CN111250096A - Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof - Google Patents
Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof Download PDFInfo
- Publication number
- CN111250096A CN111250096A CN201811457384.4A CN201811457384A CN111250096A CN 111250096 A CN111250096 A CN 111250096A CN 201811457384 A CN201811457384 A CN 201811457384A CN 111250096 A CN111250096 A CN 111250096A
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- China
- Prior art keywords
- noble metal
- mesoporous material
- dehydrogenation catalyst
- isobutane dehydrogenation
- hexagonal mesoporous
- 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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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 370
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 235
- 239000003054 catalyst Substances 0.000 title claims abstract description 190
- 239000001282 iso-butane Substances 0.000 title claims abstract description 185
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 178
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 57
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
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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 hexagonal mesoporous material raw powder; (b) carrying out template agent treatment and thermal activation treatment on the mesoporous material raw powder to obtain a hexagonal 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 hexagonal 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 hexagonal 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) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure;
(b) sequentially carrying out template agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material carrier;
(c) under the ultrasonic condition, dipping the hexagonal mesoporous material carrier in 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 hexagonal 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, 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 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 X-ray diffraction pattern of hexagonal mesoporous material carrier C1 of example 1;
fig. 2A is a nitrogen adsorption-desorption graph of the hexagonal mesoporous material support C1 of example 1;
FIG. 2B is a pore size distribution diagram of hexagonal mesoporous material support C1 of example 1;
FIG. 3 is a TEM transmission electron micrograph of the micro-morphology of the hexagonal mesoporous material support C1 of example 1;
FIG. 4 is an SEM scanning electron micrograph of the micro-morphology of the hexagonal mesoporous material support 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 producing a non-noble metal-based isobutane dehydrogenation catalyst, comprising the steps of:
(a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure;
(b) sequentially carrying out template agent treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material carrier;
(c) under the ultrasonic condition, dipping the hexagonal mesoporous material carrier in 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 present invention, in the step (a), the process of preparing the hexagonal mesoporous material raw powder having the structure of the cubic center Im3m may include: mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture. The order of the mixing and contacting is not particularly limited, and the template agent, the potassium sulfate, the acid agent and the tetraethoxysilane can be simultaneously mixed, or any two or three of the template agent, the potassium sulfate, the acid agent and the tetraethoxysilane can be mixed, and then other components are added and uniformly mixed. According to a preferred embodiment, the template agent, the potassium sulfate and the acid agent are mixed uniformly, and then the tetraethoxysilane is added and mixed uniformly.
In the present invention, the amount of the template agent, potassium sulfate and tetraethoxysilane may vary within a wide range, for example, the molar ratio of the amount of the template agent, potassium sulfate and tetraethoxysilane may be 1: 100-800: 20-200, preferably 1: 150-700: 80-180, more preferably 1: 200-400: 100-150.
In the present invention, the templating agent may be various templating agents that are conventional in the art. For example, the templating agent may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, which may be prepared by methods known to those skilled in the art, or may be obtained commercially, for example, from Fuka under the trade name Synperonic F108, formula EO132PO60EO132Average molecular weight Mn14600. Of these, polyoxyethylene-polyoxypropylene-polyoxyethyleneThe number of moles is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and for example, may be at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous hydrochloric acid solution.
The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH of the mixture is 1 to 7.
The conditions of the mixing and contacting are not particularly limited in the present invention, and for example, the conditions of the mixing and contacting may include: the temperature is 25-60 deg.C, the time is 10-240min, and the pH value is 1-7. 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 a preferred embodiment of the present invention, the process of mixing and contacting the template agent, the potassium sulfate, the acid agent and the tetraethoxysilane comprises: adding a template agent triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108 into an aqueous solution of hydrochloric acid, wherein the molar feed ratio is shown in the specification, wherein the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108: potassium sulfate: water: hydrogen chloride ═ 1: 200-400: 10000-30000: 100-900, stirring the mixture at a temperature of between 25 and 60 ℃ until the mixture is dissolved, and then adding tetraethoxysilane into the obtained solution, wherein the dosage of the tetraethoxysilane is the molar charge ratio of the triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene F108: 1-ethyl orthosilicate: 100-150 ℃ and stirring for 10-240min at the temperature of 25-60 ℃.
In the present invention, the crystallization conditions are not particularly limited, and for example, the crystallization conditions may include: the temperature is 25-60 ℃, preferably 30-55 ℃; the time is 10-72h, preferably 10-40 h. According to a preferred embodiment, the crystallization is carried out by hydrothermal crystallization.
In the present invention, the process of obtaining the hexagonal mesoporous material raw powder having the structure of the cubic center Im3m by filtration may include: after filtration, repeated washing with deionized water (washing times may be 2 to 10) and suction filtration.
According to the invention, in step (b), the method of the template removal treatment is typically a calcination method. The conditions of the template removal treatment may be conventionally selected in the art, for example, the procedure of the template removal treatment may include: calcining the hexagonal mesoporous material raw powder for 8-20h at the temperature of 300-600 ℃.
According to the present invention, in order to remove hydroxyl groups and residual moisture from the hexagonal mesoporous material carrier, a thermal activation treatment needs to be performed before the hexagonal mesoporous material carrier supports the first active non-noble metal component and the second active non-noble metal component, and the conditions of the thermal activation treatment may include: calcining the hexagonal mesoporous material carrier at the temperature of 300-900 ℃ for 7-10h in the presence of nitrogen.
According to the invention, the first active non-noble metal component and the second active non-noble metal component loaded on the hexagonal mesoporous material carrier can enter the pore channel of the hexagonal mesoporous material carrier by adopting an impregnation mode and depending on the capillary pressure of the pore channel structure of the carrier, and the first active non-noble metal component and the second active non-noble metal component can be adsorbed on the surface of the hexagonal mesoporous material carrier until the first active non-noble metal component and the second active non-noble metal component reach adsorption balance 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 hexagonal 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 a hexagonal 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 a hexagonal mesoporous material carrier loaded with a first metal component; and then carrying out second mixing contact on the hexagonal 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 hexagonal 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 hexagonal 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 hexagonal 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 used in amounts 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 hexagonal 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 hexagonal mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
According to the invention, in the preparation method of the non-noble metal isobutane dehydrogenation catalyst, due to the introduction of the hexagonal mesoporous material with the cubic center Im3m structure in the preparation process of the carrier, the carrier of the non-noble metal isobutane dehydrogenation catalyst can obtain the characteristics of a mesoporous molecular sieve material such as a porous structure, a maximum pore diameter, a large specific surface area and a large pore volume, which are good for the dispersion of an active non-noble metal component on the surface of the carrier, and effectively avoid the deep reduction and conversion of the active non-noble metal component into a pure metal in the catalytic process, and inhibit the occurrence of side reactions such as hydrogenolysis and the like in the dehydrogenation process, so as to improve the catalytic activity of the obtained isobutane dehydrogenation catalyst and the selectivity of a target dehydrogenation product, therefore, in the non-noble metal isobutane dehydrogenation catalyst, the hexagonal mesoporous material carrier only loads iron, zinc, manganese, The first active non-noble metal component of nickel, zinc, molybdenum, tungsten, manganese, tin and copper, the second active non-noble metal component selected from alkali metals or alkaline earth metals and the sulfur component can obtain higher catalytic activity, and the catalyst 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 a hexagonal mesoporous material carrier, and the hexagonal mesoporous material carrier is provided with a cubic cage-shaped pore canalThe crystal structure of the hexagonal mesoporous material carrier has a cubic-centered Im3m structure, the mode pore diameter of the hexagonal mesoporous material carrier is 4-15nm, and the specific surface area is 550-650m2Pore volume of 0.5-1.5mL/g, and average particle diameter of 0.5-10 μm.
According to the invention, the average particle size of the hexagonal mesoporous material is measured by a laser particle size distribution instrument, and the specific surface area, the pore volume and the most probable pore diameter are measured by a nitrogen adsorption method. In the present invention, the particle diameter refers to the particle size of the raw material particles, and is expressed by the diameter of the sphere when the raw material particles are spherical, by the side length of the cube when the raw material particles are cubic, and by the mesh size of the screen that can sieve out the raw material particles when the raw material particles are irregularly shaped.
According to the invention, the hexagonal mesoporous material carrier has a special cubic center crystal structure, the crystal structure of the hexagonal mesoporous material carrier has a cubic center Im3m structure, and the hexagonal mesoporous material carrier is a non-closest packing mode and is a good long-range ordered structure, so that the hexagonal mesoporous material can show high strength in a wide temperature range and a large strain state. In addition, the specific cubic cage-shaped hole structure of the hexagonal mesoporous material is matched with the narrow pore size distribution and the uniform pore channel distribution of the hexagonal mesoporous material, so that the dispersion degree of the active non-noble metal component is improved, and the prepared catalyst can achieve better dehydrogenation activity, selectivity, stability and anti-carbon deposition performance only by loading the non-noble metal component.
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 hexagonal 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 hexagonal mesoporous material carrier are controlled within the range, the carrier is ensured not to be easily agglomerated, 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 hexagonal mesoporous material carrier is less than 550m2G and/or pore volume less thanWhen the concentration is 0.5mL/g, the catalytic activity of the prepared supported catalyst is obviously reduced; when the specific surface area of the hexagonal mesoporous material carrier is more than 650m2When 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 hexagonal mesoporous material has a mode pore size of 4-12nm, such as 4nm, 4.8nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm and 12nm, and any mode pore size between any two mode pore sizes, and a specific surface area of 570-620 m-2The hexagonal mesoporous material has the advantages of large pore diameter, large pore volume and large specific surface area, so that metal components can be well dispersed on the surface of the hexagonal mesoporous material, and further the non-noble metal isobutane dehydrogenation catalyst prepared from the hexagonal mesoporous material has excellent catalytic performance, and the selectivity of target isobutene and the stability of the non-noble metal isobutane dehydrogenation catalyst are improved.
Preferably, the hexagonal mesoporous material carrier is an FDU-6 carrier.
Preferably, the most probable pore diameter of the non-noble metal isobutane dehydrogenation catalyst is 3-15nm, and the specific surface area is 550-600m2Pore volume of 0.5-1mL/g, and average particle diameter of 0.5-20 μm, preferably 0.8-15 μm.
According to the present invention, the specific surface area, pore volume and most probable pore diameter of the non-noble metal-based isobutane dehydrogenation catalyst were measured according to 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, polyoxyethylene-polyoxypropylene-polyoxyethylene was obtained from Fuka under the trade name Synperonic F108 and the formula EO132PO60EO132Average molecular weight Mn＝14600。
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 hexagonal mesoporous material carrier
2g (1.4X 10)-4mol) template F108, 5.24g (0.03mol) of K2SO4Adding into 60g hydrochloric acid solution with 2(2N) equivalent concentration, and stirring at 38 deg.C until F108 is completely dissolved; adding 4.2g (0.02mol) of tetraethoxysilane into the solution, stirring at 38 ℃ for 15min, and standing at 38 ℃ for 24 h; then adding 100g of deionized water into the mixed solution for dilution, then filtering, washing with deionized water for 4 times, and then carrying out suction filtration to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure; and calcining the raw powder with the cubic center Im3m structure in a muffle furnace at 400 ℃ for 12 hours, and removing the template agent to obtain the hexagonal mesoporous material A1. And then calcining the product hexagonal mesoporous material A1 with the template agent removed at 400 ℃ for 10 hours under the protection of nitrogen to carry out thermal activation treatment, and removing hydroxyl and residual moisture of the hexagonal mesoporous material A1 to obtain the thermally activated hexagonal 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 hexagonal mesoporous material carrier C1 prepared in the step (1), 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 a hexagonal mesoporous material carrier C1 is 79 wt%.
The hexagonal mesoporous material carrier C1 and the non-noble metal isobutane dehydrogenation catalyst Cat-1 are characterized by an XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument.
Fig. 1 is an X-ray diffraction pattern of the hexagonal mesoporous material carrier C1, wherein the abscissa is 2 θ and the ordinate is intensity, and it is apparent from the XRD pattern that the hexagonal mesoporous material carrier C1 has 1 diffraction peak (2 θ ═ 0.6 °) of (110) plane and a diffraction shoulder (2 θ ═ 1.2 °) of (200) plane in accordance with the cube center Im3m in a small angular region. (110) The diffraction peak intensity of the surface is high, the peak shape is narrow, which indicates that the hexagonal mesoporous material carrier C1 has a good long-range ordered structure, and the structure is consistent with the XRD spectrum of the FDU-6 mesoporous material reported in the literature (Chengzhong Yu, Bozhi Tian, Jie Fan, Galen D.Stucky, Dongyouan Zhuao, J.Am.chem.Soc.2002,124,4556-4557), and in addition, the position of the diffraction shoulder peak (2 theta is 1.2 degrees) of the (200) surface is completely different from the hexagonal or lamellar structure;
FIG. 2A is a graph of nitrogen adsorption-desorption curves (abscissa is relative pressure, unit is p/p) of hexagonal mesoporous material carrier C10) FIG. 2B is a diagram showing a pore size distribution (abscissa is pore size, unit is 0.1nm) of the hexagonal mesoporous material support C1, from which it can be seen that the hexagonal mesoporous material support C1 has a narrow pore size distribution and very uniform pores, and a nitrogen adsorption de-adsorption isotherm in FIG. 2A shows that the hexagonal mesoporous material support C1 is a typical IUPAC-defined class IV isothermal lineAnd (3) an adsorption-desorption isotherm, wherein a sample has an H2 type hysteresis loop, and the result proves that the hexagonal mesoporous material carrier C1 has a specific mesoporous structure with a cubic cage structure reported in literatures. Desorption branches between 0.4 and 0.5 relative partial pressure also indicate that the material has a cage-like cavity structure;
FIG. 3 is a TEM transmission electron micrograph of the micro-morphology of the hexagonal mesoporous material carrier C1, wherein the shape of the pores in the (100) crystal plane of the hexagonal mesoporous material carrier C1 can be clearly seen from FIG. 3, and the samples all have a cubic-centered Im3m structure;
fig. 4 is an SEM scanning electron micrograph of the micro-morphology of the hexagonal mesoporous material carrier C1, which shows that the micro-morphology of the hexagonal mesoporous material carrier C1 is hexagonal and the particle size is in the micrometer level.
Table 1 shows the pore structure parameters of the hexagonal mesoporous material carrier C1 and the non-noble metal isobutane dehydrogenation catalyst Cat-1.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Pore diameter of the most probable (nm) | Particle size (. mu.m) |
| Vector C1 | 598 | 0.7 | 4.8 | 0.8-10 |
| CatalysisAgent Cat-1 | 565 | 0.53 | 3.5 | 0.8-11.5 |
As can be seen from the data of table 1, the hexagonal mesoporous material support C1 has a reduced specific surface area and pore volume after supporting the Fe component, Na component and S component, which indicates that the Fe component, Na component and S component enter the inside of the hexagonal mesoporous material support C1 during the supporting 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 hexagonal mesoporous material carrier
1.46g (1X 10)-4mol) template F108, 6.96g (0.04mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved; adding 3.1g (0.015mol) of tetraethoxysilane into the solution, stirring for 15min at 38 ℃, and standing for 20h at 40 ℃; then adding 100g of deionized water into the mixed solution for dilution, then filtering, washing with deionized water for 4 times, and then carrying out suction filtration to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure; and calcining the obtained hexagonal mesoporous material raw powder with the cubic center Im3m structure in a muffle furnace at 600 ℃ for 8h, and removing the template agent to obtain the hexagonal mesoporous material A2. Then calcining the product hexagonal mesoporous material A2 of which the template agent is removed at 500 ℃ for 10 hours under the protection of nitrogen to carry out thermal activation treatment, and removing hydroxyl and residual moisture of the hexagonal mesoporous material A2 to obtain a thermally activated hexagonal mesoporous material carrier C2;
(2) preparation of initial 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 hexagonal 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 mixture was calcined in a muffle furnace at 650 ℃ for 5 hours to obtain a Mg-A2 sample loaded with a magnesium component. 9.20g of zinc nitrate hexahydrate is dissolved in 150ml of deionized water, mixed with the Mg-A2 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
Taking 10g of the initial non-noble metal isobutane dehydrogenation catalyst P2, and using H at 450 DEG C2And 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 a hexagonal mesoporous material carrier C2 is 73 wt%.
The hexagonal 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 pore structure parameters of the hexagonal mesoporous material carrier C2 and the non-noble metal isobutane dehydrogenation catalyst Cat-2.
TABLE 2
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Pore diameter of the most probable (nm) | Particle size (. mu.m) |
| Vector C2 | 580 | 0.9 | 6 | 0.9-7.5 |
| Catalyst Cat-2 | 558 | 0.6 | 4.9 | 0.9-11.2 |
As can be seen from the data of table 2, the specific surface area and the pore volume of the hexagonal mesoporous material support C2 were reduced after the Zn component, the Mg component, and the S component were supported, which indicates that the Zn component, the Mg component, and the S component entered the interior of the hexagonal mesoporous material support C2 during the supporting reaction.
Example 3
This example is used to illustrate a non-noble metal isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of hexagonal mesoporous material carrier
1.46g (1X 10)-4mol) template F108, 3.48g (0.04mol) of K2SO4Is equivalent to 60g thickThe hydrochloric acid solution with the degree of 2(2N) is stirred at 35 ℃ until F108 is completely dissolved; adding 3.1g (0.015mol) of tetraethoxysilane into the solution, stirring for 15min at 38 ℃, and standing for 18h at 50 ℃; then adding 100g of deionized water into the mixed solution for dilution, then filtering, washing with deionized water for 4 times, and then carrying out suction filtration to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure; and calcining the obtained hexagonal mesoporous material raw powder with the cubic center Im3m structure in a muffle furnace at 550 ℃ for 10 hours, and removing the template agent to obtain the hexagonal mesoporous material A3. Then calcining the product hexagonal mesoporous material A3 without the template agent at 700 ℃ for 8 hours under the protection of nitrogen to carry out thermal activation treatment, and removing hydroxyl and residual moisture of the hexagonal mesoporous material A3 to obtain a thermally activated hexagonal mesoporous material carrier C3;
(2) preparation of initial 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 hexagonal 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-A3 sample loaded with a nickel component. 0.98g of potassium chloride is dissolved in 100ml of deionized water, mixed with the Ni-A3 sample, and is immersed under stirring at 25 ℃ for 2 hours under the assistance of ultrasonic waves with the power of 150W, and then the 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 C2A nitrogen gas stream containing 0.3% by volume of S is introduced into the reactorAnd carrying out vulcanization treatment on the initial non-noble metal isobutane dehydrogenation catalyst P3 for 2 hours 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 is 3 wt% calculated by nickel element, the content of a potassium component is 4.9 wt% calculated by potassium element, the content of a sulfur component is 0.2 wt% calculated by sulfur element, and the content of a hexagonal mesoporous material carrier C3 is 89.6 wt%.
The hexagonal mesoporous material carrier C3 and the non-noble metal isobutane dehydrogenation catalyst Cat-3 are characterized by an XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument.
Table 3 shows the pore structure parameters of the hexagonal mesoporous material carrier C3 and the non-noble metal isobutane dehydrogenation catalyst Cat-3.
TABLE 3
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Pore diameter of the most probable (nm) | Particle size (. mu.m) |
| Vector C3 | 570 | 1 | 12 | 1-7 |
| Catalyst Cat-1 | 554 | 0.87 | 10.2 | 1-8.6 |
As can be seen from the data of table 3, the specific surface area and the pore volume of the hexagonal mesoporous material support C3 were reduced after the Ni component, the K component, and the S component were supported, which indicates that the Ni component, the K component, and the S component entered the inside of the hexagonal mesoporous material support C3 during the supporting 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 a hexagonal mesoporous material carrier C4 is 68 wt%.
The hexagonal mesoporous material carrier C4 and the non-noble metal isobutane dehydrogenation catalyst Cat-4 are characterized by an XRD, a scanning electron microscope, an ASAP2020-M + C type adsorption instrument and a laser particle size distribution instrument.
Table 4 shows the pore structure parameters of the hexagonal mesoporous material carrier C4 and the non-noble metal isobutane dehydrogenation catalyst Cat-4.
TABLE 4
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Pore diameter of the most probable (nm) | Particle size (. mu.m) |
| Vector C4 | 598 | 0.7 | 4.8 | 0.8-10 |
| Catalyst Cat-4 | 555 | 0.52 | 3.4 | 0.8-12.3 |
As can be seen from the data of table 4, the hexagonal mesoporous material support C4 has a reduced specific surface area and pore volume after supporting the Fe component, Na component and S component, which indicates that the Fe component, Na component and S component enter the inside of the hexagonal mesoporous material support C4 during the supporting 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 is 11.5 wt% calculated by an iron element, the content of a sodium component is 2.5 wt% calculated by a sodium element, and the content of a hexagonal 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 is 8.5 wt% calculated by an iron element, the content of a sodium component is 1.1 wt% calculated by a sodium element, the content of a sulfur component is 1 wt% calculated by a sulfur element, and the content of a hexagonal 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) And (3) replacing the nickel nitrate hexahydrate, namely, taking an active component loaded by the hexagonal 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 a hexagonal 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, and 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 20.9%, and the initial selectivity of isobutene is improved from 72.1% to 91.8%; 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 the comparative test example 1 and the 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-metal active component and the sulfur component on the hexagonal mesoporous material carrier is equivalent to that of the isobutane dehydrogenation catalyst obtained by loading the toxic metal active component Cr component and the alkali metal component on the hexagonal 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 (12)
1. A method for preparing a non-noble metal isobutane dehydrogenation catalyst is characterized by comprising the following steps:
(a) mixing and contacting a template agent, potassium sulfate, an acid agent and tetraethoxysilane, and crystallizing and filtering the obtained mixture to obtain hexagonal mesoporous material raw powder with a cubic center Im3m structure;
(b) sequentially carrying out template agent treatment and thermal activation treatment on the hexagonal mesoporous material raw powder to obtain a hexagonal mesoporous material carrier;
(c) under the ultrasonic condition, dipping the hexagonal mesoporous material carrier in 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 method of claim 1, wherein in step (a), the molar ratio of the templating agent, potassium sulfate, and ethyl orthosilicate is 1: 100-800: 20-200 parts of;
preferably, the templating agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO132PO60EO132(ii) a The acid agent is hydrochloric acid;
more preferably, the conditions of the mixing contact include: the temperature is 25-60 deg.C, the time is 10-240min, and the pH value is 1-7; the crystallization conditions include: the temperature is 25-60 ℃, and the time is 10-72 h.
3. The method of claim 1 wherein in step (b) the stripper plate agent treatment process comprises: calcining the hexagonal mesoporous material raw powder for 8-20h at the temperature of 300-600 ℃.
4. The process according to claim 1, wherein in step (c) the hexagonal mesoporous material support and the solution comprising the first active non-noble metal component precursor and the second active non-noble metal component precursor are used in amounts such that the non-noble metal based isobutane dehydrogenation catalyst is prepared in a content of the first active non-noble metal component of 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 hexagonal 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 (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-;
the drying conditions include: the temperature is 60-150 ℃, preferably 80-130 ℃; the time is 1 to 20 hours, preferably 3 to 15 hours;
the roasting conditions comprise: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10 h.
7. 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.
8. The non-noble metal-based isobutane dehydrogenation catalyst with a support of hexagonal mesoporous material prepared by the method of any one of claims 1 to 7.
9. The non-noble metal-based isobutane dehydrogenation catalyst according to claim 8, wherein said non-noble metal-based isobutane dehydrogenation catalystThe 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 carrier is a hexagonal mesoporous material carrier, the hexagonal mesoporous material carrier has a cubic cage-shaped pore channel structure, the crystal structure of the hexagonal mesoporous material carrier has a cubic-centered Im3m structure, the most probable pore diameter of the hexagonal mesoporous material carrier is 4-15nm, and the specific surface area is 550-650 m-2Pore volume of 0.5-1.5mL/g, and average particle diameter of 0.5-10 μm.
10. Non-noble metal-based isobutane dehydrogenation catalyst according to claim 9, 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 hexagonal mesoporous material carrier is 63-98 wt%, and preferably 73-96.3 wt%.
11. Use of a non-noble metal-based isobutane dehydrogenation catalyst according to any one of claims 8 to 10 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.
12. Use according to claim 11, wherein the conditions of the isobutane dehydrogenation reaction comprise: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, and the mass space velocity of the isobutane is 2-5h-1。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614097A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof |
| CN115337955A (en) * | 2021-05-12 | 2022-11-15 | 中国石油化工股份有限公司 | Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation |
| CN115487854B (en) * | 2021-06-18 | 2023-07-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB467470A (en) * | 1935-12-09 | 1937-06-17 | Bataafsche Petroleum | A process for the catalytic dehydrogenation of aliphatic hydrocarbons |
| CN102039183A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Metallocene catalyst-loaded hexagonal mesoporous material and preparation method thereof |
| CN102198948A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing mesoporous molecular sieve Fe-MCM-41 with high iron content |
| CN103521254A (en) * | 2013-10-25 | 2014-01-22 | 凯瑞化工股份有限公司 | Catalyst for catalyzing isobutane to dehydrogenize to synthesize isobutene as well as preparation method of catalyst |
| CN103861619A (en) * | 2012-12-11 | 2014-06-18 | 江苏省海洋石化股份有限公司 | Alkane dehydrogenation sulfide catalyst and alkane dehydrogenation method |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN106563452A (en) * | 2016-10-09 | 2017-04-19 | 华南理工大学 | Iron catalyst for isobutylene preparation through catalytic dehydrogenation of isobutane, preparation method and applications thereof |
| US20170247302A1 (en) * | 2014-09-29 | 2017-08-31 | Haldor Topsøe A/S | Dehydrogenation of alkanes to alkenes |
| CN108786800A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
-
2018
- 2018-11-30 CN CN201811457384.4A patent/CN111250096A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB467470A (en) * | 1935-12-09 | 1937-06-17 | Bataafsche Petroleum | A process for the catalytic dehydrogenation of aliphatic hydrocarbons |
| CN102039183A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Metallocene catalyst-loaded hexagonal mesoporous material and preparation method thereof |
| CN102198948A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing mesoporous molecular sieve Fe-MCM-41 with high iron content |
| CN103861619A (en) * | 2012-12-11 | 2014-06-18 | 江苏省海洋石化股份有限公司 | Alkane dehydrogenation sulfide catalyst and alkane dehydrogenation method |
| CN103521254A (en) * | 2013-10-25 | 2014-01-22 | 凯瑞化工股份有限公司 | Catalyst for catalyzing isobutane to dehydrogenize to synthesize isobutene as well as preparation method of catalyst |
| US20170247302A1 (en) * | 2014-09-29 | 2017-08-31 | Haldor Topsøe A/S | Dehydrogenation of alkanes to alkenes |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst used for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN106563452A (en) * | 2016-10-09 | 2017-04-19 | 华南理工大学 | Iron catalyst for isobutylene preparation through catalytic dehydrogenation of isobutane, preparation method and applications thereof |
| CN108786800A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
Non-Patent Citations (1)
| Title |
|---|
| 周庆祥等: "异丁烷直接脱氢制异丁烯的催化剂的研究进展", 《化学通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614097A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being composite material containing silica gel and hexagonal mesoporous material, and preparation method and application thereof |
| CN115337955A (en) * | 2021-05-12 | 2022-11-15 | 中国石油化工股份有限公司 | Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation |
| CN115337955B (en) * | 2021-05-12 | 2024-02-20 | 中国石油化工股份有限公司 | Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation |
| CN115487854B (en) * | 2021-06-18 | 2023-07-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method and application thereof |
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