium-zirconium solid solution.
In one embodiment of the present invention, step (2) is used to prepare a support slurry, which can be used in a subsequent step (3) to shape the catalyst from the support slurry. In another embodiment, step (2) is used to prepare a composite powder, which can be used in a subsequent step (3) to shape the catalyst from the composite powder. In both embodiments, preferably, the gallium source is a precursor of gallium oxide, preferably at least one selected from gallium chloride, gallium nitrate, gallium sulfate and gallium acetate; the indium source is a precursor of indium oxide, preferably at least one selected from the group consisting of indium chloride, indium nitrate, indium sulfate, and indium acetate.
In the present invention, the aluminum source and the silicon source may be a sol, a solution or a powder of aluminum oxide, silicon oxide and/or silicon-aluminum composite oxide, for example, an aluminum sol, a silicon sol or a silicon-aluminum sol, a mixed solution containing an aluminum precursor, a silicon precursor or both, or a powder containing aluminum oxide, silicon oxide or silicon-aluminum composite oxide, respectively. Wherein the aluminum precursor may preferably be selected from at least one of aluminum chloride, nitrate, sulfate and aluminum isopropoxide; the silicon precursor may preferably be selected from at least one of water glass, silicon tetrachloride, and alkoxysilane.
In one embodiment of the invention, in the step (2), the cerium-zirconium solid solution, the gallium source and/or the indium source, the aluminum source and/or the silicon source are mixed and pulped, and then the alkane dehydrogenation catalyst provided by the invention containing a carrier and an active component is formed in one step through the step (3). Or in another embodiment, in the step (2), the cerium-zirconium solid solution, the gallium source and/or the indium source, the aluminum source and/or the silicon source are mixed into composite powder, and then the alkane dehydrogenation catalyst provided by the invention containing a carrier and an active component is formed in one step through the step (3). The catalyst prepared by the method can provide better effect of alkane dehydrogenation to olefin.
In the present invention, the alkane dehydrogenation catalyst is prepared comprising a support and an active component. The gallium source, indium source, aluminum source, and silicon source may be used to make the carrier. The cerium zirconium solid solution may be at least part of the active component. Preferably, the gallium source, the indium source, the aluminum source and the silicon source are used in an amount sufficient to prepare the catalyst, and the carrier contains 0.5-20 wt% of gallium oxide and/or indium oxide and 80-99.5 wt% of a binder based on the total weight of the carrier contained in the catalyst, wherein the binder is at least one selected from aluminum oxide, silicon oxide and silicon-aluminum composite oxide. In the finally prepared alkane dehydrogenation catalyst, the support may comprise gallium oxide and/or indium oxide, and a binder. The binder can be prepared from an aluminum source and a silicon source which are fed in the preparation method. When a gallium source and an indium source are added simultaneously, the weight ratio of gallium oxide to indium oxide in the obtained carrier is preferably 9 to 19:1 to provide a better catalytic alkane dehydrogenation effect.
In the present invention, preferably, in the step (2), the amount of the cerium-zirconium solid solution is such that the content of the carrier is 20 to 80% by weight and the content of the active component is 20 to 80% by weight based on the total amount of the catalyst in the obtained catalyst; preferably, the carrier is present in an amount of 30to 70% by weight and the active ingredient is present in an amount of 30to 70% by weight; wherein the active component contains the cerium-zirconium solid solution.
In the present invention, corresponding to the carrier slurry or the composite powder obtained in the step (2), in the step (3), the forming method may be an embodiment of spray drying forming or extrusion forming of the carrier slurry; in another embodiment, the composite powder may be tableted. To meet the molding requirements of the catalyst, the cerium-zirconium solid solution may be pulverized and sieved to obtain particles having an average particle diameter of 2 to 5 μm. Further, the solid content of the carrier slurry can be adjusted or other reagents required for molding can be introduced according to the molding requirements, but the chemical properties of the catalyst are not affected. The conditions of each of spray-drying molding, tablet molding and bar molding may be conventional in the art. For example, extrusion may be performed after nitric acid is added to the carrier slurry.
In the invention, in the step (3), the drying temperature is 80-250 ℃, preferably 100-200 ℃ and the drying time is 5-8h; the roasting temperature is 500-800 ℃, preferably 550-700 ℃ and the roasting time is 4-7h.
In the invention, the method further comprises the steps of washing and filtering the roasted product after roasting, and then calcining to obtain the final alkane dehydrogenation catalyst. The washing may use deionized water 4 to 6 times the weight of the calcined product. The calcination temperature is 550-700 ℃ and the calcination time is 1-4h.
In a third aspect, the present invention provides an alkane dehydrogenation catalyst prepared by the process of the present invention.
The alkane dehydrogenation catalyst comprises: a carrier and an active ingredient; the carrier contains gallium oxide and/or indium oxide and a binder; the binder is at least one selected from aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2, wherein x is less than 1, and preferably x is less than or equal to 0.5. The structure and composition of the cerium-zirconium solid solution can be determined by XRD and elemental analysis. The method can also be determined by the raw material feeding of the preparation method.
In the alkane dehydrogenation catalyst, the carrier contains 0.5 to 20 weight percent of gallium oxide and/or indium oxide and 80 to 99.5 weight percent of the binder based on the total amount of the carrier.
In the alkane dehydrogenation catalyst, the content of the carrier is 20-80 wt% based on the total amount of the catalyst, and the content of the active component is 20-80 wt%; preferably, the carrier is present in an amount of 30 to 70% by weight and the active ingredient is present in an amount of 30 to 70% by weight.
The fourth aspect of the invention provides the use of the alkane dehydrogenation catalyst of the invention in the preparation of alkene by alkane dehydrogenation.
For example, propylene may be produced by dehydrogenation of propane and isobutane may be produced by dehydrogenation of isobutane.
In the following examples and comparative examples, the performance evaluation was carried out on a fixed bed microreactor apparatus in which the reaction temperature was 575℃and the mass space time was 3 h -1 in the reaction of producing isobutylene by dehydrogenating isobutane and producing propylene by dehydrogenating propane.
Example 1
(1) Cerium zirconium solid solution
Dissolving cerium nitrate and zirconium oxychloride to obtain a mixed solution, adding ammonia water to perform coprecipitation reaction to obtain mother solution, filtering and washing the mother solution, drying and roasting the obtained filter cake to obtain cerium-zirconium solid solution, and performing XRD measurement and elemental analysis, wherein the chemical structure of the solid solution is represented as Ce 0.1Zr0.9O2, and x is 0.1.
(2) Carrier slurry
The cerium-zirconium solid solution with the average grain diameter of 2.0 mu m selected by sieving and gallium chloride are added into aluminum sol for mixing and pulping, and the carrier slurry with the solid content of 38 weight percent is obtained.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 650 ℃ for 2 hours, washing and filtering the catalyst particles with 6 times of deionized water, and calcining a filter cake at 600 ℃ for 1 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 30 wt.% of a support and 70 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The catalyst evaluation result shows that the conversion rate of the isobutene is 49.85%, the yield of the isobutene is 44.80%, and the selectivity of the isobutene is 89.86%. The results are shown in Table 1.
Example 2
(1) Cerium zirconium solid solution
Dissolving cerium nitrate and zirconium chloride to obtain a mixed solution, adding ammonia water to perform coprecipitation reaction to obtain mother solution, filtering and washing the mother solution, drying and roasting the obtained filter cake to obtain cerium-zirconium solid solution, and determining by XRD, wherein the chemical structure of the solid solution is expressed as Ce 0.3Zr0.7O2, and x is 0.3.
(2) Carrier body
The sieved cerium-zirconium solid solution with the average grain diameter of 2.5 mu m, gallium acetate, indium chloride, pseudo-boehmite powder and deionized water are mixed to obtain a carrier mixture with the solid content of 55 weight percent.
(3) Catalyst preparation
Adding nitric acid into the carrier mixture, extruding and molding to obtain catalyst particles, roasting the catalyst particles at 675 ℃ for 1.5h, washing and filtering with 5 times deionized water, and roasting a filter cake at 550 ℃ for 1.5h to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 70 wt.% of a support and 30 wt.% of a cerium zirconium solid solution; the carrier contains 20wt% of gallium oxide and indium oxide (weight ratio is 10:1), and 80 wt% of aluminum oxide.
The catalyst is used for converting isobutane into isobutene. The results of the evaluation showed that the conversion of isobutane was 45.57%, the yield of isobutene was 40.55% and the selectivity to isobutene was 88.98%. The results are shown in Table 1.
Example 3
(1) Cerium zirconium solid solution
Dissolving cerium chloride and zirconium nitrate to obtain a mixed solution, mixing the mixed solution with an aqueous solution containing a coagulating agent, carrying out hydrolysis and polymerization reaction to obtain a gel product, drying and roasting to obtain a cerium-zirconium solid solution, and determining by XRD, wherein the chemical structure of the solid solution is represented as Ce 0.5Zr0.5O2, and x is 0.5.
(2) Carrier slurry
Adding the cerium-zirconium solid solution and the indium nitrate which are screened and selected and have the average grain diameter of 3.0 mu m into silica sol for mixing and pulping to obtain the carrier slurry with the solid content of 30 weight percent.
(3) Catalyst preparation
And (3) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 700 ℃ for 1h, washing and filtering the catalyst particles with 4 times of deionized water, and calcining a filter cake at 500 ℃ for 2h to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 40 wt.% of a support and 60 wt.% of a cerium zirconium solid solution; the carrier contained 0.5 wt% indium oxide and 99.5 wt% silicon oxide.
The catalyst evaluation result shows that the conversion rate of the isobutene is 44.76%, the yield of the isobutene is 39.41%, and the selectivity of the isobutene is 88.05%. The results are shown in Table 1.
Example 4
(1) Cerium zirconium solid solution
Cerium sulfate, zirconium oxychloride and urea are dissolved in water to obtain a mixed solution, the mixed solution is heated until combustion occurs to obtain cerium zirconium solid solution, and the chemical structure of the solid solution is expressed as Ce 0.7Zr0.3O2 and x is 0.7 through XRD measurement.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain diameter of 3.5 mu m selected by screening and gallium acetate into a solution containing aluminum chloride and aluminum isopropoxide for mixing and pulping to obtain carrier slurry with the solid content of 35 weight percent;
(3) Catalyst preparation
And (3) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 550 ℃ for 2 hours, washing and filtering the catalyst particles with 5 times of deionized water, and calcining a filter cake at 650 ℃ for 0.5 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 30 wt.% of a support and 70 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The evaluation result of the catalyst shows that the conversion rate of the isobutene is 42.17%, the yield of the isobutene is 36.93%, and the selectivity of the isobutene is 87.58%. The results are shown in Table 1.
Example 5
(1) Cerium zirconium solid solution
Cerium nitrate, zirconyl nitrate and tween 80 are dissolved in water to obtain a mixed solution, ammonia water is added to adjust the pH value to 10, and then the mixed solution is heated to 85 ℃ for reaction for 120 hours under stirring. The obtained reaction product is filtered, washed, dried (120 ℃ for 8 hours) and roasted (600 ℃ for 6 hours) to obtain cerium-zirconium solid solution, and the chemical structure of the solid solution is expressed as Ce 0.9Zr0.1O2 and x is 0.9 through XRD measurement.
(2) Composite powder
Mixing the sieved cerium-zirconium solid solution with the average grain diameter of 4.0 mu m with indium sulfate and silicon aluminum composite oxide powder to obtain composite powder,
(3) Catalyst preparation
Tabletting the composite powder, crushing and screening the obtained product to obtain product particles (40-60 meshes), roasting the product particles at 500 ℃ for 2.5h, washing with 4 times deionized water, filtering, and calcining a filter cake at 700 ℃ for 0.5h to obtain the alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 30 wt.% of a support and 70 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The catalyst evaluation result shows that the conversion rate of the isobutene is 41.76%, the yield of the isobutene is 36.27%, and the selectivity of the isobutene is 86.85%. The results are shown in Table 1.
Example 6
(1) Cerium zirconium solid solution
The cerium-zirconium solid solution Ce 0.09Zr0.91O2, x of 0.09 was obtained in the same manner as in step (1) of example 1.
(2) Carrier slurry
And adding the cerium-zirconium solid solution with the average particle size of 4.5 mu m and gallium chloride which are selected by sieving into an aluminum sol solution, mixing and pulping to obtain the carrier slurry with the solid content of 35 weight percent.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 650 ℃ for 2 hours, washing and filtering the catalyst particles with 6 times of deionized water, and calcining a filter cake at 600 ℃ for 1 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 30 wt.% of a support and 70 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The evaluation result of the catalyst shows that the conversion rate of propane is 47.86%, the yield of propylene is 42.76%, and the selectivity of propylene is 89.35%. The results are shown in Table 2.
Example 7
(1) Cerium zirconium solid solution
The cerium-zirconium solid solution Ce 0.29Zr0.71O2, x of 0.29 was prepared in the same manner as in step (1) of example 1.
(2) Carrier slurry
And adding the cerium-zirconium solid solution and gallium chloride which are screened and selected and have the average particle size of 5.0 mu m into the aluminum sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 40 weight percent.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 675 ℃ for 1.5 hours, washing and filtering the catalyst particles with 5 times of deionized water, and calcining a filter cake at 550 ℃ for 1.5 hours to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 70 wt.% of a support and 30 wt.% of a cerium zirconium solid solution; the carrier contained 20wt% gallium oxide and 80 wt% aluminum oxide.
The result of catalyst evaluation shows that the conversion rate of propane is 45.93%, the yield of propylene is 40.73%, and the selectivity of propylene is 88.67%. The results are shown in Table 2.
Example 8
(1) Cerium zirconium solid solution
The cerium-zirconium solid solution Ce 0.49Zr0.51O2, x of 0.49 was prepared in the same manner as in step (1) of example 1.
(2) Carrier slurry
And adding the cerium-zirconium solid solution and gallium chloride which are screened and selected and have the average particle size of 5.0 mu m into the aluminum sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 30 weight percent.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 700 ℃ for 1h, washing and filtering the catalyst particles with 4 times of deionized water, and calcining a filter cake at 500 ℃ for 2h to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 40 wt.% of a support and 60 wt.% of a cerium zirconium solid solution; the carrier contained 0.5 wt% gallium oxide and 99.5 wt% aluminum oxide.
The result of catalyst evaluation showed that the conversion of propane was 44.22%, the yield of propylene was 38.95% and the selectivity of propylene was 88.05%. The results are shown in Table 2.
Example 9
(1) Cerium zirconium solid solution
The cerium-zirconium solid solution Ce 0.69Zr0.31O2, x of 0.69 was obtained in the same manner as in step (1) of example 1.
(2) Carrier slurry
And adding the cerium-zirconium solid solution and gallium chloride which are selected by screening and have the average particle size of 2.5 mu m into the aluminum sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 40 weight percent.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 550 ℃ for 2 hours, washing and filtering the catalyst particles with 5 times of deionized water, and calcining a filter cake at 650 ℃ for 0.5 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 80 wt.% of a support and 20 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The result of catalyst evaluation shows that the conversion rate of propane is 42.75%, the yield of propylene is 37.46%, and the selectivity of propylene is 87.63%. The results are shown in Table 2.
Example 10
(1) Cerium zirconium solid solution
The cerium-zirconium solid solution Ce 0.89Zr0.11O2, x of 0.89 was prepared in the same manner as in step (1) of example 1.
(2) Carrier slurry
And adding the cerium-zirconium solid solution with the average particle size of 4.5 mu m and gallium chloride which are selected by screening into an aluminum sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 36 weight percent.
(3) Catalyst preparation
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 500 ℃ for 2.5 hours, washing and filtering the catalyst particles with 4 times of deionized water, and calcining a filter cake at 700 ℃ for 0.5 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 20 wt.% of a support and 80 wt.% of a cerium zirconium solid solution; the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The result of catalyst evaluation showed that the conversion of propane was 40.49%, the yield of propylene was 34.68% and the selectivity of propylene was 85.65%. The results are shown in Table 2.
Comparative example 1
Adding cerium nitrate, zirconium oxychloride and gallium chloride into aluminum sol for mixing and pulping to obtain carrier slurry;
And (3) spray drying the slurry to form catalyst particles, roasting the catalyst particles at 650 ℃ for 2 hours, washing and filtering the catalyst particles with 6 times deionized water, and calcining a filter cake at 600 ℃ for 1 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 30 wt% of a support and 70 wt% of ceria and zirconia (Ce: zr molar ratio of 1:9); the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The catalyst evaluation result shows that the conversion rate of the isobutene is 41.58%, the yield of the isobutene is 35.79%, and the selectivity of the isobutene is 85.07%. The results are shown in Table 1.
Comparative example 2
Cerium nitrate, zirconium oxychloride, gallium acetate, indium chloride, pseudo-boehmite powder and deionized water are mixed to obtain a carrier slurry with a solid content of 50% by weight. Adding nitric acid into the obtained carrier mixture, and extruding to form the catalyst particles.
The catalyst particles are roasted for 1.5 hours at 675 ℃, then washed and filtered by 5 times of deionized water, and the filter cake is roasted for 1.5 hours at 550 ℃ to obtain the alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 70 wt.% of a support and 30 wt.% of ceria and zirconia (Ce: zr molar ratio 3:7); the carrier contains 20 wt% of gallium oxide and indium oxide (weight ratio is 10:1), and 80 wt% of aluminum oxide.
The catalyst evaluation result shows that the conversion rate of the isobutene is 39.18%, the yield of the isobutene is 32.97%, and the selectivity of the isobutene is 84.16%. The results are shown in Table 1.
Comparative example 3
Adding cerium nitrate, zirconium oxychloride and gallium chloride into an aluminum sol solution, mixing and pulping to obtain carrier slurry with the solid content of 40 weight percent;
and (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 550 ℃ for 2 hours, washing and filtering the catalyst particles with 5 times of deionized water, and calcining a filter cake at 650 ℃ for 0.5 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 20 wt% of a support and 80 wt% of ceria and zirconia (Ce: zr molar ratio of 69:31); the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The result of catalyst evaluation shows that the conversion rate of propane is 39.18%, the yield of propylene is 33.39%, and the selectivity of propylene is 85.23%. The results are shown in Table 2.
Comparative example 4
Adding cerium nitrate, zirconium oxychloride and gallium chloride into an aluminum sol solution, mixing and pulping to obtain carrier slurry with the solid content of 36 weight percent;
And (3) spray drying the carrier slurry to form catalyst particles, roasting the catalyst particles at 550 ℃ for 2.5 hours, washing and filtering the catalyst particles with 4 times of deionized water, and calcining a filter cake at 700 ℃ for 0.5 hour to obtain an alkane dehydrogenation catalyst product.
An alkane dehydrogenation catalyst comprising 80 wt.% of a support and 20 wt.% of ceria and zirconia (Ce: zr molar ratio of 89:11); the carrier contained 12 wt% gallium oxide and 88 wt% aluminum oxide.
The result of the catalyst evaluation showed that the conversion of propane was 31.37%, the yield of propylene was 26.18% and the selectivity of propylene was 83.44%. The results are shown in Table 2.
TABLE 1
Note that: al 2O3
** SiO2
TABLE 2
Note that: al 2O3
** SiO2
From the results of the above examples, comparative examples and tables 1 and 2, it can be seen that the catalyst provided by the present invention, which contains cerium-zirconium solid solution as an active component, can obtain a better alkane conversion effect, and yield and selectivity of the target alkene by performing the dehydrogenation reaction of isobutane and propane. The catalyst provided by the invention can be free of polluted metals such as Cr, and has better environmental compatibility.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (22)

1. An alkane dehydrogenation catalyst comprising: a carrier and an active ingredient; the carrier contains gallium oxide and/or indium oxide and a binder; the binder is at least one selected from aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2, wherein x is more than 0 and less than 1.
2. The catalyst according to claim 1, wherein the active component comprises a solid solution of cerium and zirconium represented by the general formula Ce xZr1-xO2, wherein x.ltoreq.0.5.
3. Catalyst according to claim 1 or 2, wherein the support contains 0.5-20 wt.% gallium oxide and/or indium oxide, 80-99.5 wt.% of the binder, based on the total amount of the support.
4. The catalyst according to claim 1 or 2, wherein the carrier is present in an amount of 20 to 80% by weight and the active component is present in an amount of 20 to 80% by weight, based on the total amount of the catalyst.
5. The catalyst according to claim 4, wherein the carrier is present in an amount of 30 to 70% by weight and the active component is present in an amount of 30 to 70% by weight, based on the total amount of the catalyst.
6. A process for preparing an alkane dehydrogenation catalyst, the process comprising:
(1) Mixing a cerium source and a zirconium source, and preparing a cerium-zirconium solid solution represented by a general formula Ce xZr1-xO2 from the obtained mixture, wherein x is more than 0 and less than 1;
(2) Mixing and pulping the cerium-zirconium solid solution, a gallium source and/or an indium source, an aluminum source and/or a silicon source to obtain carrier slurry; or alternatively
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, the aluminum source and/or the silicon source into composite powder;
(3) And (3) forming the carrier slurry or the composite powder, and roasting, washing, filtering and calcining to obtain the alkane dehydrogenation catalyst.
7. The method according to claim 6, wherein in step (1), the cerium-zirconium solid solution is prepared by one of the following methods: coprecipitation, sol-gel, complexation, surfactant templating or solution burning.
8. The method according to claim 6, wherein in step (1), x is equal to or less than 0.5 in Ce xZr1-xO2.
9. The method of claim 6, wherein the cerium source is a precursor of cerium oxide; the zirconium source is a precursor of zirconia.
10. The method of claim 9, wherein the cerium source is selected from at least one of cerium chloride, cerium nitrate, cerium sulfate, and cerium acetate.
11. The method of claim 9, wherein the zirconium source is selected from at least one of zirconium oxychloride, zirconium chloride, zirconium nitrate, zirconyl nitrate, zirconium sulfate, and zirconium acetate.
12. The method of claim 9, wherein the molar ratio of the cerium source to the zirconium element is x: (1-x).
13. The method of claim 6, wherein in step (2), the gallium source is a precursor of gallium oxide; the indium source is a precursor of indium oxide.
14. The method of claim 6, wherein in step (2), the gallium source is selected from at least one of gallium chloride, gallium nitrate, gallium sulfate, and gallium acetate.
15. The method of claim 6, wherein in step (2), the indium source is selected from at least one of indium chloride, indium nitrate, indium sulfate, and indium acetate.
16. The method according to claim 6, wherein in the step (2), the gallium source, the indium source, the aluminum source and the silicon source are used in an amount sufficient to obtain the catalyst, and the carrier contains 0.5 to 20% by weight of gallium oxide and/or indium oxide and 80 to 99.5% by weight of a binder selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide, based on the total weight of the carrier contained in the catalyst.
17. The method according to claim 6, wherein in the step (2), the cerium-zirconium solid solution is used in an amount such that the catalyst contains a carrier in an amount of 20 to 80% by weight and an active component in an amount of 20 to 80% by weight based on the total amount of the catalyst; wherein the active component contains the cerium-zirconium solid solution.
18. The method according to claim 17, wherein in the step (2), the carrier is contained in an amount of 30 to 70% by weight and the active component is contained in an amount of 30 to 70% by weight based on the total amount of the catalyst.
19. The method of claim 6, wherein in step (3), the firing conditions are: the temperature is 500-800 ℃ and the time is 4-7h.
20. The method of claim 6, wherein in step (3), the calcining conditions are: the temperature is 500-700 ℃ and the time is 1-4h.
21. An alkane dehydrogenation catalyst obtainable by the process of any one of claims 6 to 19.
22. Use of an alkane dehydrogenation catalyst as defined in any one of claims 1-5 and 21 in the dehydrogenation of an alkane to produce an alkene.
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