CN112973661A - Alkane dehydrogenation catalyst, preparation method and application thereof - Google Patents

Alkane dehydrogenation catalyst, preparation method and application thereof Download PDF

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CN112973661A
CN112973661A CN202010227117.9A CN202010227117A CN112973661A CN 112973661 A CN112973661 A CN 112973661A CN 202010227117 A CN202010227117 A CN 202010227117A CN 112973661 A CN112973661 A CN 112973661A
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cerium
source
carrier
zirconium
oxide
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CN112973661B (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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Beijing Zhongneng Weiye Technology Development 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. An alkane dehydrogenation catalyst, its preparation and use are disclosed. The alkane dehydrogenation catalyst comprises: a carrier and an active component carried on the carrier; 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, and the active component contains cerium-zirconium solid solution CexZr1‑ xO2Wherein x is less than 1. The catalyst can be applied to a fixed bed or fluidized bed process, and can effectively realize the olefin preparation by alkane dehydrogenation.

Description

Alkane dehydrogenation catalyst, 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
Olefin is an important bulk chemical raw material for petrochemical production, and has wide application. Olefins are produced mainly by steam cracking of hydrocarbons (e.g., naphtha steam cracking), catalytic cracking of olefins (e.g., Superflex technology), catalytic cracking of heavy oils (e.g., TMP, DCC technology), and catalytic pyrolysis of heavy oils (e.g., CPP technology), and catalytic dehydrogenation of alkanes is also an important technical route for olefin production.
The catalytic dehydrogenation of alkane can obtain economically acceptable single pass conversion rate and olefin selectivity under the proper temperature condition, so that the catalytic dehydrogenation method is adopted for preparing olefin by alkane dehydrogenation.
In the prior art, dehydrogenation catalysts for the dehydrogenation of alkanes contain a group VIII metal and a metal compound which can be reduced 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 relatively quickly during the dehydrogenation reaction and may deactivate even within minutes. In the prior art, there is the incorporation of Sn in catalysts containing group VIII metals for improving the activity and lifetime of the catalysts, e.g. Pt/Sn/ZnAl2O4The catalyst has high dehydrogenation activity and olefin selectivity on alkane, however, the introduction of Sn cannot get rid of the trouble that the catalyst needs to be frequently regenerated. Such catalysts are generally classified into two types, Cr-based catalysts and Pt-based catalysts. Both the Cr-based catalyst and the Pt-based catalyst are deactivated by coking within several hours of continuous feeding, and thus the catalyst must be frequently regenerated. In addition, the Pt is expensive, the application of the Pt catalyst dehydrogenation process is limited by high investment and catalyst use cost, and the process is reasonable in economy only in countries or regions with abundant and low-cost isobutane resources. In addition, with Pt catalysts, the recycle gas must also be deoxygenated because the catalysts are very sensitive to oxygen, including molecular oxygen, methanol, MTBE, dimethyl ether, and oxygen in water; for Cr catalysts, the dehydrogenation performance of supported Cr catalysts has been nearly perfect, e.g., the Catofin process approaches conversionThe selectivity of the olefin is still above 95% at the limit of thermodynamic equilibrium, however, the environmental problem of leakage of hexavalent Cr is not insignificant.
Thus, improved catalysts are also needed for alkane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defect that the existing alkane dehydrogenation catalyst uses noble metal, and provides an alkane dehydrogenation catalyst, and 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 selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains general formula CexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein x < 1.
Preferably, the carrier contains 0.5-20 wt% of gallium oxide and/or indium oxide, and 80-99.5 wt% of the binder, based on the total amount of the carrier.
Preferably, the content of the carrier is 20-80 wt% and the content of the active component is 20-80 wt% based on the total amount of the catalyst.
In a second aspect, the present invention provides a method for preparing an alkane dehydrogenation catalyst, comprising:
(1) mixing a cerium source and a zirconium source, and obtaining the general formula Ce from the obtained mixturexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein 0 < x < 1;
(2) mixing and pulping the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain carrier slurry; or
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain composite powder;
(3) and forming the carrier slurry or the composite powder to prepare the alkane dehydrogenation catalyst.
In a third aspect, the invention provides an alkane dehydrogenation catalyst made by the process of the invention.
In a fourth aspect, the present invention provides a use of the alkane dehydrogenation catalyst of the present invention in the dehydrogenation of an alkane to produce an alkene.
Through the technical scheme, the invention provides the alkane dehydrogenation catalyst without containing noble metal. The catalyst can be applied to a fixed bed or fluidized bed process, can effectively realize the olefin preparation by alkane dehydrogenation, such as propylene preparation by propane dehydrogenation and isobutene preparation by isobutane dehydrogenation, and has the alkane once-through conversion rate of 40-50 wt% and the olefin selectivity of 85-90 wt%.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should 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 selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains general formula CexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein x < 1.
The invention provides a noble metal-free alkane dehydrogenation catalyst, which selects a carrier containing gallium oxide and/or indium oxide and uses a cerium-zirconium-containing solid solution Ce in a matching wayxZr1-xO2The active component can effectively perform alkane dehydrogenation, particularly propane dehydrogenation to prepare propylene and isobutane dehydrogenation to prepare isobutene.
In the invention, the active component contains cerium-zirconium solid solution CexZr1-xO2Among them, x is preferably 0.5 or less. Better alkane dehydrogenation effect can be realized.
In the present invention, in the composition of the alkane dehydrogenation catalyst, it is further preferred 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. When the carrier contains both gallium oxide and indium oxide, the weight ratio of gallium oxide to indium oxide is preferably 9-19: 1.
In the present invention, in the composition of the alkane dehydrogenation catalyst, it is further preferred 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; preferably, the carrier is present in an amount of 30 to 70 wt.%, and the active ingredient is present in an amount of 30 to 70 wt.%. The catalyst obtained in the above composition range can more effectively realize the dehydrogenation effect of the alkane.
In the invention, the provided catalyst composition comprises cerium-zirconium solid solution CexZr1-xO2The component is used as an active component, and can be tested by XRD to obtain Ce appearing in a spectrogramxZr1-xO2The specific composition of the cerium-zirconium solid solution can be determined by contrasting and marking an XRD spectrogram card and further combining element analysis. The composition of the cerium-zirconium solid solution can also be calculated from the raw material charge for preparing the cerium-zirconium solid solution. Namely, the value of x in the general formula of the cerium-zirconium solid solution can be determined according to the analysis result or the feeding amount.
Meanwhile, the carrier of the catalyst contains gallium oxide and/or indium oxide, and experiments prove that the carrier can provide the alkane dehydrogenation effect in cooperation with the active component.
In a second aspect, the present invention provides a method for preparing an alkane dehydrogenation catalyst, comprising:
(1) mixing a cerium source and a zirconium source, and obtaining the general formula Ce from the obtained mixturexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein 0 < x < 1;
(2) mixing and pulping the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain carrier slurry; or
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain composite powder;
(3) and forming the carrier slurry or the composite powder to prepare the alkane dehydrogenation catalyst.
In the present invention, preferably, x is 0.5 or less.
In the present invention, cerium-zirconium solid solution Ce as an active componentxZr1-xO2Can be prepared separately. Preferably, in the step (1), the cerium-zirconium solid solution is prepared by one of the following methods: coprecipitation, sol-gel, complexation, surfactant templating, or solution combustion. The preparation method of the cerium-zirconium solid solution preferably comprises a coprecipitation method or a sol-gel method.
One embodiment of the present invention may be a coprecipitation process. The cerium source and the zirconium source can be mixed into aqueous solution containing cerium and zirconium, then the obtained mixture is contacted with a precipitator for precipitation reaction, a reaction product is filtered and washed to obtain a filter cake containing precipitates of cerium and zirconium, a cerium-zirconium solid solution is obtained by drying and roasting, and the composition structure of the cerium-zirconium solid solution can be determined by XRD and element analysis. Wherein the cerium source and the zirconium source are used in amounts that 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 aqueous solution containing cerium and zirconium, then the aqueous solution is mixed with aqueous solution containing acid or alkali, hydrolysis reaction or polymerization reaction is carried out to obtain gel product, the gel product is dried and roasted to obtain cerium-zirconium solid solution, and the composition structure of the cerium-zirconium solid solution can be determined by XRD and element analysis. Wherein the cerium source and the zirconium source are used in amounts that satisfy the composition of the obtained cerium-zirconium solid solution.
Some embodiments of the present invention provide that the implementation may be a solution combustion process. The specific steps may include: soluble salts of zirconium and cerium and urea (or organic substances 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 present invention provide that the specific implementation 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 using 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 can be at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and potassium lauryl alcohol ether 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, and P123(PEO-PPO-PEO, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer); the cationic surfactant may be at least one selected from the group consisting of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, dodecyldimethylbenzylammonium chloride and octadecyldimethylbenzylammonium chloride. The pH value is adjusted to 8-12. The conditions for the heating reaction were: the reaction temperature is 60-90 ℃, and the reaction time is 24-144 h.
In the present invention, the cerium source and the zirconium source are materials 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 the group consisting of cerium chloride, cerium nitrate, cerium sulfate and cerium acetate; the zirconium source is a precursor of zirconium oxide, and is preferably at least one selected from the group consisting of zirconium oxychloride, zirconium chloride, zirconium nitrate, zirconium sulfate, and zirconium acetate.
In the present invention, preferably, the weight ratio of the cerium source to the zirconium source is x: (1-x). The cerium-zirconium solid solution provided by the invention can be obtained. Here, x is defined as the same as x in the general formula shown in the finally obtained cerium-zirconium solid solution.
In the present invention, in one embodiment, step (2) is used to prepare a carrier slurry, which can be used in the subsequent step (3) to form a catalyst by the carrier slurry. In another embodiment, step (2) is used for preparing the composite powder, and can be used for forming the catalyst through the composite powder in the subsequent step (3). In both embodiments, preferably, the gallium source is a precursor of gallium oxide, preferably at least one selected from the group consisting of gallium chloride, gallium nitrate, gallium sulfate and gallium acetate; the indium source is a precursor of indium oxide, and is 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 alumina, silica and/or a composite oxide of silica and alumina, for example, may be an aluminum sol, a silica sol or a silica-alumina sol, may be a mixed solution containing an aluminum precursor, a silica precursor or both, and may be a powder containing alumina, silica or a composite oxide of silica and alumina. Among them, the aluminum precursor may be preferably selected from at least one of chlorides, nitrates, sulfates, and aluminum isopropoxide of aluminum; the silicon precursor may preferably be selected from at least one of water glass, silicon tetrachloride, and alkoxysilane.
In one embodiment of the present 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 present invention, which comprises the carrier and the 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, and the aluminum source and/or the silicon source are mixed into a composite powder, and then the alkane dehydrogenation catalyst provided by the invention, which comprises the carrier and the active component, is formed in one step through the step (3). The catalyst prepared by the method can provide better effect of dehydrogenating alkane into alkene.
In the invention, the prepared alkane dehydrogenation catalyst comprises a carrier and an active component. The gallium source, the indium source, the aluminum source and the silicon source can be used for preparing the carrier. The cerium zirconium solid solution may be used as at least a part of the active component. Preferably, the gallium source, the indium source, the aluminum source and the silicon source are used in amounts such that the catalyst is prepared, wherein the carrier contains 0.5-20 wt% of gallium oxide and/or indium oxide and 80-99.5 wt% 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. In the finally prepared alkane dehydrogenation catalyst, the carrier may comprise gallium oxide and/or indium oxide, and a binder. The binder can be prepared from the aluminum source and the silicon source which are fed in the preparation method provided by the invention. 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 9-19:1 to provide better catalyst alkane dehydrogenation effect.
In the present invention, preferably, in the step (2), the cerium-zirconium solid solution is used in an amount such that, in the obtained catalyst, the content of the carrier is 20 to 80 wt% and the content of the active component is 20 to 80 wt%, based on the total amount of the catalyst; preferably, the carrier is contained in an amount of 30 to 70 wt%, and the active ingredient is contained in an amount of 30 to 70 wt%; wherein the active component contains the cerium-zirconium solid solution.
In the invention, corresponding to the carrier slurry or the composite powder obtained in the step (2), in the step (3), the forming method can be used for carrying out spray drying forming or extrusion molding on the carrier slurry in one embodiment; in another embodiment, the composite powder may be tableted. In order to meet the molding requirement of the catalyst, the cerium-zirconium solid solution can be crushed and sieved to obtain particles with the average particle size of 2-5 mu m. Further, the adjustment of the solid content of the carrier slurry or the introduction of other reagents required for shaping can be carried out according to the requirements of the shaping, but does not affect the chemical properties of the catalyst. The conditions for each of the spray-dry molding, the tablet-forming and the extrusion molding may be those conventional in the art. For example, the extrusion molding may be performed after adding nitric acid 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 5-8 h; the roasting temperature is 500-800 ℃, preferably 550-700 ℃, and the roasting time is 4-7 h.
In the invention, the method further comprises 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 calcining temperature is 550-700 ℃, and the time is 1-4 h.
In a third aspect, the invention provides an alkane dehydrogenation catalyst made by the process of the 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 selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains general formula CexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein x is less than 1, preferably x is less than or equal to 0.5. The structure and composition of cerium zirconium solid solutions can be determined by XRD and elemental analysis. Can also be determined by the raw material feeding of the preparation method.
In the alkane dehydrogenation catalyst, the carrier contains 0.5-20 wt% of gallium oxide and/or indium oxide and 80-99.5 wt% 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% and the content of the active component is 20-80 wt% based on the total amount of the catalyst; preferably, the carrier is present in an amount of 30 to 70 wt.%, and the active ingredient is present in an amount of 30 to 70 wt.%.
In a fourth aspect, the present invention provides a use of the alkane dehydrogenation catalyst of the present invention in the dehydrogenation of an alkane to produce an alkene.
For example, propane dehydrogenation can be used to produce propylene, and isobutane dehydrogenation can be used to produce isobutane.
In the following examples and comparative examples, the reaction for producing isobutylene by dehydrogenation of isobutane and the reaction for producing propylene by dehydrogenation of propane were carried out in performance evaluation in a fixed bed micro-reactor at 575 ℃ and 3 hours in mass space time-1。
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 a mother solution, filtering and washing the mother solution, drying and roasting an obtained filter cake to obtain a cerium-zirconium solid solution, and performing XRD (X-ray diffraction) determination and element analysis to obtain a cerium-zirconium solid solution with a chemical structure represented by Ce0.1Zr0.9O2And x is 0.1.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 2.0 mu m selected by screening and gallium chloride into alumina sol for mixing and pulping to obtain carrier slurry with the solid content of 38 weight percent.
(3) Catalyst preparation
And (3) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 650 ℃ for 2h, washing and filtering the catalyst particles by 6 times of deionized water, and calcining a filter cake at 600 ℃ for 1h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 30 weight percent of a carrier and 70 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the isobutane conversion was 49.85%, the isobutylene yield was 44.80%, and the isobutylene selectivity was 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 a mother solution, filtering and washing the mother solution, drying and roasting an obtained filter cake to obtain a cerium-zirconium solid solution, and determining by XRD that the chemical structure of the solid solution is represented as Ce0.3Zr0.7O2And x is 0.3.
(2) Carrier
And mixing the cerium-zirconium solid solution with the average particle size of 2.5 mu m, gallium acetate, indium chloride, pseudo-boehmite powder and deionized water, thereby obtaining 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 of deionized water, and roasting a filter cake at 550 ℃ for 1.5h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 70 wt% of a carrier and 30 wt% of a cerium-zirconium solid solution; the carrier contained 20 wt.% of gallium oxide and indium oxide (weight ratio 10: 1), 80 wt.% of alumina.
The catalyst is used for converting isobutane into isobutene. The evaluation results showed that the isobutane conversion was 45.57%, the isobutylene yield was 40.55%, and the isobutylene selectivity 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 coagulant, performing hydrolysis and polymerization reaction to obtain a gel product, drying and roasting to obtain a cerium-zirconium solid solution, and determining by XRD that the chemical structure of the solid solution is represented as Ce0.5Zr0.5O2And x is 0.5.
(2) Carrier slurry
Adding the screened cerium-zirconium solid solution with the average particle size of 3.0 mu m and indium nitrate into silica sol for mixing and pulping to obtain carrier slurry with the solid content of 30 weight percent.
(3) Catalyst preparation
And (2) carrying out spray drying and forming on the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 700 ℃ for 1h, then washing and filtering the catalyst particles by using 4 times of deionized water, and calcining a filter cake at 500 ℃ for 2h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 40 wt% of a carrier and 60 wt% of a cerium-zirconium solid solution; the carrier contained 0.5 wt.% indium oxide, 99.5 wt.% silicon oxide.
The catalyst evaluation results showed that the isobutane conversion was 44.76%, the isobutylene yield was 39.41%, and the isobutylene selectivity was 88.05%. The results are shown in Table 1.
Example 4
(1) Cerium zirconium solid solution
Dissolving cerium sulfate, zirconium oxychloride and urea in water to obtain a mixed solution, heating the mixed solution until combustion occurs to obtain a cerium-zirconium solid solution, and determining by XRD that the chemical structure of the solid solution is represented by Ce0.7Zr0.3O2And x is 0.7.
(2) Carrier slurry
Adding the screened cerium-zirconium solid solution with the average particle size of 3.5 mu m 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) carrying out spray drying and forming on the carrier slurry to obtain catalyst particles, roasting the catalyst particles for 2 hours at 550 ℃, then washing and filtering the catalyst particles by using 5 times of deionized water, and calcining a filter cake for 0.5 hour at 650 ℃ to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 30 weight percent of a carrier and 70 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the isobutane conversion was 42.17%, the isobutene yield was 36.93%, and the isobutene selectivity was 87.58%. The results are shown in Table 1.
Example 5
(1) Cerium zirconium solid solution
Dissolving cerium nitrate, zirconyl nitrate and tween 80 in water to obtain a mixed solution, adding ammonia water to adjust the pH to 10, and heating to 85 ℃ under stirring to react for 120 hours. Filtering, washing, drying (120 ℃, 8h) and roasting (600 ℃, 6h) the obtained reaction product to obtain a cerium-zirconium solid solution, and determining by XRD that the chemical structure of the solid solution is represented as Ce0.9Zr0.1O2And x is 0.9.
(2) Composite powder
Mixing the cerium-zirconium solid solution with the average grain diameter of 4.0 mu m, which is selected by screening, with the indium sulfate and silicon-aluminum composite oxide powder to obtain composite powder,
(3) catalyst preparation
And tabletting and molding 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 and filtering the product particles by using 4 times of deionized water, and calcining the filter cake at 700 ℃ for 0.5h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 30 weight percent of a carrier and 70 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the isobutane conversion was 41.76%, the isobutylene yield was 36.27%, and the isobutylene selectivity was 86.85%. The results are shown in Table 1.
Example 6
(1) Cerium zirconium solid solution
Cerium zirconium solid solution Ce was obtained by the method of the step (1) in example 10.09Zr0.91O2And x is 0.09.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 4.5 mu m and the gallium chloride which are selected by screening into the alumina sol solution for mixing and pulping to obtain carrier slurry with the solid content of 35 weight percent.
(3) Catalyst preparation
And (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 650 ℃ for 2h, washing and filtering the catalyst particles by 6 times of deionized water, and calcining a filter cake at 600 ℃ for 1h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 30 weight percent of a carrier and 70 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 47.86%, the propylene yield was 42.76%, and the propylene selectivity was 89.35%. The results are shown in Table 2.
Example 7
(1) Cerium zirconium solid solution
Cerium zirconium solid solution Ce was obtained by the method of the step (1) in example 10.29Zr0.71O2And x is 0.29.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 5.0 mu m and the gallium chloride which are selected by screening into the alumina sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 40 weight percent.
(3) Catalyst preparation
And (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 675 ℃ for 1.5h, washing and filtering the catalyst particles by using 5 times of deionized water, and calcining a filter cake at 550 ℃ for 1.5h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 70 wt% of a carrier and 30 wt% of a cerium-zirconium solid solution; the carrier contained 20 wt% gallium oxide and 80 wt% alumina.
The catalyst evaluation results showed that the propane conversion was 45.93%, the propylene yield was 40.73%, and the propylene selectivity was 88.67%. The results are shown in Table 2.
Example 8
(1) Cerium zirconium solid solution
Cerium zirconium solid solution Ce was obtained by the method of the step (1) in example 10.49Zr0.51O2And x is 0.49.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 5.0 mu m and the gallium chloride which are selected by screening into the alumina sol solution for mixing and pulping to obtain 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 by using 4 times of deionized water, and calcining a filter cake at 500 ℃ for 2h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 40 wt% of a carrier and 60 wt% of a cerium-zirconium solid solution; the carrier contained 0.5 wt.% gallium oxide and 99.5 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 44.22%, the propylene yield was 38.95%, and the propylene selectivity was 88.05%. The results are shown in Table 2.
Example 9
(1) Cerium zirconium solid solution
Cerium zirconium solid solution Ce was obtained by the method of the step (1) in example 10.69Zr0.31O2And x is 0.69.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 2.5 mu m and the gallium chloride which are selected by screening into the alumina sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 40 weight percent.
(3) Catalyst preparation
And (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 550 ℃ for 2h, washing and filtering the catalyst particles by using 5 times of deionized water, and calcining a filter cake at 650 ℃ for 0.5h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 80 weight percent of a carrier and 20 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 42.75%, the propylene yield was 37.46%, and the propylene selectivity was 87.63%. The results are shown in Table 2.
Example 10
(1) Cerium zirconium solid solution
Cerium zirconium solid solution Ce was obtained by the method of the step (1) in example 10.89Zr0.11O2And x is 0.89.
(2) Carrier slurry
Adding the cerium-zirconium solid solution with the average grain size of 4.5 mu m and the gallium chloride which are selected by screening into the alumina sol solution for mixing and pulping to obtain the carrier slurry with the solid content of 36 weight percent.
(3) Catalyst preparation
And (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 500 ℃ for 2.5h, washing and filtering the catalyst particles by using 4 times of deionized water, and calcining a filter cake at 700 ℃ for 0.5h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 20 weight percent of a carrier and 80 weight percent of a cerium-zirconium solid solution; the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 40.49%, the propylene yield was 34.68%, and the propylene selectivity was 85.65%. The results are shown in Table 2.
Comparative example 1
Adding cerium nitrate, zirconium oxychloride and gallium chloride into the alumina sol, mixing and pulping to obtain carrier slurry;
and (3) spray drying and forming the slurry to obtain catalyst particles, roasting the catalyst particles at 650 ℃ for 2h, washing and filtering the catalyst particles by 6 times of deionized water, and calcining a filter cake at 600 ℃ for 1h to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 30 weight percent of carrier and 70 weight percent of cerium oxide and zirconium oxide (the molar ratio of Ce to Zr is 1: 9); the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the isobutane conversion was 41.58%, the isobutene yield was 35.79%, and the isobutene selectivity was 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 carrier slurry with solid content of 50 wt%. Adding nitric acid into the obtained carrier mixture, and extruding to form to obtain the catalyst particles.
The catalyst particles are roasted for 1.5h at 675 ℃, then washed and filtered by 5 times of deionized water, and the filter cake is roasted for 1.5h at 550 ℃ to obtain the alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 70 weight percent of carrier and 30 weight percent of cerium oxide and zirconium oxide (the molar ratio of Ce to Zr is 3: 7); the carrier contained 20 wt.% of gallium oxide and indium oxide (weight ratio 10: 1), 80 wt.% of alumina.
The catalyst evaluation results showed that the isobutane conversion was 39.18%, the isobutylene yield was 32.97%, and the isobutylene selectivity was 84.16%. The results are shown in Table 1.
Comparative example 3
Adding cerium nitrate, zirconium oxychloride and gallium chloride into the alumina sol solution for mixing and pulping to obtain carrier slurry with the solid content of 40 weight percent;
and (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 550 ℃ for 2h, washing and filtering the catalyst particles by using 5 times of deionized water, and calcining a filter cake at 650 ℃ for 0.5h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 20 weight percent of carrier and 80 weight percent of cerium oxide and zirconium oxide (the molar ratio of Ce to Zr is 69: 31); the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 39.18%, the propylene yield was 33.39%, and the propylene selectivity was 85.23%. The results are shown in Table 2.
Comparative example 4
Adding cerium nitrate, zirconium oxychloride and gallium chloride into the alumina sol solution for mixing and pulping to obtain carrier slurry with the solid content of 36 weight percent;
and (2) spray drying and forming the carrier slurry to obtain catalyst particles, roasting the catalyst particles at 550 ℃ for 2.5h, washing and filtering the catalyst particles by using 4 times of deionized water, and calcining a filter cake at 700 ℃ for 0.5h to obtain an alkane dehydrogenation catalyst product.
The alkane dehydrogenation catalyst comprises 80 weight percent of carrier and 20 weight percent of cerium oxide and zirconium oxide (the molar ratio of Ce to Zr is 89: 11); the carrier contained 12 wt.% gallium oxide and 88 wt.% alumina.
The catalyst evaluation results showed that the propane conversion was 31.37%, the propylene yield was 26.18%, and the propylene selectivity was 83.44%. The results are shown in Table 2.
TABLE 1
Figure BDA0002428086530000171
Figure BDA0002428086530000181
Note: al2O3
**SiO2
TABLE 2
Figure BDA0002428086530000182
Note: al2O3
**SiO2
As can be seen from the results of the above examples, comparative examples and tables 1 and 2, the catalyst provided by the present invention, which contains a cerium-zirconium solid solution as an active component, can perform dehydrogenation reactions of isobutane and propane to obtain better alkane conversion effects and yield and selectivity of target olefins. The catalyst provided by the invention does not use polluted metal such as Cr, and has better environmental compatibility.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

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 selected from at least one of aluminum oxide, silicon oxide and silicon-aluminum composite oxide; the active component contains general formula CexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein x is less than 1, preferably x is less than or equal to 0.5.
2. The catalyst according to claim 1, wherein the carrier contains 0.5 to 20 wt% of gallium oxide and/or indium oxide and 80 to 99.5 wt% of the binder, based on the total amount of the carrier.
3. The catalyst according to claim 1 or 2, wherein the carrier is present in an amount of 20-80 wt% and the active component is present in an amount of 20-80 wt%, based on the total amount of the catalyst; preferably, the carrier is present in an amount of 30 to 70 wt.%, and the active ingredient is present in an amount of 30 to 70 wt.%.
4. A method of preparing an alkane dehydrogenation catalyst comprising:
(1) mixing a cerium source and a zirconium source, and obtaining the general formula Ce from the obtained mixturexZr1-xO2The cerium zirconium solid solution is represented by formula (I), wherein x is more than 0 and less than 1, and x is preferably less than or equal to 0.5;
(2) mixing and pulping the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain carrier slurry; or
Mixing the cerium-zirconium solid solution, the gallium source and/or the indium source, and the aluminum source and/or the silicon source to obtain composite powder;
(3) and forming the carrier slurry or the composite powder to prepare the alkane dehydrogenation catalyst.
5. The method according to claim 4, 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 combustion.
6. The method according to claim 4 or 5, wherein the cerium source is a precursor of cerium oxide, preferably at least one selected from the group consisting of 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, zirconium sulfate and zirconium acetate;
preferably, the cerium source and the zirconium source are present in a weight ratio of x: (1-x).
7. The method according to any one of claims 4 to 6, wherein in step (2), the gallium source is a precursor of gallium oxide, preferably at least one selected from the group consisting of gallium chloride, gallium nitrate, gallium sulfate and gallium acetate; the indium source is a precursor of indium oxide, preferably at least one selected from indium chloride, indium nitrate, indium sulfate and indium acetate;
preferably, the gallium source, the indium source, the aluminum source and the silicon source are used in amounts such that the catalyst is prepared, wherein 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.
8. The method according to any one of claims 4 to 7, wherein in 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 wt% and an active component in an amount of 20 to 80 wt%, based on the total amount of the catalyst; preferably, the carrier is contained in an amount of 30 to 70 wt%, and the active ingredient is contained in an amount of 30 to 70 wt%; wherein the active component contains the cerium-zirconium solid solution.
9. An alkane dehydrogenation catalyst made by the process of any of claims 4-8.
10. Use of an alkane dehydrogenation catalyst according to any one of claims 1 to 4 and 9 for the dehydrogenation of an alkane to an alkene.
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