CN112495422A - Method for preparing silicon-based chromium catalyst by in-situ roasting, product and application thereof - Google Patents
Method for preparing silicon-based chromium catalyst by in-situ roasting, product and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 80
- 239000011651 chromium Substances 0.000 title claims abstract description 80
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 25
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 24
- 238000011068 loading method Methods 0.000 claims description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- 229940117975 chromium trioxide Drugs 0.000 claims description 12
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002210 silicon-based material Substances 0.000 claims description 8
- 150000001844 chromium Chemical class 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012512 characterization method Methods 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 54
- 239000001294 propane Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000007654 immersion Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000010926 purge Methods 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 5
- -1 Ethylene, propylene Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical group [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- 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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a silicon-based chromium catalyst by in-situ roasting, a product and application thereof. According to the invention, high-dispersion and high-activity chromium species can be obtained through simple in-situ roasting, the chromium species is used for preparing olefin through alkane dehydrogenation, higher conversion rate can be obtained compared with that obtained through roasting in a common muffle furnace under the same reaction condition, the catalytic life can reach 48h without inactivation, and the surface can be seen to be reconstructed through characterization, so that high dispersion is achieved.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a method for preparing a silicon-based chromium catalyst by in-situ roasting, a product and application thereof.
Background
Ethylene, propylene and isobutylene are basic materials of various chemical products, mainly including plastics, rubbers, fuel blending agents and chemical intermediates. At present, the conventional methods for preparing olefins are mainly steam cracking and naphtha catalytic cracking. However, in recent years, with the increasing global demand for ethylene, propylene and isobutylene, the shortage of petroleum resources, the rising price and the rising day, the development of a new generation of olefin production process has become a major development trend of the petrochemical industry. The low-carbon alkane resources in China are rich, and especially with the development of shale gas mining technology in China, the catalytic dehydrogenation of ethane, propane and isobutane gradually becomes an effective way for improving the yield of ethylene, propylene and isobutene. The olefin preparation by alkane dehydrogenation not only can reduce the cost and reduce the dependence degree on naphtha cracking and catalytic cracking processes, but also can obtain high-value hydrogen so as to improve the added value of products.
The chromium-based catalyst has excellent performance in preparing olefin by alkane dehydrogenation, compared with noble metal, chromium has lower requirement on impurities in raw materials, and is low in price and easy to obtain.
Disclosure of Invention
Based on the technical problems, the invention provides a method for preparing a silicon-based chromium catalyst by in-situ roasting, and a product and application thereof. The high-dispersion high-activity chromium species (monomer hexavalent chromium) catalyst material can be obtained by in-situ roasting in a simple flowing air atmosphere, is used for preparing olefin by alkane dehydrogenation, can obtain higher conversion rate compared with common roasting under the same reaction condition, has the catalytic life of not being inactivated for 48 hours, and can be seen through characterization that the surface is reconstructed to achieve high dispersion.
The invention provides a method for preparing a silicon-based chromium catalyst by in-situ roasting, which comprises the steps of putting a silicon-based material into a chromium salt precursor solution for dipping, drying and roasting in a flowing air atmosphere to obtain the silicon-based chromium catalyst.
Based on the characteristic of weak interaction force between the chromium salt and the silicon-based carrier, the chromium-containing material is roasted in a flowing air atmosphere environment, and the chromium element is redispersed in the silicon-based material by virtue of the power of air, so that the chromium species with high dispersion and high activity components is obtained.
Further, the chromium salt precursor is one or more of ammonium chromate, ammonium dichromate, chromium nitrate, chromium sesquioxide and chromium trioxide, and the mass percent of Si in the silicon-based material is 85-95%.
Further, the silicon-based material is one of mesoporous MCM-41, mesoporous SBA-15, mesoporous SBA-16 and silicon dioxide.
Further, the theoretical loading of chromium in the silicon-based chromium catalyst is 5-20%, and the theoretical loading calculation formula is as follows:
further, the impregnation conditions are equal volume impregnation or over volume impregnation.
Further, the drying conditions are: drying for 6-14 h at 80-140 ℃.
Further, the roasting conditions in a flowing air atmosphere are as follows: the air flow rate is 10-100ml/min, the heating rate is 1-10 ℃/min, and the temperature is increased to 500-650 ℃ for roasting.
The invention also provides the silicon-based chromium catalyst prepared by the method for preparing the silicon-based chromium catalyst by in-situ roasting.
The invention also provides the application of the silicon-based chromium catalyst in preparing olefin by alkane dehydrogenation.
Further, filling a silicon-based chromium catalyst in a reactor, purging with inert gas, and introducing the gas to be treated with the alkane concentration of 50000ppm-500000ppm into the reactor to perform alkane dehydrogenation reaction to prepare alkene; wherein the reaction temperature is 500-650 ℃, and the space velocity of the gas to be treated is 750-30000 h-1。
Further, the silicon-based chromium catalyst is filled in the reactor and is sieved to 20-80 meshes.
Further, the alkane is one of ethane, propane and isobutane.
Compared with the prior art, the invention has the following beneficial effects:
the silicon-based chromium catalyst prepared by the invention has higher catalytic activity, and compared with the early 34% conversion rate of a directly-baked material, the conversion rate can reach 90% after in-situ baking in a flowing air atmosphere. When the silicon-based material is in a porous structure, chromium species are loaded in the porous material, so that the stability of chromium in the material is better, the catalytic life is long, the catalytic material roasted by the muffle furnace is completely inactivated after 30 hours, but the catalytic material subjected to in-situ roasting treatment in a flowing air atmosphere still has higher conversion rate after 48 hours; the dispersion degree of chromium species in the silicon-based chromium catalyst prepared by roasting in the flowing air atmosphere after equal volume impregnation is high, the roasted material of the muffle furnace shows that the chromium species are agglomerated together under a scanning electron microscope of 200nm, but the chromium species can be found to be well dispersed in the material after in-situ roasting treatment, so that the material is more favorable for exerting catalytic reaction activity.
Drawings
FIG. 1 is a graph comparing the conversion and yield of propylene produced by propane dehydrogenation for a silicon-based chromium catalyst prepared in example 1 and a muffle furnace treated catalyst, respectively;
FIG. 2 is a graph comparing the conversion to yield of ethylene from the dehydrogenation of ethane for the silicon-based chromium catalyst prepared in example 2 and the muffle-treated catalyst, respectively;
FIG. 3 is a graph comparing the conversion and yield of isobutylene prepared by dehydrogenation of butane for the silicon-based chromium catalyst prepared in example 3 and the muffle-treated catalyst, respectively.
FIG. 4 is a comparative electron microscopy image of the silicon-based chromium catalyst prepared in example 3 of the present invention (right) and the silicon-based chromium catalyst prepared by muffle furnace calcination (left).
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
Chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and heated to 550 ℃ by a program of 5 ℃/min at the air flow rate of 40ml/min for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h and put into a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the catalyst packing mass is 0.4g, introducing a treatment gas with the propane concentration of 140000ppm, and the total space velocity of feeding is 4200h-1The reaction system pressure is normal pressure, the reaction temperature is 600 ℃, propane dehydrogenation is carried out to prepare propylene, and the early conversion rate of propane is 87%. The service life is kept at 20% at 48 h.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 34%. The life time is inactivated at 30 h.
A graph of conversion versus yield for propane dehydrogenation to propylene for the silicon-based chromium catalyst prepared in this example and the muffle furnace treated catalyst, respectively, is shown in FIG. 1.
Example 2
Chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and heated to 550 ℃ by a program of 5 ℃/min under the air of 40ml/min for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a muffle furnace, and heated to 550 ℃ by a program of 5 ℃/min for 3h, so that the silicon-based chromium catalyst is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the packing mass of the catalyst is 0.4g, introducing a treatment gas with the ethane concentration of 140000ppm, and the total space velocity of feeding is 4200h-1The ethane dehydrogenation is carried out to prepare the ethylene under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 600 ℃, and the early conversion rate of the ethane is 30 percent. The service life is kept at 20% at 40 h.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 9%. The service life is kept at 8% at 40 h.
A graph of conversion versus yield for propane dehydrogenation to propylene for the silicon-based chromium catalyst prepared in this example and the muffle furnace treated catalyst, respectively, is shown in FIG. 2.
Example 3
Ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and subjected to temperature programming of 500000ppm to 550 ℃ at the speed of 5 ℃/min under the air of 40ml/min for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h and placed in a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the filling mass of the catalyst is 0.3g, introducing a treatment gas with isobutane concentration of 100000ppm, and the total space velocity of feeding is 720h-1And carrying out isobutane dehydrogenation to prepare isobutene under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 550 ℃, wherein the early conversion rate of isobutane is 70%. The life is kept at 53% at 6 h.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 45%. The conversion rate at 6h of the lifetime was 20%.
A graph comparing the conversion and yield of propylene produced by propane dehydrogenation for the silicon-based chromium catalyst prepared in this example and the muffle furnace treated catalyst, respectively, is shown in fig. 3;
a comparison of electron microscopy images of the silica-based chromium catalyst (right) and the silica-based chromium catalyst prepared by muffle furnace calcination (left) is shown in FIG. 4.
Example 4
Ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and subjected to temperature programming of 5 ℃/min to 550 ℃ for 3h under the air of 40ml/min, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h and placed in a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst is obtained.
The prepared silicon-based chromium catalyst is blown by nitrogen and sieved by a sieve of 80 meshes, the packing mass of the catalyst is 0.4g, 140000ppm of propane is fed in, and the total space velocity of feeding is 4200h-1The propane dehydrogenation is carried out to prepare the propylene under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 600 ℃, and the early conversion rate of the propane is 90 percent.
The muffle furnace treated catalyst was used for the above reaction to obtain an early conversion of 54%.
By comparing the data of example 1 and example 4, it can be shown that, under the premise of the same theoretical loading, the difference of the chromium salt precursor also has an influence on the catalytic effect of the prepared catalyst, and the principle is that the metal ions have different interactions with the carrier. The chromium salt precursor with the best catalytic performance is chromate because ammonium ions react with the support.
Example 5
Chromium nitrate (1.71g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min and dried for 14h at 110 ℃, the dried mixture is placed in a fixed bed reactor, and the temperature is programmed to 650 ℃ at 10 ℃/min under the air of 100ml/min and is kept for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: chromium nitrate (1.71g) is used as a precursor and loaded on mesoporous MCM-41(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h and put into a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst is obtained.
The prepared silicon-based chromium catalyst is purged by nitrogen, the filling mass of the catalyst is 0.4g, 200000ppm of propane is introduced, and the total space velocity of feeding is 30000h-1The reaction system pressure is normal pressure, the reaction temperature is 600 ℃, propane dehydrogenation is carried out to prepare propylene, and the early conversion rate of propane is 75%.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 40%.
Example 6
Chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous SBA-15(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and heated to 500 ℃ by a program of 1 ℃/min under the air of 10ml/min for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: chromium trioxide (0.42g) is used as a precursor and loaded on mesoporous SBA-15(2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, put into a muffle furnace, and heated to 550 ℃ by a program of 5 ℃/min for 3h to obtain the silicon-based chromium catalyst.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the catalyst packing mass is 0.4g, introducing 140000ppm of propane, and the total feed space velocity is 4200h-1The reaction system pressure is normal pressure, the reaction temperature is 600 ℃, propane dehydrogenation is carried out to prepare propylene, and the early conversion rate of propane is 70%.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 35%.
Example 7
Ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous SBA-15(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a fixed bed reactor, and heated to 550 ℃ by a program of 5 ℃/min under the air of 40ml/min for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Muffle furnace treated catalyst preparation: ammonium chromate (0.65g) is used as a precursor and loaded on mesoporous SBA-15(2g) by an isometric immersion method (2ml of deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, placed in a muffle furnace, and heated to 550 ℃ by a program of 5 ℃/min and kept for 3h, and the silicon-based chromium catalyst is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the catalyst packing mass is 0.4g, introducing 140000ppm of propane, and the total feed space velocity is 4200h-1The reaction system pressure is normal pressure, the reaction temperature is 600 ℃, propane dehydrogenation is carried out to prepare propylene, and the early conversion rate of propane is 75%.
The catalyst treated by the muffle furnace is used for the reaction, and the early conversion rate is 45%.
Example 8
Chromium trioxide (0.42g) is used as a precursor and loaded on silicon dioxide (2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, put into a fixed bed reactor, and heated to 650 ℃ by a program of 5 ℃/min under the air of 60ml/min for 3h, so as to obtain the silicon-based chromium catalyst.
Muffle furnace treated catalyst preparation: chromium trioxide (0.42g) is used as a precursor and loaded on silicon dioxide (2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h and put into a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 10% is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the catalyst packing mass is 0.4g, introducing 140000ppm of propane, and the total feed space velocity is 4200h-1The reaction system pressure is normal pressure, the reaction temperature is 600 ℃, propane dehydrogenation is carried out to prepare propylene, and the early conversion rate of propane is 60%.
The muffle furnace treated catalyst was used for the reaction to obtain a conversion rate of 40% at the previous stage.
Example 9
Chromium trioxide (1.2g) is used as a precursor and loaded on silicon dioxide (2g) by an isometric immersion method (2ml deionized water), the mixture is stirred for 10min, dried at 110 ℃ for 14h, put into a fixed bed reactor, and heated to 650 ℃ by a program of 5 ℃/min under the air of 60ml/min for 3h, so that the silicon-based chromium catalyst is obtained.
Muffle furnace treated catalyst preparation: chromium trioxide (1.2g) is used as a precursor and loaded on silicon dioxide (2g) by an isometric immersion method (2ml deionized water), the silicon dioxide is stirred for 10min and then dried for 14h at 110 ℃, the mixture is put into a muffle furnace, and the temperature is raised to 550 ℃ by a program of 5 ℃/min and kept for 3h, so that the silicon-based chromium catalyst with the theoretical loading of 5% is obtained.
Sieving the prepared silicon-based chromium catalyst with a 80-mesh sieve, purging with nitrogen, wherein the catalyst packing mass is 0.4g, introducing 140000ppm of propane, and the total feed space velocity is 4200h-1The propane dehydrogenation is carried out to prepare the propylene under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 600 ℃, and the early conversion rate of the propane is 78 percent.
The muffle furnace treated catalyst was used for the above reaction to obtain an early conversion of 21%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The method for preparing the silicon-based chromium catalyst by in-situ roasting is characterized in that a silicon-based material is placed in a chromium salt precursor solution for dipping, drying and roasting in a flowing air atmosphere to obtain the silicon-based chromium catalyst.
2. The method for preparing the silicon-based chromium catalyst by in-situ roasting according to claim 1, wherein the chromium salt precursor is one or more of ammonium chromate, ammonium dichromate, chromium nitrate, chromium sesquioxide and chromium trioxide, and the mass percent of Si in the silicon-based material is 85-95%.
3. The method for preparing the silicon-based chromium catalyst according to claim 1, wherein the silicon-based material is one of mesoporous MCM-41, mesoporous SBA-15, mesoporous SBA-16, and silica.
4. The method for preparing the silicon-based chromium catalyst by in-situ calcination according to claim 1, wherein the theoretical loading of chromium in the silicon-based chromium catalyst is 5-20%.
5. The method for preparing the silicon-based chromium catalyst by in-situ calcination according to claim 1, wherein the impregnation is equal volume impregnation or over volume impregnation.
6. The method for preparing the silicon-based chromium catalyst by in-situ calcination according to claim 1, wherein the drying conditions are: drying for 6-14 h at 80-140 ℃.
7. The method for preparing the silicon-based chromium catalyst by in-situ calcination according to claim 1, wherein the calcination conditions under the flowing air atmosphere are as follows: the air flow rate is 10-100ml/min, the heating rate is 1-10 ℃/min, and the temperature is increased to 500-650 ℃ for roasting.
8. A silicon-based chromium catalyst prepared by the method for preparing a silicon-based chromium catalyst by in-situ calcination according to any one of claims 1 to 7.
9. Use of the silicon-based chromium catalyst according to claim 8 for the dehydrogenation of alkanes to olefins.
10. The use of the silicon-based chromium catalyst as claimed in claim 9 for the preparation of an olefin by dehydrogenation of an alkane, wherein the silicon-based chromium catalyst is filled in a reactor, purged with an inert gas, and a gas to be treated having an alkane concentration of 50000ppm to 500000ppm is introduced into the reactor to carry out the dehydrogenation reaction of the alkane to prepare the olefin; wherein the reaction temperature is 500-650 ℃, and the space velocity of the gas to be treated is 750-30000 h-1。
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