CN111250111A - Non-noble metal isobutane dehydrogenation catalyst with eggshell-shaped mesoporous material as carrier and preparation method and application thereof - Google Patents
Non-noble metal isobutane dehydrogenation catalyst with eggshell-shaped mesoporous material as carrier and preparation method and application thereof Download PDFInfo
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- CN111250111A CN111250111A CN201811459533.0A CN201811459533A CN111250111A CN 111250111 A CN111250111 A CN 111250111A CN 201811459533 A CN201811459533 A CN 201811459533A CN 111250111 A CN111250111 A CN 111250111A
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- China
- Prior art keywords
- noble metal
- eggshell
- dehydrogenation catalyst
- mesoporous material
- isobutane dehydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J35/615—
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- B01J35/635—
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- B01J35/638—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
Abstract
The invention relates to the field of catalysts, and discloses a non-noble metal isobutane dehydrogenation catalyst, and a preparation method and application thereof. The method for preparing the non-noble metal isobutane dehydrogenation catalyst comprises the following steps: (a) providing raw powder of eggshell-shaped mesoporous material; (b) carrying out template agent treatment on the eggshell-shaped mesoporous material raw powder to obtain an eggshell-shaped mesoporous material carrier; (c) under the ultrasonic condition, loading a first active non-noble metal component and a second active non-noble metal component on the eggshell-shaped mesoporous material carrier to obtain an initial non-noble metal isobutane dehydrogenation catalyst; (d) and carrying out sulfidation treatment on the initial non-noble metal isobutane dehydrogenation catalyst by using sulfur-containing gas. The obtained non-noble metal isobutane dehydrogenation catalyst has better dehydrogenation activity, selectivity and stability.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a non-noble metal isobutane dehydrogenation catalyst with a eggshell-shaped mesoporous material as a carrier, the non-noble metal isobutane dehydrogenation catalyst prepared by the method, and application of the non-noble metal isobutane dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from an apparatus for producing ethylene by steam cracking of naphtha, the by-product C4 fraction from a refinery Fluid Catalytic Cracking (FCC) apparatus, and the by-product tert-butyl alcohol (TAB) in the synthesis of propylene oxide by the Halcon method.
In recent years, with the development and utilization of downstream products of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of the chemical industry on isobutene, so the research and development work of a new isobutene production technology becomes a hot spot of the chemical industry. Among the most competitive technologies, isobutane dehydrogenation, n-butene skeletal isomerization and isobutene production by a novel FCC unit are known. Among the methods, the research on the reaction for preparing isobutene by directly dehydrogenating isobutane is early, and the industrial production is realized. China has abundant C4 resources, but the chemical utilization rate of C4 fraction is low in China, most of isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resource is an urgent task in the petrochemical research field. Therefore, the isobutene prepared by dehydrogenating isobutane has a great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly comprise two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr2O3、V2O5、Fe2O3、MoO3ZnO, etc., and a composite oxide thereof, such as V-Sb-O, V-Mo-O, Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate, etc. Compared with noble metal catalysts, oxide catalysts are less expensive. However, the catalyst is easy to deposit carbon, and the catalytic activity, selectivity and stability are low. In addition, most oxide catalysts contain components with high toxicity, which is not favorable for environmental protection. The research on dehydrogenation reactions on noble metal catalysts has a long history, and noble metal catalysts have higher activity, better selectivity, and are more environmentally friendly than other metal oxide catalysts. However, the catalyst cost is high due to the expensive price of noble metals, and the performance of such catalysts has not yet reached a satisfactory level.
In order to improve the reaction performance of the catalyst for preparing isobutene by isobutane dehydrogenation, researchers have done a lot of work. Such as: the catalyst performance is improved by changing the preparation method of the catalyst (industrial catalysis, 2014, 22(2): 148-. However, the specific surface area of the currently used carrier is small, which is not beneficial to the dispersion of the active metal component on the surface of the carrier, and is also not beneficial to the diffusion of raw materials and products in the reaction process.
Therefore, until now, the development of a non-noble metal isobutane dehydrogenation catalyst with high activity, good stability and environmental friendliness has become a problem to be solved in the production field of isobutene preparation by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of high preparation cost and easy environmental pollution of non-noble metal isobutane dehydrogenation catalysts in the prior art, and provides a non-noble metal isobutane dehydrogenation catalyst, and a preparation method and application thereof.
In order to achieve the above object, an aspect of the present invention provides a method for preparing a non-noble metal-based isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) under the condition of solution, mixing and contacting a template agent with trimethylpentane and tetramethoxysilane to obtain solution A, and sequentially crystallizing, filtering and drying the solution A to obtain eggshell-shaped mesoporous material raw powder;
(b) carrying out template agent treatment on the eggshell-shaped mesoporous material raw powder to obtain an eggshell-shaped mesoporous material carrier;
(c) under the ultrasonic condition, carrying out dipping treatment on a eggshell-shaped mesoporous material carrier and a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(d) and carrying out sulfidation treatment on the initial non-noble metal isobutane dehydrogenation catalyst by using sulfur-containing gas.
The invention provides a non-noble metal isobutane dehydrogenation catalyst with a eggshell-shaped mesoporous material as a carrier, which is prepared by the method.
The third aspect of the invention provides an application of the non-noble metal isobutane dehydrogenation catalyst prepared by the method in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the following steps: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst.
The inventor of the invention finds that in the prior art, when the preparation research of the isobutane dehydrogenation catalyst is carried out, the defects of poor olefin selectivity and poor stability exist when the dehydrogenation catalyst is prepared by taking gamma-alumina or silicon oxide as a carrier and loading a non-noble metal component. If the non-noble metal catalyst is subjected to sulfurization treatment, S elements exist on the surface of the catalyst, and the S elements can be combined with active metal components in the reducing atmosphere of dehydrogenation reaction to generate sulfides. The existence of the non-noble metal sulfide can effectively avoid deep reduction of metal components, thereby reducing pure metal components on the surface of the catalyst and obviously inhibiting side reactions such as hydrogenolysis and the like. The selectivity and stability of the dehydrogenation catalyst after vulcanization treatment in the reaction of preparing isobutene by isobutane dehydrogenation are obviously improved. For non-noble metal alkane dehydrogenation catalysts, the S element content on the surface of the catalyst has a significant effect on the performance of the catalyst. If the S content is too low, the protection effect on the active metal component is limited, and the partially oxidized metal component is still completely reduced to be in a pure metal state in the reaction process; if the S content is too high, the "oxidation-reduction" cycle rate of the active sites on the surface of the catalyst is slowed, resulting in a slower reaction rate, which is manifested by lower catalyst activity.
In addition, the inventor of the present invention also finds that, in the preparation process of the non-noble metal isobutane dehydrogenation catalyst provided by the present invention, an ultrasonic auxiliary method is introduced to promote the active components to be better dispersed on the surface of the mesoporous carrier, so as to obtain the non-noble metal isobutane dehydrogenation catalyst with better catalytic activity.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the non-noble metal isobutane dehydrogenation catalyst does not contain noble metals, so that the preparation cost of the dehydrogenation catalyst can be effectively reduced;
(2) the non-noble metal isobutane dehydrogenation catalyst provided by the preferred scheme of the invention does not contain chromium, and is environment-friendly;
(3) in the non-noble metal isobutane dehydrogenation catalyst, the main component of the carrier is SiO2The surface has no acid sites, and the carbon deposition in the reaction process of preparing olefin by dehydrogenating low-carbon alkane can be obviously reducedRisks and improves the selectivity of the target product;
(4) the dehydrogenation catalyst shows good catalytic performance when used for preparing isobutene by directly dehydrogenating isobutane, and has high alkane conversion rate, high target product selectivity and good catalyst stability;
(5) the preparation method of the non-noble metal isobutane dehydrogenation catalyst is simple in process, easy to control conditions and good in product repeatability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD spectrum of a eggshell-shaped mesoporous material carrier C1 of example 1;
FIG. 2A is a graph showing the pore size distribution of the eggshell-shaped mesoporous material carrier C1 of example 1;
FIG. 2B is a nitrogen desorption isotherm of the eggshell-shaped mesoporous material carrier C1 of example 1;
FIG. 3A is a scanning electron micrograph (magnification 500K) of an eggshell-shaped mesoporous material carrier C1 of example 1;
FIG. 3B is a scanning electron micrograph (magnification 3000K) of an eggshell-shaped mesoporous material carrier C1 of example 1.
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.
As described above, the first aspect of the present invention provides a method for preparing a non-noble metal-based isobutane dehydrogenation catalyst, comprising the steps of:
(a) under the condition of solution, mixing and contacting a template agent with trimethylpentane and tetramethoxysilane to obtain solution A, and sequentially crystallizing, filtering and drying the solution A to obtain eggshell-shaped mesoporous material raw powder;
(b) carrying out template agent treatment on the eggshell-shaped mesoporous material raw powder to obtain an eggshell-shaped mesoporous material carrier;
(c) under the ultrasonic condition, carrying out dipping treatment on a eggshell-shaped mesoporous material carrier and a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(d) and carrying out sulfidation treatment on the initial non-noble metal isobutane dehydrogenation catalyst by using sulfur-containing gas.
According to the invention, in step (a), the conditions of the mixing contact comprise: the temperature is 10-60 ℃, the time is 0.2-100h, and the pH is 1-6; the pH can be established, for example, by adding hydrochloric acid. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions.
According to the present invention, in the step (a), the solution condition may be an aqueous solution condition. Preferably, to facilitate the dissolution of the templating agent, a buffered solution of acetic acid and sodium acetate at a pH of 1-6 may be used to create solution conditions, and, for example, an alcoholic reagent (e.g., methanol, ethanol, n-propanol, isopropanol, etc.) is added.
Preferably, the weight ratio of the template, the trimethylpentane and the tetramethoxysilane is 1: (1.2-20): (0.1-15); more preferably 1: (2-12): (0.5-10).
According to the present invention, in step (a), the template is preferably selected such that the obtained raw powder of eggshell-shaped mesoporous material has a two-dimensional hexagonal pore channel distribution structure, for example, the template can be triblock copolymer polyethylene glycol-polyGlycerol-polyethylene glycol. Wherein the templating agent is commercially available (e.g., from Aldrich under the trade name P123, formula EO)20PO70EO20) It can also be prepared by various conventional methods. When the template agent is polyethylene glycol-polyglycerol-polyethylene glycol, the mole number of the template agent is calculated according to the average molecular weight of the polyethylene glycol-polyglycerol-polyethylene glycol.
Preferably, in step (a), the crystallization conditions include: the temperature is 30-150 ℃ and the time is 4-72 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
Preferably, in step (a), the filtering may include: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration.
Preferably, in step (a), the drying may be performed in a drying oven. The drying conditions may include: the temperature is 110-150 ℃ and the time is 3-6 h.
According to a preferred embodiment of the present invention, in step (a), the method of performing the mixing contact comprises: under the condition of solution, firstly, a template agent is in first contact with trimethylpentane; and then carrying out second contact on the mixture obtained after the first contact and tetramethoxysilane.
Preferably, the conditions of the first contacting include: the temperature is 10-60 deg.C, the time is 0.1-20h, and the pH value is 1-6.
Preferably, the conditions of the second contacting include: the temperature is 10-60 deg.C, the time is 0.1-80h, and the pH value is 1-6.
According to the present invention, in the step (b), the template removal treatment comprises: calcining the eggshell-shaped mesoporous material raw powder at the temperature of 300-600 ℃; preferably, the calcination time is 8-36 h.
According to the present invention, in step (c), the eggshell-shaped mesoporous material carrier supporting the first active non-noble metal component and the second active non-noble metal component may adopt an impregnation manner, and the first active non-noble metal component and the second active non-noble metal component enter the pore channel of the eggshell-shaped mesoporous material carrier depending on the capillary pressure of the pore channel structure of the carrier, and at the same time, the first active non-noble metal component and the second active non-noble metal component may be adsorbed on the surface of the eggshell-shaped mesoporous material carrier until the first active non-noble metal component and the second active non-noble metal component reach adsorption equilibrium on the surface of the carrier. The dipping treatment may be a co-dipping treatment or a stepwise dipping treatment.
When the impregnation treatment is a co-impregnation treatment, the conditions of the co-impregnation treatment preferably include: under the condition of ultrasonic assistance, the eggshell-shaped mesoporous material carrier is mixed and contacted with a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, the impregnation temperature can be 10-100 ℃, and the impregnation time can be 30-120 min.
When the impregnation treatment is a stepwise impregnation treatment, the conditions of the impregnation treatment preferably include: under the condition of ultrasonic assistance, firstly, carrying out first mixing contact on an eggshell-shaped mesoporous material carrier and a solution containing a first active non-noble metal component precursor, and then sequentially carrying out solvent removal, drying and roasting to obtain the eggshell-shaped mesoporous material carrier loaded with a first metal component; and then carrying out second mixing contact on the eggshell-shaped mesoporous material carrier loaded with the first metal component and a solution containing a precursor of a second active non-noble metal component, and then sequentially removing the solvent, drying and roasting to obtain the eggshell-shaped mesoporous material carrier loaded with the first metal component and the second active non-noble metal component, namely the initial isobutane catalyst. The sequence of the step-by-step dipping treatment can also be adjusted to load the second active non-noble metal component by dipping the eggshell-shaped mesoporous material carrier, and then load the first active non-noble metal component by dipping. In the step impregnation treatment, the conditions of each impregnation treatment may include: the soaking temperature is 10-100 deg.C, and the soaking time is 30-120 min.
In the method for preparing a non-noble metal-based isobutane dehydrogenation catalyst provided by the present invention, in step (c), in order to promote uniform dispersion of the first active non-noble metal component and the second active non-noble metal component, 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.
According to the invention, in step (c), the usage amounts of the eggshell-shaped mesoporous material carrier and the solution containing the first active non-noble metal component precursor and the second active non-noble metal component precursor are such that the content of the first active non-noble metal component in the prepared non-noble metal isobutane dehydrogenation catalyst is 1-25 wt%, preferably 3-20 wt%, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst; the content of the second active non-noble metal component, calculated as the second active non-noble metal element, is 0.1-10 wt.%, preferably 0.5-5 wt.%; the content of the eggshell-shaped mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
According to the invention, in step (c), the solution containing the precursor of the first active non-noble metal component may be at least one of soluble salt solutions of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper; the solution containing the precursor of the second active non-noble metal component is at least one of soluble salt solutions of alkali metals or alkaline earth metals.
According to the present invention, the concentrations of the soluble salt of the first active metal and the soluble salt of the second active metal in the solution containing the first active non-noble metal component precursor and the solution containing the second active non-noble metal component precursor are not particularly limited, and for example, the concentration of the soluble salt of the first active metal in the solution containing the first active non-noble metal component precursor may be 0.05 to 0.25mol/L, and the concentration of the soluble salt of the second active metal in the solution containing the second active non-noble metal component precursor may be 0.025 to 0.15 mol/L. The soluble salt in the present invention preferably means a water-soluble salt.
According to the present invention, when the concentrations of the solution containing the first active non-noble metal component precursor and the solution containing the second active non-noble metal component precursor are within the above ranges, the amount of the solution containing the first active non-noble metal component precursor may be 50 to 150mL, and the amount of the solution containing the second active non-noble metal component precursor may be 50 to 150 mL.
According to the present invention, in the step (c), the solvent removing treatment may be carried out by a method conventional in the art, for example, a rotary evaporator may be used to remove the solvent in the system.
According to the present invention, in the step (c), the drying may be performed in a drying oven, and the firing may be performed in a muffle furnace. The drying may be performed in a drying oven and the firing may be performed in a muffle furnace. The drying conditions may include: the temperature is 60-150 ℃, preferably 80-130 ℃; the time is 1 to 20 hours, preferably 3 to 15 hours; the conditions for the firing may include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10 h.
According to the present invention, in the step (d), in order to obtain a good catalytic effect by allowing the obtained non-noble metal-based isobutane dehydrogenation catalyst to contain a specific content of sulfur components, the sulfur-containing gas is preferably at least one of nitrogen, helium and argon containing hydrogen sulfide. More preferably, the hydrogen sulfide is contained in the sulfur-containing gas in an amount of 0.1 to 5% by volume, and still more preferably 0.3 to 2% by volume.
According to the present invention, in order to make the obtained non-noble metal isobutane dehydrogenation catalyst contain a sulfur component with a specific content, and to be matched with a first active non-noble metal component and a second active non-noble metal component with a specific content, in the process of catalyzing isobutane dehydrogenation to prepare isobutene in the non-noble metal isobutane dehydrogenation catalyst, a sulfur element may be combined with the first active non-noble metal component and the second active non-noble metal component to produce a sulfide, so as to effectively prevent the first active non-noble metal component and the second active non-noble metal component from being deeply reduced, reduce a pure metal component in the catalyst, effectively inhibit occurrence of side reactions such as hydrogenolysis, and improve selectivity of target isobutene and stability of the non-noble metal isobutane dehydrogenation catalyst, in step (d), the condition of the sulfurization treatment preferably includes: the temperature is 400-700 ℃, and the time is 1-15 h; more preferably, the conditions of the vulcanization treatment include: the temperature is 450-650 ℃, and the time is 2-8 h.
According to the invention, if the relative content of the elemental sulfur component is too low, the protective effect on the first active non-noble metal component and the second active non-noble metal component is limited, and the partially oxidized metal component is still completely reduced to a pure metal state in the reaction process; if the relative amount of the elemental sulfur component is too high, the rate of the "oxidation-reduction" cycle of the active sites on the surface of the catalyst will be slowed, resulting in a slower reaction rate, indicative of less catalyst activity. In order to better exert the synergistic effect of each component, the conditions of the sulfurization treatment provided by the invention are preferably such that the content of sulfur element in the non-noble metal-based isobutane dehydrogenation catalyst is 0.1-5 wt%, more preferably 0.2-2 wt%, based on the total weight of the non-noble metal-based isobutane dehydrogenation catalyst.
According to the method for preparing the non-noble metal isobutane dehydrogenation catalyst, the content of the first active non-noble metal component in the non-noble metal isobutane dehydrogenation catalyst is 1-25 wt%, preferably 3-20 wt%, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst; the content of the second active non-noble metal component, calculated as the second active non-noble metal element, is 0.1-10 wt.%, preferably 0.5-5 wt.%; the content of the elemental sulfur component is 0.1 to 5% by weight, preferably 0.2 to 2% by weight; the content of the eggshell-shaped mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
According to the preparation method of the non-noble metal isobutane dehydrogenation catalyst, due to the fact that the eggshell-shaped mesoporous material with the two-dimensional hexagonal pore channel distribution structure is introduced in the preparation process of the carrier, the good dispersion of the active non-noble metal component on the surface of the carrier can be effectively improved by means of the morphological characteristics of the hollow structure of the eggshell-shaped mesoporous material. When the initial non-noble metal isobutane dehydrogenation catalyst is subjected to sulfidation treatment by using sulfur-containing gas, the active non-noble metal component can be effectively prevented from being deeply reduced and converted into pure metal in the catalytic process, the occurrence of side reactions such as hydrogenolysis and the like in the dehydrogenation process is inhibited, and the catalytic activity of the obtained isobutane dehydrogenation catalyst and the selectivity of a target dehydrogenation product are further improved, so that in the non-noble metal isobutane dehydrogenation catalyst, the eggshell-shaped mesoporous material carrier only loads a first active non-noble metal component selected from iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper, a second active non-noble metal component selected from alkali metal or alkaline earth metal and a sulfur component, and the higher catalytic activity can be obtained, and the eggshell-shaped mesoporous material carrier is particularly suitable for the dehydrogenation reaction of isobutane.
The invention also provides the non-noble metal isobutane dehydrogenation catalyst prepared by the method.
According to the invention, the non-noble metal isobutane dehydrogenation catalyst comprises a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur element component which are 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 an eggshell-shaped mesoporous material carrier, the eggshell-shaped mesoporous material carrier has a two-dimensional hexagonal pore channel distribution structure, the pore volume of the eggshell-shaped mesoporous material is 0.5-1.5mL/g, and the specific surface area is 100-500 m-2(ii) a pore diameter of 5 to 15nm in terms of a mode of maximum diameter, and an average particle diameter of 3 to 25 μm.
According to the invention, in the non-noble metal isobutane dehydrogenation catalyst, the average particle size of the eggshell-shaped mesoporous material serving as the carrier is measured by using a laser particle size distribution instrument, and the specific surface area, the pore volume and the most probable pore diameter of the eggshell-shaped mesoporous material carrier are measured according to a nitrogen adsorption method.
In the present invention, the average particle diameter refers to the particle size of the raw material particles, and is expressed by the diameter of the spheres when the raw material particles are spheres, by the side length of the cubes when the raw material particles are cubes, and by the mesh size of the screen that is just capable of screening out the raw material particles when the raw material particles are irregularly shaped.
According to the invention, the eggshell-shaped mesoporous material carrier has a larger maximum aperture, which is beneficial to forming a large number of active center sites, and the eggshell-shaped mesoporous material is adopted as the carrier in the preparation process of the isobutane dehydrogenation catalyst, so that the dispersion degree of active non-noble metal components is improved, and the prepared catalyst can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance only by loading the non-noble metal components.
Because the sulfur component with the specific content exists in the non-noble metal isobutane dehydrogenation catalyst and is matched with the first active non-noble metal component and the second active non-noble metal component with the specific content, in the process of catalyzing isobutane to dehydrogenate to prepare isobutene in the non-noble metal isobutane dehydrogenation catalyst, the sulfur element can be combined with the first active non-noble metal component and the second active non-noble metal component to produce sulfides, so that the first active non-noble metal component and the second active non-noble metal component are effectively prevented from being deeply reduced, the pure metal components in the catalyst are reduced, the occurrence of side reactions such as hydrogenolysis and the like is effectively inhibited, and the selectivity of target isobutene and the stability of the non-noble metal isobutane dehydrogenation catalyst are improved.
According to the invention, if the relative content of the elemental sulfur component is too low, the protective effect on the first active non-noble metal component and the second active non-noble metal component is limited, and the partially oxidized metal component is still completely reduced to a pure metal state in the reaction process; if the relative amount of the elemental sulfur component is too high, the rate of the "oxidation-reduction" cycle of the active sites on the surface of the catalyst will be slowed, resulting in a slower reaction rate, indicative of less catalyst activity. In order to better exert the synergistic effect of each component, in the non-noble metal isobutane dehydrogenation catalyst provided by the invention, the content of the first active non-noble metal component calculated by the first active non-noble metal element is 1-25 wt%, preferably 3-20 wt%, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst; the content of the second active non-noble metal component, calculated as the second active non-noble metal element, is 0.1-10 wt.%, preferably 0.5-5 wt.%; the content of the elemental sulfur component is 0.1 to 5% by weight, preferably 0.2 to 2% by weight; the content of the eggshell-shaped mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
According to the invention, the preparation cost and the environmental friendliness are considered, and the dehydrogenation activity and the selectivity of the prepared non-noble metal isobutane dehydrogenation catalyst are considered, wherein in the non-noble metal isobutane dehydrogenation catalyst, the first active non-noble metal component is preferably selected from at least one of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper components; the second active non-noble metal component is preferably selected from at least one of the alkali metals (e.g., alkali metals such as sodium, potassium, rubidium, and cesium) and the alkaline earth metals (e.g., alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium).
According to the invention, the structural parameters of the eggshell-shaped mesoporous material carrier are controlled within the range, so that the carrier is not easy to agglomerate, and the conversion rate of reaction raw materials in the reaction process of preparing isobutene by isobutane dehydrogenation can be improved by the prepared supported catalyst. When the specific surface area of the eggshell-shaped mesoporous material carrier is less than 100m2When the volume/g and/or pore volume is less than 0.5mL/g, the catalytic activity of the prepared supported catalyst is remarkably reduced; when the specific surface area of the eggshell-shaped mesoporous material carrier is more than 500m2When the volume/g and/or the pore volume is more than 1.5mL/g, the prepared supported catalyst is easy to agglomerate in the reaction process of preparing isobutene by isobutane dehydrogenation, so that the conversion rate of reaction raw materials in the reaction process of preparing isobutene by isobutane dehydrogenation is influenced.
Preferably, the pore volume of the eggshell-shaped mesoporous material carrier is 0.5-1.2mL/g, and the specific surface area is 150-350m2(ii)/g, the mode pore diameter is 7-12nm, and the average particle diameter is 3-22 μm.
Preferably, the non-noble metal isobutane dehydrogenation catalyst has a pore volume of 0.5-1mL/g and a specific surface area of 120-300m2(ii)/g, the mode pore diameter is 7-12nm, and the average particle diameter is 3-25 μm.
According to the invention, the average particle size of the non-noble metal isobutane dehydrogenation catalyst is measured by using a laser particle size distribution instrument, and the specific surface area, the pore volume and the most probable pore diameter of the non-noble metal isobutane dehydrogenation catalyst are measured by using a nitrogen adsorption method.
As mentioned above, the present invention also provides an application of the non-noble metal isobutane dehydrogenation catalyst prepared by the foregoing method in preparing isobutene by isobutane dehydrogenation, wherein the method for preparing isobutene by isobutane dehydrogenation comprises: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst.
When the non-noble metal isobutane dehydrogenation catalyst provided by the invention is used for catalyzing isobutane dehydrogenation, the conversion rate of isobutane and the selectivity of isobutene can be greatly improved.
According to the invention, the isobutane dehydrogenation reaction conditions comprise: the reaction temperature is 600-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the isobutane is 2-5h-1。
According to the present invention, in order to increase the isobutane conversion rate and prevent the catalyst from coking, it is preferable to add an inert gas as a diluent to the reaction raw material 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: 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 40-60h, 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 polyethylene glycol-polyglycerol-polyethylene glycol was purchased from Aldrich and abbreviated as P123 and its molecular formula was 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 adsorber, available from Micromeritics, USA, and BET method was used for the specific surface area and pore volume calculation of the sample; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. 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 isobutane was ═ amount of isobutane-content of isobutane in the reaction product ÷ amount of isobutane × 100%;
selectivity (%) of isobutylene ÷ actual yield of isobutylene ÷ theoretical yield of isobutylene × 100%.
Example 1
This example is used to illustrate a non-noble metal isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of egg shell-like mesoporous material carrier
Adding 1.0 g of three-dimensional block copolymer polyethylene glycol-polyglycerol-polyethylene glycol P123 and 1.69 g of ethanol into 28mL of buffer solution of acetic acid and sodium acetate with the pH value of 4.4, and stirring at 15 ℃ until the polyethylene glycol-polyglycerol-polyethylene glycol P123 is completely dissolved; then 6g of trimethylpentane is added into the solution, 2.13 g of tetramethoxysilane is added into the solution after stirring for 8h at 15 ℃, the solution is transferred into a reaction kettle with a polytetrafluoroethylene lining after stirring for 20h at 15 ℃, crystallization is carried out for 24h at 60 ℃, and then raw powder of the eggshell-shaped mesoporous material is obtained after filtration, washing and drying. Calcining the eggshell-shaped mesoporous material raw powder in a muffle furnace at 550 ℃ for 24h, and removing the template agent to obtain the eggshell-shaped mesoporous material carrier C1.
(2) Preparation of initial non-noble metal isobutane dehydrogenation catalyst
8.66g of ferric nitrate nonahydrate and 0.93g of sodium nitrate are dissolved in 100ml of deionized water, and are mixed with 10g of the eggshell-shaped mesoporous material carrier C1 prepared in the step (1), and the mixture is stirred and immersed for 60 minutes at 40 ℃ under the assistance of ultrasonic waves with the power of 200W, and then the solvent 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 6 hours. Then roasting the mixture for 8 hours in a muffle furnace at the temperature of 600 ℃ to obtain the initial non-noble metal isobutane dehydrogenation catalyst P1.
(3) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst P1, and using H at 550 DEG C2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst P1 for 5 hours by using nitrogen gas flow with the volume content of S being 1.5%, so as to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-1.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-1, based on the total weight of the Cat-1, the content of an iron component in terms of iron element is 11.5 wt%, the content of a sodium component in terms of sodium element is 2.5 wt%, the content of a sulfur component in terms of sulfur element is 1 wt%, and the content of an eggshell-shaped mesoporous material carrier C1 is 79.2 wt%.
XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument are used for characterizing the eggshell-shaped mesoporous material carrier C1 and the non-noble metal isobutane dehydrogenation catalyst Cat-1.
FIG. 1 is an XRD spectrum of a carrier C1 made of eggshell-shaped mesoporous material. The small-angle spectral peak of the XRD spectrogram shows that the XRD spectrogram of the eggshell-shaped mesoporous material carrier C1 has a 2D hexagonal pore channel structure which is unique to mesoporous materials.
Fig. 2A is a pore size distribution graph of the eggshell-shaped mesoporous material carrier C1, and fig. 2B is a nitrogen adsorption and desorption isotherm of the eggshell-shaped mesoporous material C1. As can be seen from the pore size distribution curve chart and the nitrogen adsorption and desorption isotherm spectrum, the eggshell-shaped mesoporous material carrier C1 has a sharp IV-type isotherm of the capillary condensation rate, and the isotherm has an H1 hysteresis loop, which indicates that the sample has uniform pore size distribution.
Fig. 3A and 3B are Scanning Electron Micrographs (SEM) of the eggshell-shaped mesoporous material carrier C1 (500K and 3000K magnifications, respectively). As can be seen, the particle size of the samples was between 3 and 22 μm.
Table 1 shows the structural parameters of the eggshell-shaped mesoporous material carrier C1 and the non-noble metal isobutane dehydrogenation catalyst Cat-1.
TABLE 1
| Sample (I) | Specific surface area/m2/g | Pore volume/mL/g | Most probable pore diameter/nm | Particle size/. mu.m |
| Vector C1 | 261 | 0.8 | 9.8 | 3-22 |
| Catalyst Cat-1 | 240 | 0.6 | 7.0 | 3-23.5 |
As can be seen from the data of table 1, the eggshell-shaped mesoporous material support has a reduced specific surface area and pore volume after loading the Fe component, Na component and S component, which indicates that the Fe component, Na component and S component enter the interior of the eggshell-shaped mesoporous material support during the loading reaction.
Example 2
This example is used to illustrate a non-noble metal isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of egg shell-like mesoporous material carrier
Adding 1.0 g of three-dimensional block copolymer polyethylene glycol-polyglycerol-polyethylene glycol P123 and 1.84 g of ethanol into 28mL of buffer solution of acetic acid and sodium acetate with the pH value of 5, and stirring at 40 ℃ until the polyethylene glycol-polyglycerol-polyethylene glycol is completely dissolved; then adding 9.12g of trimethylpentane into the solution, stirring for 6h at 40 ℃, then adding 3.04 g of tetramethoxysilane into the solution, stirring for 15h at 40 ℃, then transferring the solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 10h at 100 ℃, and then filtering, washing and drying to obtain the eggshell-shaped mesoporous material raw powder. Calcining the eggshell-shaped mesoporous material raw powder in a muffle furnace at 600 ℃ for 8h, and removing the template agent to obtain the eggshell-shaped mesoporous material carrier C2.
(2) Preparation of non-noble metal isobutane dehydrogenation catalyst
0.53g of magnesium nitrate hexahydrate is dissolved in 70ml of deionized water, and is mixed with 10g of the eggshell-shaped mesoporous material carrier C2 prepared in the step (1), the mixture is stirred and immersed for 30 minutes at 50 ℃ under the assistance of ultrasonic waves with the power of 250W, and then solvent water in the system is distilled off by a rotary evaporator to obtain a solid product M. The solid product M was dried in a drying oven at 120 ℃ for 3 hours. Then, the magnesium alloy is roasted in a muffle furnace at the temperature of 650 ℃ for 5 hours to obtain a Mg-C2 sample loaded with the magnesium component. 9.20g of zinc nitrate hexahydrate is dissolved in 150ml of deionized water, mixed with the Mg-C2 sample, immersed under stirring at 50 ℃ for 30 minutes with the assistance of ultrasonic waves with the power of 250W, and then the solvent water in the system is distilled off by a rotary evaporator to obtain a solid product N. The solid product N was dried in a drying oven at 120 ℃ for 3 hours. Then roasting the mixture for 5 hours in a muffle furnace at the temperature of 650 ℃ to obtain the initial non-noble metal isobutane dehydrogenation catalyst P2.
(3) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
10g of the initial non-noble metal system is taken for isobutane removalHydrogen catalyst P2, at 450 ℃ using H2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst P2 for 8 hours by using nitrogen gas flow with the volume content of S being 2% to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-2.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-2, based on the total weight of the Cat-2, the content of a zinc component in terms of zinc element is 19.9 wt%, the content of a magnesium component in terms of magnesium element is 0.5 wt%, the content of a sulfur component in terms of sulfur element is 1.8 wt%, and the content of an eggshell-shaped mesoporous material carrier C2 is 73.4 wt%.
The eggshell-shaped mesoporous material carrier C2 and the non-noble metal isobutane dehydrogenation catalyst Cat-2 are characterized by an XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument.
Table 2 shows the structural parameters of the eggshell-shaped mesoporous material carrier C2 and the non-noble metal isobutane dehydrogenation catalyst Cat-2.
TABLE 2
| Sample (I) | Specific surface area/m2/g | Pore volume/mL/g | Most probable pore diameter/nm | Particle size/. mu.m |
| Vector C2 | 263 | 0.8 | 9.6 | 3-12.5 |
| Catalyst Cat-2 | 235 | 0.65 | 7.3 | 3-14.6 |
As can be seen from the data in table 2, the specific surface area and the pore volume of the eggshell-shaped mesoporous material carrier are reduced after being loaded with the Zn component, the Mg component and the S component, which indicates that the Zn component, the Mg component and the S component enter the inside of the eggshell-shaped mesoporous material carrier during the loading reaction.
Example 3
(1) Preparation of egg shell-like mesoporous material carrier
Adding 1.0 g of three-dimensional block copolymer polyethylene glycol-polyglycerol-polyethylene glycol P123 and 2.76 g of ethanol into 28mL of acetic acid with the pH value of 3 and sodium acetate buffer solution, and stirring at 15 ℃ until the polyethylene glycol-polyglycerol-polyethylene glycol is completely dissolved; then 5.7g of trimethylpentane is added into the solution, stirring is carried out for 8h at 15 ℃, 2.13 g of tetramethoxysilane is added into the solution, stirring is carried out for 10h at 40 ℃, then the solution is transferred into a reaction kettle with a polytetrafluoroethylene lining, crystallization is carried out for 40h at 40 ℃, and then filtration, washing and drying are carried out to obtain the eggshell-shaped mesoporous material raw powder. Calcining the eggshell-shaped mesoporous material raw powder in a muffle furnace at 450 ℃ for 36h, and removing the template agent to obtain the eggshell-shaped mesoporous material carrier C3.
(2) Preparation of non-noble metal isobutane dehydrogenation catalyst
1.52g of nickel nitrate hexahydrate is dissolved in 100ml of deionized water, and is mixed with 10g of the eggshell-shaped mesoporous material carrier C3 prepared in the step (1), the mixture is stirred and immersed for 2 hours at 25 ℃ under the assistance of ultrasonic waves with the power of 150W, and then solvent water in the system is distilled off by a rotary evaporator to obtain a solid product P. The solid product P was dried in a drying oven at 130 ℃ for 3 hours. Then, the sample was calcined in a muffle furnace at 625 ℃ for 6 hours to obtain a Ni-C3 sample loaded with a nickel component. 0.98g of potassium chloride is dissolved in 100ml of deionized water, mixed with the Ni-C3 sample, and is continuously stirred and immersed for 2 hours at 25 ℃ under the assistance of ultrasonic waves with the power of 150W, and then solvent water in the system is distilled off by a rotary evaporator to obtain a solid product Q. The solid product Q was dried in a drying oven at 130 ℃ for 3 hours. Then roasting the mixture for 6 hours in a muffle furnace at the temperature of 625 ℃ to obtain the initial non-noble metal isobutane dehydrogenation catalyst P3.
(3) Method for preparing non-noble metal isobutane dehydrogenation catalyst by sulfurizing initial non-noble metal isobutane dehydrogenation catalyst
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst P3, and using H at 650 DEG C2And carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst P3 for 2 hours by using nitrogen gas flow with the volume content of S being 0.3%, so as to obtain a non-noble metal isobutane dehydrogenation catalyst Cat-3.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-3, based on the total weight of the Cat-3, the content of a nickel component in terms of nickel element is 3 wt%, the content of a potassium component in terms of potassium element is 4.9 wt%, the content of a sulfur component in terms of sulfur element is 0.2 wt%, and the content of an eggshell-shaped mesoporous material carrier C3 is 89.5 wt%.
XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument are used for characterizing the eggshell-shaped mesoporous material carrier C3 and the non-noble metal isobutane dehydrogenation catalyst Cat-3.
Table 3 shows the structural parameters of the eggshell-shaped mesoporous material carrier C3 and the non-noble metal isobutane dehydrogenation catalyst Cat-3.
TABLE 3
| Sample (I) | Specific surface area/m2/g | Pore volume/mL/g | Most probable pore diameter/nm | Particle size/. mu.m |
| Vector C3 | 258 | 1.0 | 9.7 | 5-16.2 |
| Catalyst Cat-3 | 243 | 0.88 | 7.7 | 5-18.1 |
As can be seen from the data in table 3, the specific surface area and the pore volume of the eggshell-shaped mesoporous material carrier are reduced after the Ni component, the K component and the S component are loaded, which indicates that the Ni component, the K component and the S component enter the inside of the eggshell-shaped mesoporous material carrier during the loading reaction.
Example 4
This example is used to illustrate a non-noble metal isobutane dehydrogenation catalyst and a method for preparing the same.
A non-noble metal-based isobutane dehydrogenation catalyst Cat-4 was prepared according to the method of example 1, except that the amount of ferric nitrate nonahydrate used in step (2) was 7.4g and the amount of sodium nitrate used was 0.15 g.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-4, based on the total weight of the Cat-4, the content of an iron component is 20.5 wt% calculated by an iron element, the content of a sodium component is 0.4 wt% calculated by a sodium element, the content of a sulfur component is 0.1 wt% calculated by a sulfur element, and the content of an eggshell-shaped mesoporous material carrier C4 is 69.2 wt%.
XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument are used for characterizing the eggshell-shaped mesoporous material carrier C4 and the non-noble metal isobutane dehydrogenation catalyst Cat-4.
Table 4 shows the pore structure parameters of the eggshell-shaped mesoporous material carrier C4 and the non-noble metal isobutane dehydrogenation catalyst Cat-4.
TABLE 4
| Sample (I) | Specific surface area/m2/g | Pore volume/mL/g | Most probable pore diameter/nm | Particle size/. mu.m |
| Vector C4 | 261 | 0.8 | 9.8 | 3-22 |
| Catalyst Cat-4 | 233 | 0.6 | 7.2 | 3-23.8 |
As can be seen from the data of table 4, the eggshell-shaped mesoporous material support has a reduced specific surface area and pore volume after loading the Fe component, Na component and S component, which indicates that the Fe component, Na component and S component enter the interior of the eggshell-shaped mesoporous material support during the loading reaction.
Comparative example 1
This comparative example is used to illustrate a reference non-noble metal isobutane dehydrogenation catalyst and a method for its preparation.
A non-noble metal isobutane dehydrogenation catalyst was prepared according to the method of example 1, except that step (3) was omitted, the initial non-noble metal isobutane dehydrogenation catalyst was not sulfided with a sulfur-containing gas, and the surface of the non-noble metal isobutane dehydrogenation catalyst Cat-D1 contained no S component.
In the non-noble metal isobutane dehydrogenation catalyst Cat-D1, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-D1, the content of an iron component in terms of iron element is 11.5 wt%, the content of a sodium component in terms of sodium element is 2.5 wt%, and the content of the eggshell-shaped mesoporous material carrier C1 is 80 wt%.
Comparative example 2
This comparative example is used to illustrate a reference non-noble metal isobutane dehydrogenation catalyst and a method for its preparation.
A non-noble metal-based isobutane dehydrogenation catalyst Cat-D2 was prepared according to the method of example 1, except that the ultrasonic dispersion in step (2) was eliminated.
In the non-noble metal isobutane dehydrogenation catalyst Cat-D2, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst Cat-D2, the content of an iron component in terms of iron element is 8.5 wt%, the content of a sodium component in terms of sodium element is 1.1 wt%, the content of a sulfur component in terms of sulfur element is 1 wt%, and the content of the eggshell-shaped mesoporous material carrier C1 is 85.4 wt%.
Comparative example 3
This comparative example is used to illustrate a reference non-noble metal isobutane dehydrogenation catalyst and a method for its preparation.
A non-noble metal-based isobutane dehydrogenation catalyst was prepared according to the method of example 3, except that in step (2), 2.9g of chromium sulfate (Cr)2(SO4)3) Replacing the nickel nitrate hexahydrate, i.e. the eggshellAnd (3) taking the active component loaded by the flaky mesoporous material carrier C3 as a toxic metal Cr component, and canceling the step (3), wherein the initial non-noble metal isobutane dehydrogenation catalyst is not subjected to sulfuration treatment by using sulfur-containing gas, so that the non-noble metal isobutane dehydrogenation catalyst Cat-D3 is obtained.
According to the determination of an X-ray fluorescence spectrometer, in the non-noble metal isobutane dehydrogenation catalyst Cat-D3, based on the total weight of the Cat-D3, the content of a chromium component in terms of chromium elements is 7.2 wt%, the content of a potassium component in terms of potassium elements is 4.9 wt%, and the content of an eggshell-shaped mesoporous material carrier C3 is 83.6 wt%.
Test example
Test of performance of non-noble metal isobutane dehydrogenation catalyst in reaction for preparing isobutene through isobutane dehydrogenation
Respectively loading 0.5g of the non-noble metal isobutane dehydrogenation catalyst prepared in the above examples and comparative examples into a fixed bed quartz reactor, controlling the reaction temperature at 600 ℃, the reaction pressure at 0.1MPa, and the reaction pressure of isobutane: the molar ratio of helium is 1: 1, the mass space velocity of the isobutane is 5.0h-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 5.
TABLE 5
The results in table 5 show that the non-noble metal isobutane dehydrogenation catalyst prepared by the method of the present invention has excellent performance when used for catalyzing the reaction of preparing isobutene by isobutane dehydrogenation. The experimental results of the test example 1 and the test example 5 are compared to find that the performance of the sulfur-containing non-noble metal isobutane dehydrogenation catalyst Cat-1 is obviously superior to that of the sulfur-free non-noble metal isobutane dehydrogenation catalyst Cat-D1, the initial conversion rate of isobutane is improved by 21.2%, and the initial selectivity of isobutene is improved to 89.9% from 71.1%; in the reaction process of 6 hours, the conversion rate of the non-noble metal isobutane dehydrogenation catalyst Cat-1 to isobutane and the selectivity of isobutene are hardly reduced, while the selectivity of the non-noble metal isobutane dehydrogenation catalyst Cat-D1 is obviously reduced. The results show that the existence of sulfur on the surface of the sulfur-containing non-noble metal isobutane dehydrogenation catalyst can effectively improve the dehydrogenation activity, isobutene selectivity and stability of the non-noble metal isobutane dehydrogenation catalyst.
The experimental results of comparative test example 1 and test example 6 show that the non-noble metal isobutane dehydrogenation catalyst with better performance can be obtained by promoting the dispersion of the active metal component by using an ultrasonic auxiliary method in the metal component element loading process.
The experimental results of test example 1 and test example 7 show that the catalytic performance of the isobutane dehydrogenation catalyst obtained by loading the first non-noble metal active component, the second non-noble metal active component and the sulfur component on the eggshell-shaped mesoporous material carrier is equivalent to that of the isobutane dehydrogenation catalyst obtained by loading the toxic metal active component, the Cr component and the alkali metal component on the eggshell-shaped mesoporous material carrier.
Furthermore, the experimental results of comparative test example 1 and test example 4 can find that when the loadings of the first and second active non-noble metal components are within the preferred ranges of the present invention, a dehydrogenation catalyst with better performance can be obtained.
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 (11)
1. A method for preparing a non-noble metal isobutane dehydrogenation catalyst is characterized by comprising the following steps:
(a) under the condition of solution, mixing and contacting a template agent with trimethylpentane and tetramethoxysilane to obtain solution A, and sequentially crystallizing, filtering and drying the solution A to obtain eggshell-shaped mesoporous material raw powder;
(b) carrying out template agent treatment on the eggshell-shaped mesoporous material raw powder to obtain an eggshell-shaped mesoporous material carrier;
(c) under the ultrasonic condition, carrying out dipping treatment on a eggshell-shaped mesoporous material carrier and a solution containing a first active non-noble metal component precursor and a second active non-noble metal component precursor, and then sequentially removing a solvent, drying and roasting to obtain an initial non-noble metal isobutane dehydrogenation catalyst;
(d) and carrying out sulfidation treatment on the initial non-noble metal isobutane dehydrogenation catalyst by using sulfur-containing gas.
2. The process of claim 1, wherein in step (a), the conditions of the mixing contact comprise: the temperature is 10-60 ℃, the time is 0.2-100h, and the pH value is 1-6;
preferably, the weight ratio of the template, the trimethylpentane and the tetramethoxysilane is 1: (1.2-20): (0.1-15);
preferably, the template agent is triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol EO20PO70EO20；
Preferably, the crystallization conditions include: the temperature is 30-150 ℃ and the time is 4-72 h.
3. The method of claim 1 wherein in step (b) the stripper plate agent treatment process comprises: calcining the eggshell-shaped mesoporous material raw powder for 8-36h at the temperature of 300-600 ℃.
4. The method of claim 1, wherein in step (c), 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 usage amounts of the eggshell-shaped mesoporous material carrier and the solution containing the first active non-noble metal component precursor and the second active non-noble metal component precursor are such that, in the prepared non-noble metal isobutane dehydrogenation catalyst, based on the total weight of the non-noble metal isobutane dehydrogenation catalyst, the content of the first active non-noble metal component calculated by the first active non-noble metal element is 1-25 wt%, preferably 3-20 wt%; the content of the second active non-noble metal component, calculated as the second active non-noble metal element, is 0.1-10 wt.%, preferably 0.5-5 wt.%; the content of the eggshell-shaped mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
5. The method of claim 1 or 4, wherein the solution containing the first active non-noble metal component precursor is at least one of a soluble salt solution of iron, nickel, zinc, molybdenum, tungsten, manganese, tin, and copper; the solution containing the second active non-noble metal component precursor is at least one of a soluble salt solution of an alkali metal or an alkaline earth metal.
6. The method of claim 1, wherein, in step (d), the sulfur-containing gas is at least one of nitrogen, helium, and argon containing hydrogen sulfide;
preferably, the hydrogen sulphide is present in the sulphur-containing gas in an amount of 0.1-5% by volume, more preferably 0.3-2%;
more preferably, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃, and the time is 1-15 h; preferably, the conditions of the vulcanization treatment include: the temperature is 450-650 ℃, and the time is 2-8 h;
further preferably, the condition of the sulfurization treatment is such that the content of elemental sulfur in the non-noble metal-based isobutane dehydrogenation catalyst is 0.1 to 5 wt%, preferably 0.2 to 2 wt%, based on the total weight of the non-noble metal-based isobutane dehydrogenation catalyst.
7. The non-noble metal isobutane dehydrogenation catalyst supported by the method of any one of claims 1 to 6, which is a eggshell-shaped mesoporous material.
8. The non-noble metal-based isobutane dehydrogenation catalyst according to claim 7, wherein the non-noble metal-based isobutane dehydrogenation catalyst comprises a carrier, and a first active non-noble metal component, a second active non-noble metal component and a sulfur component supported on the carrier, wherein the carrier is an eggshell-shaped mesoporous material carrier, the eggshell-shaped mesoporous material carrier has a two-dimensional hexagonal pore distribution structure, the pore volume of the eggshell-shaped mesoporous material is 0.5-1.5mL/g, and the specific surface area is 100-2(ii) a pore diameter of 5 to 15nm in terms of a mode of maximum diameter, and an average particle diameter of 3 to 25 μm.
9. Non-noble metal-based isobutane dehydrogenation catalyst according to claim 8, wherein the content of the first active non-noble metal component, calculated as first active non-noble metal element, is from 1 to 25 wt. -%, preferably from 3 to 20 wt. -%, based on the total weight of the non-noble metal-based isobutane dehydrogenation catalyst; the content of the second active non-noble metal component, calculated as the second active non-noble metal element, is 0.1-10 wt.%, preferably 0.5-5 wt.%; the content of the elemental sulfur component is 0.1 to 5% by weight, preferably 0.2 to 2% by weight; the content of the eggshell-shaped mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
10. Use of a non-noble metal-based isobutane dehydrogenation catalyst according to any one of claims 7 to 9 for the preparation of isobutene by the dehydrogenation of isobutane, wherein said process for the preparation of isobutene by the dehydrogenation of isobutane comprises: isobutane was subjected to a dehydrogenation reaction in the presence of a catalyst.
11. Use according to claim 10, wherein the conditions of the isobutane dehydrogenation reaction comprise: the reaction temperature is 550 ℃ and 650 ℃, and the reaction pressure is 0.05-0.2MPa, and the mass space velocity of isobutane is 2-5h-1。
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