CN110614116A - Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation - Google Patents

Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation Download PDF

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CN110614116A
CN110614116A CN201810639008.0A CN201810639008A CN110614116A CN 110614116 A CN110614116 A CN 110614116A CN 201810639008 A CN201810639008 A CN 201810639008A CN 110614116 A CN110614116 A CN 110614116A
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noble metal
molecular sieve
low
mesoporous molecular
silicon
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刘红梅
亢宇
刘东兵
薛琳
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petrochemical Corp
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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • B01J35/617—
    • B01J35/635—
    • B01J35/638—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • 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

Abstract

The invention relates to the field of catalysts, and discloses a method for preparing a non-noble metal low-carbon alkane dehydrogenation catalyst, which comprises the following steps: (a) under the ultrasonic condition, contacting an all-silicon SBA-15 mesoporous molecular sieve material with an aqueous solution containing sulfate and/or sulfite, and then sequentially removing a solvent, drying and roasting to obtain a modified all-silicon SBA-15 mesoporous molecular sieve carrier; (b) dipping the modified all-silicon SBA-15 mesoporous molecular sieve carrier obtained in the step (a) in a solution containing an active non-noble metal component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting. The non-noble metal low-carbon alkane dehydrogenation catalyst can achieve better dehydrogenation activity, selectivity and stability in the reactions of preparing propylene by propane dehydrogenation and preparing isobutene by isobutane dehydrogenation.

Description

Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation
Technical Field
The invention relates to the field of catalysts, in particular to a non-noble metal low-carbon alkane dehydrogenation catalyst, a preparation method thereof, the non-noble metal low-carbon alkane dehydrogenation catalyst prepared by the method, and a method for preparing low-carbon olefin by low-carbon alkane dehydrogenation.
Background
The low-carbon olefin (mainly comprising propylene, isobutene and the like) is a very important organic chemical raw material. The propylene can be used for producing chemical products such as polypropylene, acrolein, acrylic acid, glycerol, isopropanol, polyacrylonitrile, butanol and octanol; isobutene is used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. At present, propylene and isobutene are mainly derived from refinery by-products and steam cracking co-production. Recently, with the rapid development of coal chemical industry, the realization of MTP process has effectively increased the source of propylene. Even so, the gaps in propylene and isobutylene are still not made up. In the above background, dehydrogenation of lower alkanes makes one of the important ways to increase the sources of propylene and isobutylene. The dehydrogenation technology of the low-carbon alkane is mainly divided into direct dehydrogenation and oxidative dehydrogenation, wherein the direct dehydrogenation technology has realized industrial production in 90 years in the 20 th century. The low-carbon alkane direct dehydrogenation catalyst for industrial application mainly comprises a Cr series catalyst and a Pt series catalyst. There are a Catofin process developed by Lummus, a Linde process developed by Linde & BASF, and an FBD process developed by Snamprogetti using Cr-series catalysts, an Oleflex process developed by UOP, and a Star process developed by Phillips using Pt-series catalysts. The Cr-based catalyst is low in price but easy to deactivate, and the heavy metal chromium causes serious environmental pollution. Relatively speaking, the Pt catalyst has high activity, good selectivity and stability, but the noble metal platinum is expensive and the catalyst cost is high. Therefore, until now, the development of non-noble metal based low-carbon alkane dehydrogenation catalysts with higher activity, better stability and environmental friendliness is still the main research direction for producing low-carbon olefins.
In order to improve various performance indexes of non-noble metal low-carbon alkane dehydrogenation catalysts, researchers have made a lot of work to improve Cr-series catalysts and Pt-series catalysts. Such as: the reaction performance of the Pt catalyst is improved by an oxide carrier modification method (CN106607100A, CN106607099A), the catalyst activity is improved by an improved catalyst preparation method (CN103418376A, CN106944081A), and the catalytic performance of the Cr catalyst is improved by an additive method (CN 104549220A). However, the specific surface area of the currently-used carrier is small, which is not beneficial to the dispersion of active non-noble metal components on the surface of the carrier, and is also not beneficial to the diffusion of raw materials and products in the reaction process. Therefore, the selection of a proper carrier with excellent performance is an urgent problem to be solved in the field of low-carbon alkane dehydrogenation.
In 1998, Zhao Dongyuan et al successfully synthesized the mesoporous silica molecular sieve SBA-15(Science,1998,279(5350): 548-552). The SBA-15 mesoporous molecular sieve is obtained by hydrothermal synthesis under an acidic condition by using a triblock copolymer as a template agent and tetraethoxysilane as a silicon source. Compared with the common alumina carrier, the SBA-15 has higher specific surface area and is more beneficial to the dispersion of active components. In addition, different from other mesoporous materials, the template used for preparing SBA-15 does not cause environmental pollution. Therefore, the SBA-15 and the modified material thereof are suitable to be used as carriers of non-noble metal series low-carbon alkane dehydrogenation catalysts.
However, the conventional SBA-15 molecular sieve material still has an acid site, and when the material is used as a catalyst carrier, the defects of easy carbon deposition and the like still exist, and the selectivity of a target product is to be further improved.
Therefore, how to improve the reaction performance of the non-noble metal-based low-carbon alkane dehydrogenation catalyst by improving the carrier performance of the supported non-noble metal-based low-carbon alkane dehydrogenation catalyst and cooperatively supporting a proper active component is an urgent problem in the field of low-carbon olefin preparation through low-carbon alkane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of high cost and environmental pollution easily caused by non-noble metal low-carbon alkane dehydrogenation catalysts in the prior art, and provides a non-noble metal low-carbon alkane dehydrogenation catalyst and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing a non-noble metal-based light alkane dehydrogenation catalyst, comprising the steps of:
(a) under the ultrasonic condition, contacting an all-silicon SBA-15 mesoporous molecular sieve material with an aqueous solution containing sulfate and/or sulfite, and then sequentially removing a solvent, drying and roasting to obtain a modified all-silicon SBA-15 mesoporous molecular sieve carrier;
(b) dipping the modified all-silicon SBA-15 mesoporous molecular sieve carrier obtained in the step (a) in a solution containing an active non-noble metal component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
The invention provides a non-noble metal-based low-carbon alkane dehydrogenation catalyst prepared by the method.
The third aspect of the present invention provides a method for preparing a low carbon olefin by dehydrogenating a low carbon alkane, the method comprising: and carrying out dehydrogenation reaction on the low-carbon alkane in the presence of a catalyst and inert gas, wherein the catalyst is the non-noble metal low-carbon alkane dehydrogenation catalyst.
The carrier structure of the dehydrogenation catalyst (including physical structures such as specific surface area, pore volume and pore size distribution, and chemical structures such as surface acid sites and electronic properties) not only has an important influence on the dispersion of active components, but also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity and stability, depend both on the catalytic characteristics of the active component and on the characteristics of the catalyst support. Currently, the non-noble metal low-carbon alkane dehydrogenation catalyst used in industry generally uses alumina as a carrier. However, most commercially available activated aluminas have a low specific surface area and are too acidic with too many surface hydroxyl groups. When the aluminum oxide is used as a carrier to prepare the dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon in the reaction process, and the rapid inactivation is caused.
The inventor of the invention discovers through research that the non-noble metal-based low-carbon alkane dehydrogenation catalyst with good performance can be obtained by using the all-silicon SBA-15 mesoporous molecular sieve modified by the method provided by the invention as a carrier and loading a non-noble metal component as an active component.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the non-noble metal low-carbon alkane dehydrogenation catalyst does not contain noble metal, so that the preparation cost of the dehydrogenation catalyst can be effectively reduced;
(2) the non-noble metal low-carbon alkane dehydrogenation catalyst provided by the preferred scheme of the invention does not contain chromium element, and the non-ionic surfactant is used as a template agent in the preparation process of the carrier SBA-15 mesoporous molecular sieve, so that the catalyst is environment-friendly;
(3) in the non-noble metal low-carbon alkane dehydrogenation catalyst, the main component of the carrier is SiO2The surface has no acid sites, so that the carbon deposition risk in the reaction process of preparing olefin by dehydrogenating low-carbon alkane can be obviously reduced, and the selectivity of a target product is improved;
(4) the dehydrogenation catalyst shows good catalytic performance when used for preparing olefin by directly dehydrogenating low-carbon alkane, and has high alkane conversion rate, high target product selectivity and good catalyst stability;
(5) the preparation method of the non-noble metal low-carbon alkane dehydrogenation catalyst has the advantages of simple process, easily controlled conditions and good product repeatability.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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.
As described above, the first aspect of the present invention provides a method for preparing a non-noble metal-based low-carbon alkane dehydrogenation catalyst, which comprises the following steps:
(a) under the ultrasonic condition, contacting an all-silicon SBA-15 mesoporous molecular sieve material with an aqueous solution containing sulfate and/or sulfite, and then sequentially removing a solvent, drying and roasting to obtain a modified all-silicon SBA-15 mesoporous molecular sieve carrier;
(b) dipping the modified all-silicon SBA-15 mesoporous molecular sieve carrier obtained in the step (a) in a solution containing an active non-noble metal component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
In the method provided by the invention, in the step (a), the source of the all-silicon SBA-15 mesoporous molecular sieve material is not particularly required, and can be a commercially available all-silicon SBA-15 mesoporous molecular sieve material, or can be prepared by a conventional method to obtain SBA-15, for example, the preparation method of the all-silicon SBA-15 mesoporous molecular sieve preferably comprises the following steps: under the condition of hydrolysis glue making, mixing a template agent, a silicon source and an acidic aqueous solution for hydrolysis glue making to obtain a gel mixture, sequentially crystallizing, filtering and drying the gel mixture obtained after mixing and contacting to obtain the raw powder of the all-silicon SBA-15 mesoporous molecular sieve, and then treating the raw powder of the all-silicon SBA-15 mesoporous molecular sieve with a template agent to obtain the all-silicon SBA-15 mesoporous molecular sieve material.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the molar ratio of the template agent, the silicon source, the acidic substance in the acidic aqueous solution and the water in the acidic aqueous solution is preferably 1: 40-100: 120-400: 6000-10000, more preferably 1: 50-80: 150-300: 7000-9500.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, a template agent used for synthesizing the SBA-15 molecular sieve conventionally can be adopted, for example, the template agent can be a nonionic surfactant, and the template agent is preferably EO with the general formulaaPObEOaThe triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene; more preferably, wherein a has a value of 5 to 140, b has a value of 30 to 100; p123 (EO) is particularly preferred20PO70EO20)、F108(EO132PO50EO132)、P103(EO17PO55EO17) And F127 (EO)106PO70EO106) One or more of (a).
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the silicon source can be organosilicate, and the organosilicate comprises at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and is more preferably tetraethoxysilane and/or tetraethoxysilane.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the selectable range of the molar concentration of the acidic aqueous solution is wide, and preferably, the molar concentration of the solute in the acidic aqueous solution is 0.5-3mol/L, and more preferably 1-2 mol/L. The invention has no special requirements on the type of the acidic aqueous solution, and can be carried out by referring to the prior art, but preferably, the acidic aqueous solution is one or more of hydrochloric acid, sulfuric acid aqueous solution and nitric acid aqueous solution, and more preferably hydrochloric acid aqueous solution.
In the method for preparing the all-silicon SBA-15 mesoporous molecular sieve, the amount of the acidic aqueous solution to be used is not particularly limited, and may be varied within a wide range, and it is preferable that the pH of the contact system is 1 to 6.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the conditions for preparing the gel by hydrolysis can comprise the following steps: the temperature is 20-60 ℃, the time is 12-36h, and more preferably, the conditions for preparing the glue by hydrolysis comprise: the temperature is 30-50 ℃, and the time is 18-30 h;
in the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the crystallization conditions preferably include: the temperature is 70-150 ℃ and the time is 8-72h, and more preferably, the crystallization conditions comprise: the temperature is 80-120 ℃, and the time is 20-30 h. The crystallization is preferably carried out in a hydrothermal kettle.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the conditions of filtering and drying do not have special requirements, and the filtering can be carried out according to a conventional method, and preferably, the filtering process can comprise the following steps: after filtering, repeatedly washing with deionized water (the washing times can be 2-10), and then carrying out suction filtration; the drying temperature is 70-120 ℃, and the drying time is 3-10 h.
In the method for preparing the all-silicon SBA-15 mesoporous molecular sieve, the conditions for the treatment with the mold-releasing agent are preferably performed under the reflux condition of the organic extractant, for example, the conditions for the treatment with the mold-releasing agent may include: extracting the raw powder of the all-silicon SBA-15 mesoporous molecular sieve by using an organic extractant at the temperature of 80-120 ℃ for 5-20 h.
In the preparation method of the all-silicon SBA-15 mesoporous molecular sieve, the organic extractant is preferably at least one of acidified methanol, acidified ethanol and acidified tetrahydrofuran. In the present invention, the acidified methanol refers to a mixture of hydrochloric acid and methanol, and the acidified ethanol refers to a mixture of hydrochloric acid and ethanol, which are known to those skilled in the art and will not be described herein again.
In the method for preparing a non-noble metal-based light alkane dehydrogenation catalyst, in the step (a), the ultrasonic conditions preferably include: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-; more preferably, the ultrasonic conditions comprise: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
In the method for preparing a non-noble metal-based light alkane dehydrogenation catalyst, in the step (a), the sulfate and/or sulfite-containing aqueous solution is preferably used in an amount of 0.05 to 0.15 mol in terms of sulfate and/or sulfite, relative to 100 parts by weight of the all-silicon SBA-15 mesoporous molecular sieve material. For example: the concentration of the aqueous solution containing sulfate and/or sulfite may be 0.02 to 2.0mol/L, preferably 0.1 to 1.0mol/L, and the amount of the aqueous solution containing sulfate and/or sulfite may be 50 to 200mL, preferably 80 to 150 mL.
According to the invention, the sulphate and/or sulphite is preferably at least one of ammonium sulphate, ammonium bisulphate, ammonium sulphite and ammonium bisulphite.
In the method for preparing a non-noble metal-based light alkane dehydrogenation catalyst provided by the present invention, in the step (a), the contacting is preferably performed under stirring conditions, and the stirring conditions in the present invention are not particularly limited and may be conventional conditions in the art.
In the method for preparing a non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (a), the solvent removal treatment can be performed by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
In the method for preparing the non-noble metal-based light alkane dehydrogenation catalyst, in the step (a), the drying can be performed in a drying oven, and the specific implementation conditions can be determined according to the drying conditions conventional in the art, for example, the drying conditions generally include that the drying temperature can be 60-160 ℃, and preferably 80-130 ℃; the drying time may be 1 to 20 hours, preferably 2 to 5 hours.
In the method for preparing the non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (a), the calcination can be performed in a muffle furnace, and the specific implementation conditions can be determined according to calcination conditions conventional in the art, for example, the calcination conditions generally include that the calcination temperature can be 450-; the calcination time may be 2 to 15 hours, preferably 3 to 10 hours.
In the method for preparing the non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (b), the modified all-silicon SBA-15 mesoporous molecular sieve carrier loaded with the active non-noble metal component can adopt an impregnation mode, the active non-noble metal component enters the pore channel of the modified all-silicon SBA-15 mesoporous molecular sieve carrier by virtue of capillary pressure of the pore channel structure of the carrier, and meanwhile, the active non-noble metal component can be adsorbed on the surface of the modified all-silicon SBA-15 mesoporous molecular sieve carrier until the active non-noble metal component reaches adsorption balance on the surface of the carrier. The conditions of the impregnation treatment preferably include: mixing and contacting the modified all-silicon SBA-15 mesoporous molecular sieve carrier with a solution containing an active non-noble metal component precursor, wherein the impregnation temperature can be 25-50 ℃, and the impregnation time can be 2-6 h.
In the method for preparing the non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (b), the modified all-silicon SBA-15 mesoporous molecular sieve and the solution containing the active non-noble metal component precursor are preferably used in amounts such that the content of the active non-noble metal component in the prepared non-noble metal-based low-carbon alkane dehydrogenation catalyst is 2-40 wt%, preferably 3-30 wt%, based on the total weight of the non-noble metal-based low-carbon alkane dehydrogenation catalyst; the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is 60-98 wt%, and preferably 70-97 wt%.
In the method for preparing the non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (b), the solution containing the active non-noble metal component precursor is preferably at least one of soluble salt solutions of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper.
According to the present invention, the concentration of the soluble salt of the active non-noble metal component in the solution containing the precursor of the active non-noble metal component is not particularly limited, and for example, the concentration of the soluble salt of the active non-noble metal component in the solution containing the precursor of the active non-noble metal component may be 0.04 to 0.25 mol/L. The soluble salt in the present invention preferably means a water-soluble salt.
According to the invention, when the concentration of the solution containing the active non-noble metal component precursor is in the above range, the amount of the solution containing the active non-noble metal component precursor can be 50-150 mL.
According to the invention, the sulfate and/or sulfite modified all-silicon SBA-15 mesoporous molecular sieve carrier obtained by the method can dissolve the amorphous phase in the molecular sieve pore channel, simultaneously reduces the channel resistance along with the formation of internal silanol groups, improves the relative crystallinity and hydrothermal stability of the obtained modified all-silicon SBA-15 mesoporous molecular sieve carrier, can also improve the specific combination effect of the all-silicon SBA-15 mesoporous molecular sieve material and the active non-noble metal component after loading the active non-noble metal component, leads the non-noble metal component and the sulfur element existing in the modified all-silicon SBA-15 mesoporous molecular sieve carrier to form sulfide, effectively prevents the active non-noble metal component from being deeply reduced and converted into pure metal in the catalytic process, and inhibits side reactions such as hydrogenolysis and the like in the dehydrogenation process, and further, the catalytic activity of the obtained dehydrogenation catalyst and the selectivity of a target dehydrogenation product are improved, so that in the non-noble metal dehydrogenation catalyst, the modified all-silicon SBA-15 mesoporous molecular sieve carrier only loads iron, nickel, zinc, molybdenum, tungsten, manganese, tin, copper and respective oxide active components thereof to obtain higher catalytic activity, and is particularly suitable for dehydrogenation reaction of low-carbon alkane.
According to the present invention, in the non-noble metal-based low-carbon alkane dehydrogenation catalyst, the content of the active non-noble metal component in terms of the active metal element oxide is preferably 2 to 40 wt%, and more preferably 3 to 30 wt%, based on the total weight of the non-noble metal-based low-carbon alkane dehydrogenation catalyst; the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is preferably 60-98 wt%, and more preferably 70-97 wt%.
According to the present invention, in the non-noble metal-based low-carbon alkane dehydrogenation catalyst, the active non-noble metal component is at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, copper, and oxides thereof.
In the method for preparing a non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (b), the solvent removal treatment can be performed by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
In the method for preparing a non-noble metal-based low-carbon alkane dehydrogenation catalyst, in the step (b), the drying may be performed in a drying oven, and the calcination may be performed in a muffle furnace. The drying conditions may include: the temperature is 60-160 ℃, preferably 80-130 ℃, and the time is 1-20h, preferably 2-5 h; the conditions for the firing may include: the temperature is 450-700 ℃, preferably 500-650 ℃, and the time is 2-15h, preferably 3-10 h.
The invention provides a non-noble metal-based low-carbon alkane dehydrogenation catalyst prepared by the method.
The third aspect of the invention also provides a non-noble metal-based low-carbon alkane dehydrogenation catalyst, which comprises a carrier and an active non-noble metal component loaded on the carrier, wherein the active non-noble metal component is a non-noble metal and/or a non-noble metal oxide, the carrier is a modified all-silicon SBA-15 mesoporous molecular sieve carrier, and the specific surface area of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is 600-950m2(iii) a pore volume of 0.8 to 1.5 mL/g.
Preferably, the specific surface area of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is 650-1000m2(iii) a pore volume of 0.8 to 1.2 mL/g.
In the non-noble metal based low-carbon alkane dehydrogenation catalyst provided by the invention, the content of the active non-noble metal component calculated by the active metal element oxide is 2-40 wt%, preferably 3-30 wt% based on the total weight of the non-noble metal based low-carbon alkane dehydrogenation catalyst; the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is 60-98 wt%, and preferably 70-97 wt%.
In the non-noble metal based low-carbon alkane dehydrogenation catalyst provided by the invention, the active non-noble metal component is at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, copper and oxides thereof.
The fourth aspect of the present invention provides a method for preparing a low carbon olefin by dehydrogenating a low carbon alkane, the method comprising: and carrying out dehydrogenation reaction on the low-carbon alkane in the presence of a catalyst and inert gas, wherein the catalyst is the non-noble metal low-carbon alkane dehydrogenation catalyst.
According to the method for preparing the low-carbon olefin by the dehydrogenation of the low-carbon alkane provided by the invention, the low-carbon alkane refers to a straight-chain or branched-chain alkane with the carbon atom number of 1-4, correspondingly, the low-carbon olefin is a straight-chain or branched-chain monoolefin with the carbon atom number of 1-4, preferably, the low-carbon alkane is propane or isobutane, and correspondingly, the low-carbon olefin is propylene or isobutene. The conditions for dehydrogenation reaction of the low-carbon alkane preferably comprise: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the low-carbon alkane is 1-10h-1。
According to a preferred embodiment of the present invention, when the lower alkane is propane, it is preferable to add an inert gas as a diluent to the reaction raw material to reduce the partial pressure of propane in the reaction system in order to increase the conversion of propane and prevent coking of the catalyst. Wherein the inert gas comprises at least one of nitrogen, helium and argon. The molar ratio of the amount of propane to the amount of inert gas is 0.2-5: 1. the conditions of the dehydrogenation reaction may include: the reaction temperature is 600-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 40-60h, and the propane mass space velocity is 2-5h-1。
According to another preferred embodiment of the present invention, when the low-carbon alkane is isobutane, in order to increase the isobutane conversion rate and prevent the catalyst from coking, an inert gas is preferably added to the reaction raw material as a diluent to reduce the partial pressure of isobutane in the reaction system. Wherein the inert gas comprises at least one of nitrogen, helium and argon. The molar ratio of the consumption of the isobutane to the consumption of the inert gas is 0.2-5.0: 1. the conditions of the dehydrogenation reaction may include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, available from Aldrich, is abbreviated as P123 and has the formula EO20PO70EO20The substance having a registration number of 9003-11-6 in the American chemical Abstract had an average molecular weight Mn of 5800.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on an ASAP2020-M + C type adsorption apparatus, available from Micromeritics, USA, and the sample was degassed at 350 ℃ in vacuum for 4 hours before measurement, and the BET method was used to calculate the specific surface area of the sample, and the BJH model was used to calculate the pore volume; the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A; the muffle furnace is manufactured by CARBOLITE corporation, and is of a model CWF 1100; the ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component load capacity of the low-carbon alkane dehydrogenation catalyst is measured on a wavelength dispersion X-ray fluorescence spectrometer which is purchased from Parnacidae, Netherlands and has the model of Axios-Advanced; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
In the following experimental examples and experimental comparative examples, the conversion (%) of low-carbon alkane is ═ (amount of low-carbon alkane used-content of low-carbon alkane in the reaction product) ÷ amount of low-carbon alkane used × 100%;
selectivity (%) of the low carbon olefin is the amount of low carbon alkane consumed to produce the low carbon olefin ÷ total consumption of the low carbon alkane × 100%.
Example 1
(1) Preparation of all-silicon SBA-15 molecular sieve
Adding 24.0g of nonionic surfactant P123 into 600g of hydrochloric acid aqueous solution with the concentration of 2mol/L, and stirring at 35 ℃ for 1 hour; adding 51.2g of tetraethoxysilane into the solution, and stirring for 24 hours at 35 ℃; transferring the mixture to a hydrothermal kettle, and carrying out hydrothermal crystallization at 100 ℃ for 24 hours. And after the hydrothermal reaction is finished, separating the solid product from the mother liquor, washing the solid product to be neutral by using deionized water, and drying the solid product for 3 hours at the temperature of 110 ℃ to obtain the all-silicon SBA-15 raw powder. Mixing 20.0g of all-silicon SBA-15 raw powder with 200ml of acidified methanol (the volume ratio of the methanol to the concentrated hydrochloric acid is 20: 1), extracting under reflux at 80 ℃ for 10 hours, filtering, washing, and drying under vacuum at 120 ℃ for 3 hours to obtain the all-silicon SBA-15 molecular sieve.
(2) Modification of full-silicon SBA-15 mesoporous molecular sieve
10.0g of the all-silicon SBA-15 molecular sieve obtained in the above step was mixed with 100ml of an aqueous ammonium sulfate solution having a concentration of 0.5mol/L, and stirred and reacted for 60 minutes with the aid of ultrasonic waves having a power of 200W at a temperature of 50 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 5 hours. Then roasting the mixture for 5 hours in a muffle furnace at the temperature of 550 ℃ to obtain the modified all-silicon SBA-15 mesoporous molecular sieve carrier S1.
(3) Preparation of non-noble metal low-carbon alkane dehydrogenation catalyst
3.25g of iron sulfate (Fe)2(SO4)3) Dissolving in 100ml deionized water, mixing with 10g of modified all-silicon SBA-15 mesoporous molecular sieve carrier S1 prepared in the step (1), and continuously stirring and reacting for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 110 ℃ for 3 hours. And then roasting the mixture for 6 hours in a muffle furnace at the temperature of 550 ℃ to obtain the non-noble metal low-carbon alkane dehydrogenation catalyst Cat-1. The specific surface area of the catalyst Cat-1 is 642m2Pore volume was 1.05 mL/g.
Measured by an X-ray fluorescence spectrometer, in the non-noble metal propane dehydrogenation catalyst Cat-1, the iron component is iron oxide (Fe) based on the total weight of the Cat-12O3) The content of the modified all-silicon SBA-15 mesoporous molecular sieve is 11.5 weight percentThe content of carrier S1 was 88.5 wt%.
Example 2
(1) Preparation of all-silicon SBA-15 molecular sieve
Adding 30.6g of nonionic surfactant P123 into 400g of hydrochloric acid aqueous solution with the concentration of 1mol/L, and stirring for 1 hour at 40 ℃; 40.1g of methyl orthosilicate was added dropwise to the above solution, and stirred at 40 ℃ for 24 hours; transferring the mixture to a hydrothermal kettle, and carrying out hydrothermal crystallization at 100 ℃ for 24 hours. And after the hydrothermal reaction is finished, separating the solid product from the mother liquor, washing the solid product to be neutral by using deionized water, and drying the solid product for 3 hours at the temperature of 110 ℃ to obtain the all-silicon SBA-15 raw powder. Mixing 20.0g of all-silicon SBA-15 raw powder with 200g of tetrahydrofuran, carrying out reflux extraction at 70 ℃ for 6 hours, then filtering, washing and carrying out vacuum drying at 120 ℃ for 3 hours to obtain the all-silicon SBA-15 molecular sieve.
(2) Modification of full-silicon SBA-15 mesoporous molecular sieve
10.0g of the all-silicon SBA-15 molecular sieve obtained in the above step was mixed with 150ml of an aqueous ammonium sulfite solution having a concentration of 0.1mol/L, and stirred and reacted for 30 minutes with the aid of ultrasonic waves having a power of 250W at a temperature of 80 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 130 ℃ for 3 hours. Then roasting the mixture for 3 hours in a muffle furnace at the temperature of 650 ℃ to obtain the modified all-silicon SBA-15 mesoporous molecular sieve carrier S2.
(3) Preparation of non-noble metal low-carbon alkane dehydrogenation catalyst
1.06g of nickel sulfate hexahydrate is dissolved in 100ml of deionized water, and is mixed with 10g of modified SBA-15 mesoporous molecular sieve carrier S2 prepared in the step (1), and the mixture is continuously stirred and reacted for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 130 ℃ and dried for 2 hours. Then roasting the mixture for 3 hours in a muffle furnace at the temperature of 650 ℃ to obtain the non-noble metal low-carbon alkane dehydrogenation catalyst Cat-2. The specific surface area of the catalyst Cat-2 was 618m2Pore volume was 0.98 mL/g.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal propane dehydrogenation catalyst Cat-2, the content of a nickel component in terms of nickel oxide (NiO) is 3 wt% and the content of a modified all-silicon SBA-15 mesoporous molecular sieve carrier S2 is 97 wt% based on the total weight of the Cat-2.
Example 3
(1) Preparation of all-silicon SBA-15 molecular sieve
16.0g of nonionic surfactant P123 was added to 800g of a 1.5M aqueous hydrochloric acid solution, and stirred at 40 ℃ for 1 hour; 34.9g of water glass (SiO)2Content 28.26 wt.%) was added to the above solution and stirred at 40 ℃ for 24 hours; transferring the mixture to a hydrothermal kettle, and carrying out hydrothermal crystallization at 100 ℃ for 24 hours. And after the hydrothermal reaction is finished, separating the solid product from the mother liquor, washing the solid product to be neutral by using deionized water, and drying the solid product for 3 hours at the temperature of 110 ℃ to obtain the all-silicon SBA-15 raw powder. Mixing 20.0g of all-silicon SBA-15 raw powder with 200ml of acidified ethanol (the volume ratio of ethanol to concentrated hydrochloric acid is 20: 1), extracting under reflux at 90 ℃ for 18 hours, filtering, washing, and drying under vacuum at 120 ℃ for 3 hours to obtain the all-silicon SBA-15 molecular sieve.
(2) Modification of full-silicon SBA-15 mesoporous molecular sieve
10.0g of the all-silicon SBA-15 molecular sieve obtained in the above step was mixed with 80ml of an aqueous ammonium bisulfate solution having a concentration of 1.0mol/L, and stirred and reacted for 120 minutes with the aid of ultrasonic waves having a power of 150W at a temperature of 20 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 80 ℃ for 10 hours. Then roasting the mixture in a muffle furnace at the temperature of 500 ℃ for 12 hours to obtain the modified all-silicon SBA-15 mesoporous molecular sieve carrier S3.
(3) Preparation of non-noble metal low-carbon alkane dehydrogenation catalyst
7.28g of zinc nitrate hexahydrate is dissolved in 100ml of deionized water, and is mixed with 10g of the modified all-silicon SBA-15 mesoporous molecular sieve carrier S3 prepared in the step (1), and the mixture is continuously stirred and reacted for 5 hours at room temperature. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 80 ℃ for 5 hours. Then roasting the mixture for 10 hours in a muffle furnace at the temperature of 500 ℃ to obtain non-noble metal low-carbon alkane dehydrogenationCatalyst Cat-3. The specific surface area of the catalyst Cat-3 is 587m2Pore volume was 0.86 mL/g.
Measured by an X-ray fluorescence spectrometer, in the non-noble metal propane dehydrogenation catalyst Cat-3, based on the total weight of the Cat-3, the content of a zinc component (calculated by zinc oxide (ZnO)) is 16.6 wt%, and the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier S3 is 83.4 wt%.
Comparative example 1
A non-noble metal-based light alkane dehydrogenation catalyst Cat-D1 was prepared according to the method of example 1, except that the ultrasonic dispersion in step (2) was eliminated.
Comparative example 2
A non-noble metal-based light alkane dehydrogenation catalyst Cat-D2 was prepared according to the method of example 1 except that step (2) was eliminated.
Comparative example 3
A lower alkane dehydrogenation catalyst Cat-D3 was prepared according to the method of example 2, except that in step (2), 0.8g of chromium sulfate (Cr)2(SO4)3) Replacing the nickel sulfate hexahydrate, namely, taking an active component loaded by the modified all-silicon SBA-15 mesoporous molecular sieve carrier S2 as a noble metal Cr component to obtain the low-carbon alkane dehydrogenation catalyst Cat-D3.
The chromium component is chromium oxide (Cr) in the low-carbon alkane dehydrogenation catalyst Cat-D3 by the determination of an X-ray fluorescence spectrometer, wherein the total weight of the Cat-D3 is taken as a reference2O3) The content is 3 wt%, and the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier S2 is 97 wt%.
Test example 1
Test of performance of low-carbon alkane dehydrogenation catalyst in reaction for preparing propylene by propane dehydrogenation
0.5g of the low-carbon alkane dehydrogenation catalysts prepared in the above examples and comparative examples were respectively charged into a fixed bed quartz reactor, and the reaction temperature was controlled at 600 ℃, the reaction pressure was 0.1MPa, and the ratio of propane: the molar ratio of helium is 1: 1, the mass space velocity of propane is 5.0h-1The reaction time is 6 h. By Al2O3Reaction product separated by-S molecular sieve column is directly usedThe sample was subjected to on-line analysis by an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID). And calculating the conversion rate of propane and the selectivity of propylene according to the reaction data, and judging the stability of the catalyst according to the gradual reduction amplitude of the conversion rate of propane and the selectivity of propylene along with the prolonging of the reaction time in the reaction process.
The test results are shown in Table 1.
TABLE 1
Test example 2
Test of performance of low-carbon alkane dehydrogenation catalyst in reaction for preparing isobutene through isobutane dehydrogenation
0.5g of the low-carbon alkane dehydrogenation catalysts prepared in the above examples and comparative examples were respectively loaded into a fixed bed quartz reactor, the reaction temperature was controlled to 580 ℃, the reaction pressure was 0.1MPa, and the reaction pressure was controlled to be isobutane: the molar ratio of helium is 1: 1, the mass space velocity of the isobutane is 2.0h-1The reaction time is 6 h. By Al2O3The reaction product separated by the S molecular sieve column directly enters an Agilent 7890A gas chromatograph provided with a hydrogen flame detector (FID) for on-line analysis. And (3) calculating the isobutane conversion rate and the isobutene selectivity according to the reaction data, and judging the stability of the catalyst according to the gradual reduction amplitude of the isobutane conversion rate and the isobutene selectivity along with the prolonging of the reaction time in the reaction process.
The test results are shown in Table 2.
TABLE 2
The results in table 1 show that, when the dehydrogenation catalyst Cat-1 prepared by using the modified all-silicon SBA-15 mesoporous molecular sieve as the carrier is used for propylene preparation through propane dehydrogenation, the catalytic performance of the dehydrogenation catalyst Cat-1 is obviously superior to that of the catalyst Cat-D2 prepared by using the unmodified all-silicon SBA-15 mesoporous molecular sieve as the carrier, the propane conversion rate and the propylene selectivity are obviously improved, and the catalyst stability is also obviously improved. In addition, the experimental results of comparative test example 1 and test examples 1-D1 show that the modified all-silicon SBA-15 mesoporous molecular sieve carrier with better performance can be obtained by adopting an ultrasonic auxiliary method in the modification process of the all-silicon SBA-15 mesoporous molecular sieve, and further the dehydrogenation catalyst with better performance can be obtained. In addition, the experimental results of the comparative test example 1 and the test examples 1 to D3 show that the low-carbon alkane dehydrogenation catalyst obtained by loading the non-noble metal active component on the modified all-silicon SBA-15 mesoporous molecular sieve carrier has equivalent catalytic performance when catalyzing propane dehydrogenation to the low-carbon alkane dehydrogenation catalyst obtained by loading the toxic metal active component Cr on the modified all-silicon SBA-15 mesoporous molecular sieve carrier.
Similarly, it can be seen from the results in table 2 that the method for preparing the non-noble metal-based low-carbon alkane dehydrogenation catalyst provided by the invention can also effectively improve the activity, selectivity and stability of the catalyst in the reaction of preparing isobutene by dehydrogenating isobutane. By comparing the experimental results of test example 2 and test examples 2-D3, it can be found that the low-carbon alkane dehydrogenation catalyst obtained by loading the non-noble metal active component on the modified all-silicon SBA-15 mesoporous molecular sieve carrier has equivalent catalytic performance when catalyzing isobutane to dehydrogenate as compared with the low-carbon alkane dehydrogenation catalyst obtained by loading the toxic metal active component Cr on the modified all-silicon SBA-15 mesoporous molecular sieve carrier.
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. A method for preparing a non-noble metal-based low-carbon alkane dehydrogenation catalyst is characterized by comprising the following steps of:
(a) under the ultrasonic condition, contacting an all-silicon SBA-15 mesoporous molecular sieve material with an aqueous solution containing sulfate and/or sulfite, and then sequentially removing a solvent, drying and roasting to obtain a modified all-silicon SBA-15 mesoporous molecular sieve carrier;
(b) dipping the modified all-silicon SBA-15 mesoporous molecular sieve carrier obtained in the step (a) in a solution containing an active non-noble metal component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
2. The process of claim 1, wherein in step (a), the all-silicon SBA-15 mesoporous molecular sieve is prepared by a process comprising: under the condition of hydrolysis glue making, carrying out hydrolysis glue making on a template agent, a silicon source and an acidic aqueous solution to obtain a gel mixture, sequentially crystallizing, filtering and drying the gel mixture obtained after mixing and contacting to obtain the raw powder of the all-silicon SBA-15 mesoporous molecular sieve, and then carrying out template agent treatment on the raw powder of the all-silicon SBA-15 mesoporous molecular sieve to obtain the all-silicon SBA-15 mesoporous molecular sieve material.
3. The method of claim 2, wherein the templating agent, the silicon source, the acidic species in the acidic aqueous solution, and the water in the acidic aqueous solution are used in a molar ratio of 1: 40-100: 120-400: 6000-10000, more preferably 1: 50-80: 150-300: 7000-9500;
preferably, the template agent is triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, and the silicon source comprises at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and is more preferably methyl orthosilicate and/or ethyl orthosilicate;
further preferably, the conditions for preparing the glue by hydrolysis comprise: the temperature is 20-60 ℃, the time is 12-36h, and more preferably, the conditions for preparing the glue by hydrolysis comprise: the temperature is 30-50 ℃, and the time is 18-30 h;
further preferably, the crystallization conditions include: the temperature is 70-150 ℃ and the time is 8-72h, and more preferably, the crystallization conditions comprise: the temperature is 80-120 ℃, and the time is 20-30 h;
further preferably, the conditions of the stripper plate agent treatment include: and extracting the raw powder of the all-silicon SBA-15 mesoporous molecular sieve by using an organic extraction solvent at the temperature of 80-120 ℃ for 5-20 h.
4. The method of claim 1, wherein in step (a), the ultrasound conditions comprise: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-;
preferably, the ultrasound conditions comprise: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-;
preferably, the aqueous solution containing sulfate and/or sulfite is used in an amount of 0.05 to 0.15 mole in terms of sulfate and/or sulfite with respect to 100 parts by weight of the all-silicon SBA-15 mesoporous molecular sieve material;
more preferably, the sulfate and/or sulfite is at least one of ammonium sulfate, ammonium bisulfate, ammonium sulfite, and ammonium bisulfite.
5. The process of claim 1, wherein, in step (b), the modified all-silicon SBA-15 mesoporous molecular sieve and the solution containing the active non-noble metal component precursor are used in amounts such that the non-noble metal-based light alkane dehydrogenation catalyst is prepared in an amount of from 2 to 40 wt%, preferably from 3 to 30 wt%, based on the total weight of the non-noble metal-based light alkane dehydrogenation catalyst, of the active non-noble metal component; the content of the modified all-silicon SBA-15 mesoporous molecular sieve carrier is 60-98 wt%, and preferably 70-97 wt%.
6. The method of claim 1 or 5, wherein the solution containing precursors of active non-noble metal components is at least one of a soluble salt solution of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, and copper.
7. A non-noble metal-based light alkane dehydrogenation catalyst prepared by the process of any of claims 1-6.
8. The non-noble metal-based light alkane dehydrogenation catalyst of claim 7, wherein the active non-noble metal component is at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, copper, and their respective oxides.
9. A method for preparing low-carbon olefin by dehydrogenating low-carbon alkane comprises the following steps: in the presence of a catalyst, carrying out dehydrogenation reaction on the low-carbon alkane, wherein the catalyst is the non-noble metal-based low-carbon alkane dehydrogenation catalyst according to claim 7 or 8.
10. The method of claim 9, wherein the lower alkane is propane and/or isobutane and the dehydrogenation reaction conditions of the lower alkane comprise: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the low-carbon alkane is 1-10h-1。
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Application publication date: 20191227