CN115337955A - Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation - Google Patents

Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation Download PDF

Info

Publication number
CN115337955A
CN115337955A CN202110517357.7A CN202110517357A CN115337955A CN 115337955 A CN115337955 A CN 115337955A CN 202110517357 A CN202110517357 A CN 202110517357A CN 115337955 A CN115337955 A CN 115337955A
Authority
CN
China
Prior art keywords
metal component
dehydrogenation catalyst
kit
catalyst
novel
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.)
Granted
Application number
CN202110517357.7A
Other languages
Chinese (zh)
Other versions
CN115337955B (en
Inventor
刘红梅
刘东兵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN202110517357.7A priority Critical patent/CN115337955B/en
Publication of CN115337955A publication Critical patent/CN115337955A/en
Application granted granted Critical
Publication of CN115337955B publication Critical patent/CN115337955B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the field of catalysts, and discloses a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparation of isobutene through isobutane dehydrogenation. The novel dehydrogenation catalyst comprises a carrier and a first metal component, a second metal component and a non-metal component which are loaded on the carrier; wherein the carrier is Al 2 O 3 -KIT-6 cubic composite, and the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%, based on the total weight of the novel dehydrogenation catalyst. The novel dehydrogenation catalyst can achieve better isobutane dehydrogenation activity, isobutene selectivity and stability under the condition of not using noble metals and metal components seriously polluted.

Description

Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation
Technical Field
The invention relates to the field of catalysts, in particular to a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparation of isobutene through isobutane dehydrogenation.
Background
Isobutene is an important basic petrochemical raw material, has wide application, and can be used for synthesizing various organic raw materials and fine chemicals such as methyl tert-butyl ether, ethyl tert-butyl ether, butyl rubber, polyisobutylene, methacrylate, methyl methacrylate, isoprene, tert-butyl phenol, tert-butylamine, 1, 4-butanediol, ABS resin and the like. However, isobutene has no natural source and mainly comes from C in catalytic cracking liquefied petroleum gas 4 Component C and byproduct C in ethylene preparation by naphtha steam cracking 4 C in olefins and natural gas 4 And (4) components. In the above-mentioned background, the dehydrogenation of isobutane to isobutene becomes one of the important ways to increase the source of isobutene. At present, there are three main reaction routes developed in the research field of isobutene preparation by isobutane dehydrogenation: (1) direct dehydrogenation of isobutane; (2) oxidative dehydrogenation of isobutane; and (3) carrying out membrane catalytic dehydrogenation on the isobutane. The technology for preparing isobutene by direct catalytic dehydrogenation of isobutane realizes industrial production in 90 years in the 20 th century, and the main technologies comprise a Catofin process developed by ABB Lummus company, an Oleflex process developed by UOP company, a Star process developed by Phillips company, an FBD-4 process developed by Snamprogetti-Yarsintez company and a Linde process developed by Linde company. The five processes all use Pt (Oleflex and Star process) or Cr (Catofin, FBD-4 and Linde process) catalysts. The noble metal catalyst has high activity and good selectivity, and is more environment-friendly. However, it is possible to use a single-layer,the Pt-based catalyst has the disadvantages of complex operation process, high operation requirement and high cost. Relatively speaking, cr series catalysts are low in price, but the catalysts are easy to deposit carbon, are quick in deactivation and need frequent regeneration, once leakage happens, environmental pollution is caused, and carcinogen Cr is generated 6+ It is not favorable for environmental protection. Therefore, for various processes for preparing isobutene by isobutane dehydrogenation, the development of a catalyst which does not use a non-metal component with serious environmental pollution, has high dehydrogenation catalytic activity and good stability is a main technical problem to be solved urgently at present.
Many studies have been made to improve various performance indexes of the Cr-based dehydrogenation catalyst. Such as: the catalytic performance of the Cr catalyst is improved by a method of adding an auxiliary agent (CN 104549220A), the addition of a Cr component is avoided by the development of a multi-component catalyst formula (CN 102451677B and CN 104607168A), and the reaction performance of a non-noble metal dehydrogenation catalyst is improved by the improvement of a catalyst preparation method (ACS Catal.2015,5, 3494-3503).
Although the prior art improves the industrial application of Cr catalysts to a certain extent, the problems of complex catalyst components, complex preparation process and further improvement of catalyst performance still exist.
Disclosure of Invention
The invention aims to overcome the defects that the existing catalyst for preparing isobutene by dehydrogenating isobutane has high cost or is easy to cause environmental pollution, and provides a novel dehydrogenation catalyst, a preparation method thereof and application thereof in preparing isobutene by dehydrogenating isobutane.
In order to achieve the above object, a first aspect of the present invention provides a novel dehydrogenation catalyst, wherein the novel dehydrogenation catalyst comprises a support, and a first metal component, a second metal component and a non-metal component supported on the support; wherein the carrier is Al 2 O 3 -KIT-6 cubic composite, and the first based on the total weight of the novel dehydrogenation catalystThe content of the metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the nonmetal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%.
In a second aspect, the present invention provides a preparation method of the above-mentioned novel dehydrogenation catalyst, wherein the preparation method comprises: under the ultrasonic-assisted condition, a solution containing a first metal component precursor and a second metal component precursor is mixed with Al 2 O 3 Contacting the KIT-6 cubic structure composite material, performing immersion treatment, removing the solvent, drying and roasting to obtain an initial catalyst; and then contacting the initial catalyst with sulfur-containing gas for sulfurization treatment to obtain the novel dehydrogenation catalyst.
The third aspect of the invention provides an application of the novel dehydrogenation catalyst in the reaction of preparing isobutene by dehydrogenating isobutane.
Through the technical scheme, the technical scheme provided by the invention has the following advantages:
(1) The novel dehydrogenation catalyst does not contain noble metals, and can effectively reduce the preparation cost of the dehydrogenation catalyst;
(2) The novel dehydrogenation catalyst disclosed by the invention does not contain chromium element, and is environment-friendly;
(3) The novel dehydrogenation catalyst shows good catalytic performance when used for preparing isobutene by isobutane dehydrogenation, and has high isobutane conversion rate, high isobutene selectivity and good catalyst stability;
(4) The preparation method of the novel dehydrogenation catalyst is simple in process, easy in condition control and good in product repeatability.
Drawings
FIG. 1 is Al prepared in example 1 2 O 3 -small angle XRD spectrum of KIT-6 cubic composite a;
FIG. 2 shows Al prepared in example 1 2 O 3 -wide angle XRD spectrum of KIT-6 cubic composite a;
FIG. 3 shows Al prepared in example 1 2 O 3 Distribution of pore size of-KIT-6 cubic composite A。
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.
The invention provides, in a first aspect, a novel dehydrogenation catalyst, wherein the novel dehydrogenation catalyst comprises a carrier and, supported on the carrier, a first metal component, a second metal component and a non-metal component; wherein the carrier is Al 2 O 3 -KIT-6 cubic composite, and the content of the first metal component is 3-25 wt%, the content of the second metal component is 0.1-10 wt%, the content of the non-metal component is 0.1-5 wt%, and the content of the carrier is 60-97 wt%, based on the total weight of the novel dehydrogenation catalyst.
The inventors of the present invention, when conducting an isobutane dehydrogenation catalyst preparation study, found that: compared with the Pt-based dehydrogenation catalyst, the Cr-based catalyst is lower in cost, but is inferior in stability and serious in pollution. In order to maintain low catalyst cost while considering environmental requirements, non-noble metal elements have been used in the prior art to replace Cr to prepare dehydrogenation catalysts. However, the performance of the substitute catalyst still can not completely reach the level of Cr-series catalysts, and is mainly reflected in the aspects of low selectivity, poor stability and the like. For non-noble metal catalysts, pure metal components are readily formed if the oxidized metal component is deeply reduced in the reducing atmosphere of the isobutane dehydrogenation reaction. While the pure metal component has very strong dehydrogenation performance, which leads to deep dehydrogenation or hydrogenolysis of isobutane, the selectivity of isobutene is seriously reduced. In addition, in the prior art, the gamma-alumina or silicon oxide is used as a carrier to load a non-noble metal component to prepare the isobutane dehydrogenation catalyst, so that the defects of poor olefin selectivity and poor stability exist.
The inventors of the present invention have surprisingly found that: although the alumina carrier or the silica carrier sold in the market is low in price, the pore size distribution is uneven, the specific surface area is small, and the dispersion of active metal components on the surface of the carrier and the diffusion of raw materials and products in the reaction process are not facilitated. In comparison, the mesoporous molecular sieve KIT-6 has large specific surface area, large pore volume and uniform pore channel size, and is more favorable for the diffusion of reactant molecules and product molecules in the reaction. However, the KIT-6 molecular sieve has a small bulk density, and the volume of the prepared catalyst is too large, so that the industrial application of the catalyst is limited. The inventor of the invention finds that the advantage of good caking property of the alumina is utilized to combine the structural characteristics of the alumina and the KIT-6 molecular sieve to prepare the formed Al 2 O 3 the-KIT-6 cubic structure composite material is further prepared into the isobutane dehydrogenation catalyst, so that the current situation of poor performance of the isobutane dehydrogenation catalyst in the prior art can be effectively improved.
Further, the inventors of the present invention found that: 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.
Further, the inventors of the present invention found that: if a small amount of alkali metal or alkaline earth metal is introduced to the surface of the isobutane dehydrogenation catalyst, a small amount of acid centers on the surface of a catalyst carrier can be effectively balanced, so that the occurrence of side reactions is reduced, and the selectivity of a target product is improved.
According to the present invention, it is preferred that the first metal component is present in an amount of from 5 to 20 wt.%, the second metal component is present in an amount of from 0.5 to 5 wt.%, the non-metal component is present in an amount of from 0.2 to 2 wt.%, and the support is present in an amount of from 72 to 95 wt.%, based on the total weight of the novel dehydrogenation catalyst; more preferably, the first metal component is present in an amount of 6.2 to 19.2 wt.%, the second metal component is present in an amount of 0.5 to 3.9 wt.%, the non-metal component is present in an amount of 0.7 to 1.7 wt.%, and the support is present in an amount of 75.2 to 92.6 wt.%, based on the total weight of the novel dehydrogenation catalyst. In the invention, the contents of the first metal component, the second metal component, the nonmetal component and the carrier are limited to be in the aforementioned ranges, so that the requirements on the quantity and quality of active centers on the surface of the catalyst can be met, and the diffusion of reactant molecules and product molecules can be promoted through a special carrier pore channel structure.
According to the invention, the Al 2 O 3 The specific surface area of the-KIT-6 cubic structure composite material is 300-700m 2 The pore volume is 0.6-1.4mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7-9nm and 10-15nm respectively; preferably, the Al 2 O 3 The specific surface area of the-KIT-6 composite material is 483-545m 2 The pore volume is 0.9-1.1mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7.8-8.2nm and 11.8-12.5nm respectively.
According to the invention, the first metal component is selected from one or more of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper; preferably, the first metal component is selected from one or more of iron, nickel, zinc, molybdenum and tin; more preferably, the non-noble metal is selected from one or more of iron, nickel and zinc.
According to the invention, the second metal component is an alkali metal and/or an alkaline earth metal; preferably, the second metal component is selected from one or more of sodium, magnesium, potassium, calcium and lithium; more preferably, the second metal component is selected from one or more of sodium, magnesium and potassium.
According to the invention, the non-metallic component is S.
According to the invention, the Al 2 O 3 The preparation method of the KIT-6 cubic structure composite material comprises the following steps:
(1) Under the condition of hydrolysis gel making, a template solvent, a silicon source, n-butanol and hydrochloric acid are contacted and mixed to obtain a gel mixture; crystallizing the gel mixture; then, filtering, washing, first drying and first roasting the crystallized product to obtain a KIT-6 mesoporous molecular sieve;
(2) Mixing the KIT-6 mesoporous molecular sieve, the alumina precursor and the extrusion aid in the presence of dilute nitric acid, then carrying out extrusion forming, carrying out second drying and second roasting treatment to obtain Al 2 O 3 -KIT-6 cubic structure composite.
According to the invention, the template agent is a non-ionic surfactant; preferably, the templating agent is a polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer; more preferably P123 (formula EO) 20 PO 70 EO 20 )。
According to the invention, the silicon source is a silicon-containing organic compound and/or a silicon-containing inorganic compound; preferably a silicon-containing organic compound; more preferably one or more of ethyl orthosilicate, methyl orthosilicate, or butyl orthosilicate.
According to the invention, the molar ratio of the amounts of the plate agent, the silicon source, the n-butanol, the hydrochloric acid and the water is 1: (10-150): (20-200): (200-1200): (5000-20000); preferably 1: (30-100): (50-120): (500-900): (8000-13500).
According to the invention, the conditions for preparing the glue by hydrolysis comprise: the temperature is 20-50 deg.C, and the time is 5-30h.
According to the present invention, the crystallization conditions include: the temperature is 80-120 ℃, and the time is 10-40h. As is well known to those skilled in the art, the crystallization is generally carried out in a hydrothermal kettle, and will not be described herein.
According to the present invention, there is no particular requirement for the filtration process, and filtration means known in the art may be used, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the filtering process specifically includes: using a filter flask, vacuumizing the bottom side of the funnel or filtering by using a centrifugal filter.
According to the present invention, the washing process may include: after filtration, a solid product is obtained, which is repeatedly washed with distilled water (the number of washing times may be 2 to 10 times), and then subjected to suction filtration.
According to the invention, the conditions of the first drying comprise: the temperature is 70-140 ℃ and the time is 4-20h.
According to the invention, the conditions of the first firing include: the temperature is 400-600 ℃, and the time is 8-60h.
According to the invention, the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; the extrusion aid is one or more of sesbania powder, polyacrylamide or cellulose, and preferably sesbania powder.
According to the invention, the dilute nitric acid may have a mass concentration of 1 to 20%, preferably 2 to 10%.
According to the invention, the weight ratio of the usage amounts of the KIT-6 mesoporous molecular sieve, the alumina precursor, the extrusion aid and the dilute nitric acid is 1: (0.3-5): (0.02-0.5): (0.2-5), preferably 1: (0.5-3): (0.05-0.2): (0.5-2).
According to the present invention, the conditions of the second drying include: the temperature is 70-150 ℃ and the time is 3-16h.
According to the present invention, the conditions of the second firing include: the temperature is 450-650 ℃, and the time is 3-15h.
In a second aspect, the present invention provides a preparation method of the above-mentioned novel dehydrogenation catalyst, wherein the preparation method comprises: under the ultrasonic-assisted condition, a solution containing a first metal component precursor and a second metal component precursor is mixed with Al 2 O 3 -contacting a KIT-6 cubic structure composite material, performing immersion treatment, removing a solvent, drying and roasting to obtain an initial catalyst; and then contacting the initial catalyst with sulfur-containing gas for sulfurization treatment to obtain the novel dehydrogenation catalyst.
According to the invention, the ultrasound-assisted conditions comprise: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-300W; preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
According to the invention, the impregnation conditions include: the temperature is 20-100 ℃, preferably 40-80 ℃; the time is 0.5-10h, preferably 2-8h. In the present invention, co-impregnation and/or stepwise impregnation may be used.
According to the present invention, the first metal component precursor is selected from nitrates, sulfites, sulfates or metal chlorides containing one or more elements of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper.
According to the present invention, the second metal component precursor is selected from nitrates, sulfites, sulfates or metal chlorides containing alkali metals and/or alkaline earth metals.
According to the present invention, the solution containing the first metal component precursor and the second metal component precursor is an aqueous solution or an ethanol solution containing the metal component precursor; the mass concentration of the solution is preferably 0.5 to 10%.
According to the present invention, the method for removing the solvent is not particularly limited, and may be a method known in the art, such as: the solvent is removed by evaporation using a rotary evaporator or by heating with stirring.
According to the invention, the conditions of drying include: the temperature is 60-150 ℃, preferably 80-130 ℃; the time is 1-20h, preferably 3-15h.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10h.
According to the invention, the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1-5%, preferably 0.3-2%.
According to the invention, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃, and the time is 1-15h; preferably, the treatment conditions include: the temperature is 450-650 ℃, and the time is 2-8h.
The novel dehydrogenation catalysts according to the present invention may be in the shape of spheres, pellets, bars, cylinders, and the like.
The third aspect of the invention provides an application of the novel dehydrogenation catalyst in the reaction of preparing isobutene by dehydrogenating isobutane.
According to the invention, said application comprises: the reaction raw material isobutane is contacted with the novel dehydrogenation catalyst.
According to the invention, the contact conditions comprise: the contact temperature is 500-650 ℃, the partial pressure of the raw material gas is 0.02-0.5MPa, and the mass space velocity of the propane is 1.0-10.0h -1 。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) The pore structure parameter analysis of the samples was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA. The samples were degassed at 350 ℃ for 4 hours under vacuum prior to measurement, and the specific surface area of the samples was calculated by the BET method and the pore volume calculated by the BJH model.
(2) The elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, USA.
(3) The ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner produced by ultrasonic instruments Limited in Kunshan, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
(4) The rotary evaporator is produced by German IKA company and has the model of RV10 digital;
(5) The drying box is produced by Shanghai-Hengheng scientific instruments Co., ltd., model number DHG-9030A.
(6) The muffle furnace is manufactured by CARBOLITE corporation, model CWF1100.
(7) The reagents used in the examples and comparative examples were purchased from national pharmaceutical group chemical agents, ltd, and the purity of the reagents was analytical grade.
(8) The isobutane conversion was calculated as follows:
isobutane conversion = amount of isobutane consumed for reaction/initial amount of isobutane × 100%;
the isobutene selectivity was calculated as follows:
isobutylene selectivity = amount of isobutane consumed for production of isobutylene/total consumption of isobutane × 100%.
Example 1
This example is intended to illustrate the supports, supported catalysts and applications prepared by the process of the present invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Dissolving 11.6g of triblock copolymer surfactant P123 in 4113.9M hydrochloric acid solution at the temperature of 35 ℃, and stirring for 4 hours until the P123 is completely dissolved to form a transparent solution; adding 11.8g of n-butanol into the solution and continuing stirring for 1 hour; then, 25g of ethyl orthosilicate was slowly added dropwise to the solution, and stirred at 35 ℃ for 24 hours to obtain a gel mixture. And transferring the gel mixture to a hydrothermal reaction kettle, and crystallizing for 24 hours at 100 ℃. And repeatedly washing and filtering the crystallized product by using deionized water to obtain a KIT-6 mesoporous material filter cake. Drying the KIT-6 mesoporous material filter cake at 100 ℃ for 12h, and calcining at 500 ℃ for 24h to remove the template agent to obtain the KIT-6 mesoporous molecular sieve A.
Uniformly mixing 250g of the KIT-6 mesoporous molecular sieve A prepared in the step with 300g of pseudo-boehmite and 25g of sesbania powder, adding 380g of 5% dilute nitric acid, uniformly stirring, performing extrusion forming, and cutting into cylinders with the diameter of 2mm and the length of 1-2 mm; drying at 100 deg.C for 10h, and calcining at 600 deg.C for 6h to obtain Al 2 O 3 -KIT-6 cubic composite a.
For Al 2 O 3 -KIT-6 cubic composite A, the pore structure parameters of which are listed in Table 1.
FIG. 1 is Al prepared in example 1 2 O 3 -a small angle XRD spectrum of KIT-6 cubic structure mesoporous molecular sieve a; al is known from small-angle spectral peaks appearing in XRD spectrogram 2 O 3 The ordered mesoporous part of the mesoporous molecular sieve A with the-KIT-6 cubic structure has a typical three-dimensional cubic mesoporous structure.
FIG. 2 shows Al prepared in example 1 2 O 3 The wide-angle XRD pattern of the mesoporous molecular sieve A with the KIT-6 cubic structure can be seen from figure 2: the typical gamma-alumina diffraction pattern is shown in a wide-angle XRD spectrogram, which indicates the disordered pore channel of the alumina-two-dimensional hexagonal mesoporous molecular sieve composite material AThe part of the material is composed of alumina, and the crystalline phase structure of the alumina is gamma-alumina.
FIG. 3 is Al prepared in example 1 2 O 3 -a pore size distribution profile of KIT-6 cubic composite a, the pore size of the sample being bimodal, the first mode pore size being 8nm, contributed mainly by the mesoporous molecular sieve; the second mode pore size is 12nm, mainly contributed by alumina.
(2) Novel dehydrogenation catalyst preparation
10.4g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of anhydrous ethanol, and mixed with 10g of Al 2 O 3 Mixing the-KIT-6 cubic structure composite material A, and stirring and reacting for 60min under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, the solvent ethanol in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was dried for 5h in a drying cabinet at 100 ℃. Then calcined in a muffle furnace at 550 ℃ for 5h to obtain the initial catalyst A.
Taking 10g of the above-mentioned initial catalyst A in H 2 Treating the mixture for 5 hours at 550 ℃ in nitrogen gas flow with the S content of 1.5 percent to obtain the novel dehydrogenation catalyst A.
The novel dehydrogenation catalyst A comprises the following components in percentage by weight: 13.4 percent of iron element, 2.5 percent of sodium element, 1.3 percent of sulfur element and the balance of carrier.
(3) Performance evaluation of catalyst in reaction for preparing isobutene by dehydrogenating isobutane
The evaluation of the reaction performance of the catalyst was carried out on a fixed bed reactor. 2.0 g of catalyst A was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 580 ℃, the reaction pressure was 0.1MPa, isobutane: the molar ratio of helium is 1:1, the mass space velocity of the isobutane is 2.0h-1, and the reaction time is 6h. By Al 2 O 3 The reaction product separated by the S molecular sieve column directly enters an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis.
The reaction results are shown in Table 3. 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.
Example 2
This example is intended to illustrate supports, supported catalysts and applications prepared by the process of the present invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 -KIT-6 parameters of the preparation of the cubic composite, example 2, obtaining Al 2 O 3 -KIT-6 cubic composite B.
Al 2 O 3 The structural parameters of KIT-6 cubic composite B are listed in Table 1.
(2) Novel dehydrogenation catalyst preparation
10.4g of iron nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of absolute ethanol, and 10g of Al 2 O 3 Mixing the-KIT-6 cubic structure composite material A, and stirring and reacting for 60min under the assistance of ultrasonic waves with the power of 200W, wherein the temperature is 50 ℃. After the reaction is finished, the solvent ethanol in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was placed in a drying cabinet at 100 ℃ and dried for 5h. Then calcined in a muffle furnace at 550 ℃ for 5h to obtain the initial catalyst A.
0.53g of magnesium nitrate hexahydrate was dissolved in 70ml of deionized water, and 10g of Al 2 O 3 Mixing the-KIT-6 cubic structure composite material B, and stirring and reacting for 30min at 80 ℃ under the assistance of ultrasonic waves with the power of 250W. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was placed in a drying cabinet at 80 ℃ and dried for 15h. Then roasting the mixture for 3 hours in a muffle furnace at the temperature of 650 ℃ to obtain Mg-Al 2 O 3 -KIT-6 sample. 9.20g of zinc nitrate hexahydrate was dissolved in 150mL of deionized water with the Mg-Al solution described above 2 O 3 Mixing the-KIT-6 samples, and stirring and reacting for 30min under the assistance of ultrasonic waves with the power of 250W, wherein the temperature is 80 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. Drying the solid product at 80 deg.CAnd drying for 15h in the box. Then calcined in a muffle furnace at 650 ℃ for 3h to obtain the initial catalyst B.
Taking 10g of the above-mentioned initial catalyst B in H 2 Treating the mixture for 8 hours at 450 ℃ in nitrogen gas flow with the S content of 2.0 percent to obtain the novel dehydrogenation catalyst B.
The novel dehydrogenation catalyst B comprises the following components in percentage by weight: 19.2 percent of zinc element, 0.5 percent of magnesium element, 1.7 percent of sulfur element and the balance of carrier.
(3) Performance evaluation of catalyst in reaction for preparing isobutene through isobutane dehydrogenation
The performance of the reaction for preparing isobutene by dehydrogenating isobutane with the catalyst B was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Example 3
This example is intended to illustrate the supports, supported catalysts and applications prepared by the process of the present invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 Example 3 was carried out for each parameter in the preparation of 3-KIT-6 cubic composite to obtain Al 2 O 3 -KIT-6 cubic composite material C. Al (Al) 2 O 3 The structural parameters of KIT-6 cubic composite C are listed in Table 1.
(2) Novel dehydrogenation catalyst preparation
10.4g of ferric nitrate nonahydrate and 0.93g of sodium nitrate were dissolved in 100g of absolute ethanol, mixed with 10g of A, and reacted for 60min with stirring under the assistance of ultrasonic waves of 200W at a temperature of 50 ℃. After the reaction is finished, the solvent ethanol in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was placed in a drying cabinet at 100 ℃ and dried for 5h. Then calcined in a muffle furnace at 550 ℃ for 5h to obtain the initial catalyst A.
3.12g of nickel nitrate hexahydrate was dissolved in 100mL of deionized water with 10gAl 2 O 3 Mixing the-KIT-6 cubic structure composite material C, stirring and reacting for 120min under the assistance of ultrasonic waves with the power of 150W, wherein the temperature isAt 20 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 130 ℃ and dried for 3h. Then roasting the mixture for 10 hours in a muffle furnace at the temperature of 500 ℃ to obtain Ni-Al 2 O 3 -KIT-6 sample. 0.79g of potassium chloride was dissolved in 100mL of deionized water, and mixed with the above Ni-Al 2 O 3 Mixing the-KIT-6 samples, and stirring and reacting for 120min under the assistance of ultrasonic waves with the power of 150W, wherein the temperature is 20 ℃. After the reaction is finished, water in the system is distilled off by a rotary evaporator to obtain a solid product. The solid product was placed in a drying cabinet at 130 ℃ and dried for 3h. Then calcined in a muffle furnace at 500 ℃ for 10h to obtain the initial catalyst C.
10g of the above-mentioned initial catalyst C were taken and treated at 650 ℃ for 2H in a stream of nitrogen having a H2S content of 1.0% to give the novel dehydrogenation catalyst C.
The novel dehydrogenation catalyst C comprises the following components in percentage by weight: 6.2 percent of nickel element, 3.9 percent of potassium element, 0.7 percent of sulfur element and the balance of carrier.
(3) Performance evaluation of catalyst in reaction for preparing isobutene through isobutane dehydrogenation
The performance of the isobutane dehydrogenation catalyst C for the preparation of isobutene was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Example 4
This example is intended to illustrate supports, supported catalysts and applications prepared by the process of the present invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 -KIT-6 respective parameters of the process for the preparation of a composite material with cubic structure, example 4 being carried out, al being obtained 2 O 3 -KIT-6 cubic composite D.
Al 2 O 3 The structural parameters of KIT-6 cubic composite D are set forth in Table 1.
(2) Novel dehydrogenation catalyst preparation
The conditions in the preparation of the novel dehydrogenation catalyst in step (2) of example 1 were changed so that the specific gravity of each component of the prepared novel dehydrogenation catalyst D was: 4.2 percent of iron element, 7.3 percent of sodium element, 3.4 percent of sulfur element and the balance of carrier.
(3) Performance evaluation of catalyst in reaction for preparing isobutene by dehydrogenating isobutane
The performance of the reaction for preparing isobutene by dehydrogenating isobutane with the catalyst D was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Example 5
This example is intended to illustrate supports, supported catalysts and applications prepared by the process of the present invention.
(1)Al 2 O 3 Preparation of-KIT-6 cubic structure composite material
Modification of Al in step (1) of example 1 2 O 3 -KIT-6 respective parameters of the process for the preparation of a composite material with cubic structure, example 5 being carried out, al being obtained 2 O 3 -KIT-6 cubic composite material E.
Al 2 O 3 The structural parameters of KIT-6 cubic composite E are listed in Table 1.
(2) Novel dehydrogenation catalyst preparation
The conditions in the preparation of the novel dehydrogenation catalyst in step (2) of example 1 were changed so that the specific gravity of each component of the prepared novel dehydrogenation catalyst D was: 27.1 weight percent of iron element, 0.4 weight percent of sodium element, 0.3 weight percent of sulfur element and the balance of carrier.
(3) Performance evaluation of catalyst in reaction for preparing isobutene by dehydrogenating isobutane
The performance of the catalyst E for the reaction of preparing isobutene by dehydrogenating isobutane was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Comparative example 1
A supported catalyst D1 was prepared in the same manner as in example 1, except that: step (1) of example 1 was eliminated and in step (2), commercial alumina was used in place of Al 2 O 3 -KIT-6 cubic composite a as a catalyst support; and with catalyst D1Based on the total weight, the content of metallic element iron is 13.4 weight percent, the content of metallic element sodium is 2.5 weight percent, the content of S is 1.3 weight percent, and the rest is carrier alumina.
The performance of the reaction for preparing isobutene by dehydrogenating isobutane with the catalyst D1 was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Comparative example 2
A supported catalyst D2 was prepared in the same manner as in example 1, except that: the catalyst preparation conditions were adjusted so that the content of the metallic element iron was 1.5% by weight, the content of the metallic element sodium was 0.3% by weight, the content of S was 3.0% by weight, and the balance was the carrier, based on the total weight of the catalyst D2.
The performance of the reaction for preparing isobutene by dehydrogenating isobutane with the catalyst D2 was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
Comparative example 3
A supported catalyst D3 was prepared in the same manner as in example 1, except that: the sulfidation treatment of the initial catalyst was eliminated so that the content of the metallic element iron was 13.4 wt%, the content of the metallic element sodium was 2.5 wt%, and the balance was the carrier, based on the total weight of the catalyst D3.
The performance of the reaction for preparing isobutene by dehydrogenating isobutane with the catalyst D3 was tested according to the method of step (3) in example 1, and the reaction results are shown in table 2.
TABLE 1
Figure BDA0003062140340000161
Figure BDA0003062140340000171
TABLE 2
Figure BDA0003062140340000181
As can be seen from Table 3, the novel dehydrogenation catalyst prepared by the method of the present invention has excellent performance when used in the reaction of preparing isobutene by dehydrogenating isobutane. As a result of comparing the experimental results of test example 1 and comparative example 1, it was found that Al was used 2 O 3 The performance of the catalyst A prepared from the-KIT-6 cubic structure composite material is obviously superior to that of the catalyst D1 prepared from commercial alumina serving as a carrier, and the alkane conversion rate, the olefin selectivity and the catalyst stability are greatly improved. The above results show that Al 2 O 3 The KIT-6 cubic structure composite material is more beneficial to the reaction of preparing isobutene by dehydrogenating isobutane. The experimental results of the comparative test example 1 and the comparative example 3 show that the performance of the catalyst A subjected to the vulcanization treatment is obviously superior to that of the catalyst D3 without sulfur, and the conversion rate of isobutene and the selectivity of isobutene are obviously improved; the performance of catalyst A hardly decreased during the 6-hour reaction, while the isobutene conversion and isobutene selectivity of D1 catalyst were both significantly decreased. The above results indicate that the presence of S element on the surface of the catalyst is effective in improving the dehydrogenation activity of the catalyst, the selectivity of the objective olefin and the stability of the catalyst.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A novel dehydrogenation catalyst comprising a support and, supported on said support, a first metal component, a second metal component and a non-metal component; wherein the carrier is Al 2 O 3 -KIT-6 cubic composite and the content of the first metal component is 3 to 25 wt%, the content of the second metal component is 0.1 to 10 wt%, and the content of the non-metal component is 0, based on the total weight of the novel dehydrogenation catalyst.1-5 wt%, and the content of the carrier is 60-97 wt%.
2. The novel dehydrogenation catalyst of claim 1 wherein the first metal component is present in an amount of from 5 to 20 weight percent, the second metal component is present in an amount of from 0.5 to 5 weight percent, the non-metal component is present in an amount of from 0.2 to 2 weight percent, and the support is present in an amount of from 72 to 95 weight percent, based on the total weight of the novel dehydrogenation catalyst;
preferably, the first metal component is present in an amount of 6.2 to 19.2 wt.%, the second metal component is present in an amount of 0.5 to 3.9 wt.%, the non-metal component is present in an amount of 0.7 to 1.7 wt.%, and the support is present in an amount of 75.2 to 92.6 wt.%, based on the total weight of the novel dehydrogenation catalyst.
3. The novel dehydrogenation catalyst of claim 1 or 2, wherein the Al is 2 O 3 The specific surface area of the-KIT-6 cubic structure composite material is 300-700m 2 The pore volume is 0.6-1.4mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7-9nm and 10-15nm respectively;
preferably, the Al is 2 O 3 The specific surface area of the-KIT-6 composite material is 483-545m 2 The pore volume is 0.9-1.1mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7.8-8.2nm and 11.8-12.5nm respectively.
4. The novel dehydrogenation catalyst of any of claims 1-3 wherein the Al is 2 O 3 The preparation method of the KIT-6 cubic structure composite material comprises the following steps:
(1) Under the condition of hydrolysis gel making, a template solvent, a silicon source, n-butanol and hydrochloric acid are contacted and mixed to obtain a gel mixture; crystallizing the gel mixture; then, filtering, washing, first drying and first roasting the crystallized product to obtain a KIT-6 mesoporous molecular sieve;
(2) In the presence of dilute nitric acidMixing the KIT-6 mesoporous molecular sieve, an alumina precursor and an extrusion aid, then carrying out extrusion forming, and carrying out secondary drying and secondary roasting treatment to obtain Al 2 O 3 -KIT-6 cubic structure composite.
5. The novel dehydrogenation catalyst of claim 4 wherein the templating agent is a nonionic surfactant; the silicon source is a silicon-containing organic compound and/or a silicon-containing inorganic compound;
preferably, the molar ratio of the dosage of the plate agent, the silicon source, the n-butanol, the hydrochloric acid and the water is 1: (10-150): (20-200): (200-1200): (5000-20000);
preferably, the conditions for preparing the glue by hydrolysis comprise: the temperature is 20-50 deg.C, and the time is 5-30h.
6. The novel dehydrogenation catalyst of claim 4 wherein the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite, and boehmite;
preferably, the weight ratio of the KIT-6 mesoporous molecular sieve to the alumina precursor to the extrusion assistant to the dilute nitric acid is 1: (0.3-5): (0.02-0.5): (0.2-5).
7. A novel dehydrogenation catalyst according to claim 1 or 2, wherein the first metal component is selected from one or more of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper;
preferably, the second metal component is an alkali metal and/or an alkaline earth metal;
preferably, the non-metallic component is S.
8. A method of preparing a novel dehydrogenation catalyst according to any one of claims 1-7, comprising: under the ultrasonic-assisted condition, a solution containing a first metal component precursor and a second metal component precursor is mixed with Al 2 O 3 -KIT-6 cubic structure composite materialAfter contact impregnation treatment, removing the solvent, drying and roasting to obtain an initial catalyst; and then contacting the initial catalyst with sulfur-containing gas for sulfurization treatment to obtain the novel dehydrogenation catalyst.
9. The method of manufacturing of claim 8, wherein the ultrasound-assisted conditions comprise: the temperature is 10-100 ℃, the time is 10-180min, and the power is 100-300W;
preferably, the impregnation conditions include: the temperature is 20-100 ℃, and the time is 0.5-10h;
preferably, the first metal component precursor is selected from nitrates, sulfites, sulfates or metal chlorides containing one or more elements of iron, nickel, zinc, molybdenum, tungsten, manganese, tin and copper;
preferably, the second metal component precursor is selected from the group consisting of nitrates, sulfites, sulfates or metal chlorides containing alkali metals and/or alkaline earth metals;
preferably, the conditions of the calcination include: the temperature is 400-700 ℃, and the time is 2-15h;
preferably, the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1-5%;
preferably, the conditions of the vulcanization treatment include: the temperature is 400-700 ℃, and the time is 1-15h.
10. Use of a novel dehydrogenation catalyst according to any of claims 1-7 in the dehydrogenation of isobutane to isobutene.
CN202110517357.7A 2021-05-12 2021-05-12 Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation Active CN115337955B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110517357.7A CN115337955B (en) 2021-05-12 2021-05-12 Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110517357.7A CN115337955B (en) 2021-05-12 2021-05-12 Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation

Publications (2)

Publication Number Publication Date
CN115337955A true CN115337955A (en) 2022-11-15
CN115337955B CN115337955B (en) 2024-02-20

Family

ID=83977628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110517357.7A Active CN115337955B (en) 2021-05-12 2021-05-12 Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation

Country Status (1)

Country Link
CN (1) CN115337955B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016017994A1 (en) * 2014-07-28 2016-02-04 롯데케미칼 주식회사 Dehydrogenation catalyst, and preparation method therefor
KR20180079178A (en) * 2016-12-29 2018-07-10 주식회사 효성 Composite catalyst support, dehydrogenation catalysts and preparation method thereof
CN110732341A (en) * 2018-07-19 2020-01-31 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with spherical aluminum-containing double mesoporous molecular sieve silica gel composite as carrier and preparation method and application thereof
CN110732342A (en) * 2018-07-19 2020-01-31 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof
CN111250096A (en) * 2018-11-30 2020-06-09 中国石油化工股份有限公司 Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016017994A1 (en) * 2014-07-28 2016-02-04 롯데케미칼 주식회사 Dehydrogenation catalyst, and preparation method therefor
KR20180079178A (en) * 2016-12-29 2018-07-10 주식회사 효성 Composite catalyst support, dehydrogenation catalysts and preparation method thereof
CN110732341A (en) * 2018-07-19 2020-01-31 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with spherical aluminum-containing double mesoporous molecular sieve silica gel composite as carrier and preparation method and application thereof
CN110732342A (en) * 2018-07-19 2020-01-31 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof
CN111250096A (en) * 2018-11-30 2020-06-09 中国石油化工股份有限公司 Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
崔丹丹;周广林;陈志伟;蒋晓阳;周红军;: "正丁烷脱氢异构制异丁烯的研究进展", 工业催化, no. 12, pages 900 - 904 *
李丽, 阎子峰: "异丁烷脱氢催化剂的研究", 化学进展, no. 04, pages 651 - 659 *

Also Published As

Publication number Publication date
CN115337955B (en) 2024-02-20

Similar Documents

Publication Publication Date Title
Rahmani et al. The beneficial utilization of natural zeolite in preparation of Cr/clinoptilolite nanocatalyst used in CO2-oxidative dehydrogenation of ethane to ethylene
CN110614116A (en) Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation
RU2687100C2 (en) Mesoporous catalyst for hydroconversion of residues and method for production thereof
Tanabe et al. Surface property and catalytic activity of MgO TiO2
CN103394367B (en) Utilize coal ash for manufacturing for the method for ZSM-5 molecular sieve nucleocapsid double-layer catalyst
Mishra et al. Transition metal pillared clay 4. A comparative study of textural, acidic and catalytic properties of chromia pillared montmorillonite and acid activated montmorillonite
CN111250144A (en) Non-noble metal propane dehydrogenation catalyst with modified spherical mesoporous silica as carrier and preparation method and application thereof
CN111135853A (en) Non-noble metal propane dehydrogenation catalyst with rod-shaped mesoporous molecular sieve as carrier and preparation method and application thereof
CN111250096A (en) Non-noble metal isobutane dehydrogenation catalyst with hexagonal mesoporous material as carrier and preparation method and application thereof
CN108285151B (en) Ce isomorphous substituted LTL molecular sieve and preparation method thereof
CA3201469A1 (en) Silica-alumina composition comprising from 1 to 30 wt.% of crystalline ammonium aluminum carbonate hydroxide and method for making the same
CN113546674B (en) Catalytic cracking catalyst, preparation method and application thereof, and catalytic cracking method
CN115337955A (en) Novel dehydrogenation catalyst, preparation method thereof and application of novel dehydrogenation catalyst in preparation of isobutene through isobutane dehydrogenation
CN111135852A (en) Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof
CN111298799A (en) Preparation method and application of reduced NiMo bifunctional catalyst
CN115487854B (en) Isobutane dehydrogenation catalyst and preparation method and application thereof
CN110614120A (en) Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation
CA2969359C (en) Catalyst and preparation method thereof, and method for preparing isobutylene by applying the same
CN115337956B (en) Supported catalyst, preparation method thereof and application thereof in propylene preparation by propane dehydrogenation
CN116532148A (en) Spherical isobutane dehydrogenation catalyst and preparation method and application thereof
CN111250097A (en) Non-noble metal isobutane dehydrogenation catalyst with spherical mesoporous silica as carrier and preparation method and application thereof
CN108786898B (en) Supported catalyst, preparation method and application thereof, and method for preparing propylene by propane dehydrogenation
CN113713850B (en) MTBE cracking propylene preparation catalyst and preparation method and application thereof
CN113731477B (en) Catalyst for preparing propylene and preparation method and application thereof
CN112756009B (en) C4 olefin cracking catalyst containing three-dimensional cubic mesoporous molecular sieve, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant