CN111644197A - Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application - Google Patents
Catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, preparation method and application Download PDFInfo
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- CN111644197A CN111644197A CN202010412621.6A CN202010412621A CN111644197A CN 111644197 A CN111644197 A CN 111644197A CN 202010412621 A CN202010412621 A CN 202010412621A CN 111644197 A CN111644197 A CN 111644197A
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- catalyst
- molecular sieve
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- molybdenum
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 178
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 227
- 239000002808 molecular sieve Substances 0.000 claims abstract description 110
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 110
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 49
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 41
- 239000011733 molybdenum Substances 0.000 claims abstract description 41
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 26
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical group N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000004687 hexahydrates Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- VVKBUFYSWPMDNG-UHFFFAOYSA-N nitroxyl anion platinum(2+) Chemical compound N(=O)[Pt]N=O VVKBUFYSWPMDNG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 230000002779 inactivation Effects 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 description 26
- 238000011049 filling Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 23
- 239000012495 reaction gas Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910002847 PtSn Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
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- B01J35/19—
-
- 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively 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
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B01J35/50—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, a preparation method and application, wherein the catalytic system comprises: molybdenum-based molecular sieve catalysts and catalysts with iron oxide as a carrier; the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10; wherein the active component of the molybdenum-based molecular sieve catalyst is Mo,the mass percentage of the active component Mo in the molybdenum-based molecular sieve catalyst is 1-10%; in the catalyst using iron oxide as carrier, carrier Fe2O3Is in the form of powder, and the mass percentage content of the ferric oxide is 1-10%. The catalytic system converts methane into aromatic hydrocarbon raw materials with high added value at a lower temperature, and improves the utilization value of methane. The selectivity of the generated product is good, the selectivity of aromatic hydrocarbon can reach 70%, the stability of the catalyst is good, and the catalyst can continuously react for 100 hours without inactivation.
Description
Technical Field
The present invention relates to the field of methane conversion reactions. More particularly, relates to a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion, a preparation method and an application.
Background
After the 21 st century, with the development of shale gas and marine "combustible ice", the reserves of natural gas were further enriched, and the reserves of methane, which is a main component of natural gas, were also greatly increased. Methane can further generate chemical products with high added value through catalytic reaction, and under the background that the global petroleum resources are gradually exhausted at present, the effective utilization of methane is concerned by numerous scholars all over the world.
The methane conversion pathway is largely divided into indirect and direct processes. The indirect method is that methane is firstly prepared into CO and H with a certain proportion by reforming or partial oxidation under the condition of high temperature2The synthesis gas is then used to produce required organic chemical material directly or indirectly in the presence of catalyst. The direct method is that methane is directly converted into chemical products with high added value under the action of a catalyst. The indirect method has complex process technology and high energy consumption, and the direct method has lower energy consumption and higher methane utilization rate, so the direct conversion of methane is widely concerned in recent years.
Among the direct methane conversion, the oxygen-free conversion is widely studied due to its advantages of high atom utilization, environmental friendliness, etc. The methane molecule is a regular tetrahedron structure, consists of weakly polarized C-H bonds, and has very stable chemical and thermodynamic properties. In the absence of a catalyst, thousands of high temperatures are required to break the C-H bonds of methane. In 1993, Wang et al reported that methane conversion of 7.2% and benzene selectivity of an anaerobic aromatization reaction of 973K under a continuous flow mode on a Mo/HZSM-5 molecular sieve catalyst become important milestones in the anaerobic methane conversion process, and a lot of scientists have made a lot of research around the anaerobic methane conversion process. Koerts et al designed a catalytic reaction system from methane to ethane, propane, butane and pentane in two steps from a reaction mechanism: the first step is that methane is desorbed and adsorbed on a transition metal catalyst to generate surface carbon species and hydrogen, and the required temperature is about 400 ℃; the second step is the hydrogenation of carbon species to produce small alkanes at temperatures around 100 deg.C (Chemnform, 1993,24(8): 101-. Barrabes et al found that transition metals can activate methane at lower temperatures (appl. catal.b: Environ,2009,87: 84-91). Vesna et al studied the methane chemisorption of Pt-containing catalysts at low temperatures (200-450 ℃ C.) in fixed bed reactors (Applied Catalysis AGEneral,2014,488: 138-. Duygu et al found that the supported SiO2And Pt and PtSn catalysts on HZSM-5 can be used for methane conversion under non-oxidative conditions, adding Sn to Pt/SiO2 can synthesize more active ethylene forming catalysts, preparing Pt and PtSn catalysts supported on HZSM-5 zeolite can improve activity and selectivity to non-coke products, these catalysts operate by a bifunctional mechanism in which ethylene is first produced on highly dispersed PtSn nanoparticles, followed by a catalyst supported on a zeolite carrier
Conversion to benzene and naphthalene at the acid site (Acs Catalysis,2017,7 (3)). Bao et al insert a single-center low-valence iron atom with high catalytic activity into a silicon oxide or silicon carbide lattice to form a high-temperature stable catalytic activity center, so that the conversion per pass of methane reaches 48.1%, the selectivity of ethylene is 48.4%, and the selectivity of all products (ethylene, benzene and naphthalene) is 48.1%>99% (Science Foundation in China,2014,344, 616-. Although these methods reduce the methane conversion temperature, the catalyst preparation and reaction conditions are difficult to industrialize, and the catalyst is rapidly deactivated due to the carbon deposition problem of the catalyst during the reaction process.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion. The catalytic system converts methane into aromatic hydrocarbon raw materials with high added value at a lower temperature, and improves the utilization value of methane. The selectivity of the generated product is good, the selectivity of aromatic hydrocarbon can reach 70%, the stability of the catalyst is good, and the catalyst can continuously react for 100 hours without inactivation.
The second technical problem to be solved by the invention is to provide a preparation method of a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion.
The third technical problem to be solved by the invention is to provide the application of the catalytic system in preparing aromatic hydrocarbon by low-temperature methane conversion.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion comprises:
molybdenum-based molecular sieve catalysts and catalysts with iron oxide as a carrier;
the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10;
wherein, the active component of the molybdenum-based molecular sieve catalyst is Mo, and the mass percentage content of the active component Mo in the molybdenum-based molecular sieve catalyst is 1-10%;
in the catalyst using iron oxide as carrier, carrier Fe2O3Is in the form of powder, and the mass percentage content of the ferric oxide is 1-10%.
Preferably, the molecular sieve in the molybdenum-based molecular sieve catalyst is one or more selected from HZSM-5 molecular sieve, SAPO-34 molecular sieve, H beta molecular sieve, MCM-41 molecular sieve, Q10 molecular sieve and HY molecular sieve.
Preferably, the molecular sieve has a molar ratio of the silicon to aluminum components of 20 to 150: 1.
Preferably, in the catalyst taking iron oxide as a carrier, the active metal is one or more of Pt, Pd, Ru, Ni, Mn, Cu, Co, Zr, Mg, Cr, Zn, Ce, K, Al, Ag and Rh.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a preparation method of a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
preparing a molybdenum-based molecular sieve catalyst and a catalyst taking ferric oxide as a carrier by adopting an impregnation method, wherein the two catalysts are mixed according to a mass ratio of 1:1-10, fully grinding until the mixture is uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
Preferably, the preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following specific steps:
1) roasting the molecular sieve carrier at 400-550 ℃ for 2-12 h;
2) preparing a molybdenum-based molecular sieve catalyst by adopting an excess impregnation method, weighing a Mo precursor and a molecular sieve carrier according to a proportion, dissolving the Mo precursor and the molecular sieve carrier in deionized water, stirring and evaporating at 55-65 ℃, drying at 115-125 ℃ for 10-15h, and roasting at 540-560 ℃ to obtain the molybdenum-based molecular sieve catalyst;
3) preparing a catalyst taking iron oxide as a carrier by adopting an excess impregnation method: weighing the transition metal precursor and Fe according to the proportion2O3Dissolving the powder in a proper amount of glycol or deionized water, uniformly stirring, drying at 120-150 ℃ for 10-15h, and roasting at 380-420 ℃ to obtain a catalyst taking iron oxide as a carrier;
4) fully grinding the molybdenum-based molecular sieve catalyst and the catalyst taking ferric oxide as a carrier according to the mass ratio until the molybdenum-based molecular sieve catalyst and the catalyst are uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
Preferably, in the step 1), the molecular sieve carrier is selected from one or more of HZSM-5 molecular sieve, SAPO-34 molecular sieve, H beta molecular sieve, MCM-41 molecular sieve, Q10 molecular sieve and HY molecular sieve.
Preferably, in the step 2), the Mo precursor is ammonium molybdate tetrahydrate crystals; the amount of the deionized water for dissolving the Mo precursor and the molecular sieve carrier is 2-6mL/g, and the roasting time is 2-12 h.
Preferably, in the step 3), the transition metal precursor is selected from one or more of chloroplatinic acid hexahydrate crystals, dinitrosoplatinum solution, palladium chloride powder, palladium nitrate solution, ruthenium nitrate solution and nickel nitrate hexahydrate crystals; the dissolved transition metal precursor and Fe2O3The quantity of the ethylene glycol or the deionized water of the powder is 0-1mL/g, and the roasting time is 2-12 h.
Preferably, in the step 4), the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10.
In order to solve the third technical problem, the application of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion of the invention comprises the following specific steps:
11) the reaction is carried out in a fixed bed reactor, and the catalyst is placed in a quartz glass tube;
12) introducing reducing gas to activate the catalyst, wherein the activation temperature is 300-500 ℃, and the maintaining time is 1-10 h;
13) introducing raw material gas for reaction, wherein the raw material gas is methane gas with the concentration of 90% (10% Ar is used as internal standard gas), the reaction temperature is 350-cat·h。
Preferably, in step 12), the reducing gas is one or more of hydrogen and syngas.
Preferably, in the step 13), an auxiliary agent is added during the reaction, and the auxiliary agent is selected from one or more of benzene, toluene and xylene.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
the invention can complete the conversion of methane at the low temperature of 350-600 ℃, and the catalyst has the advantages of simple preparation method, convenient operation, good selectivity of the generated product, aromatic selectivity over 70 percent, stable catalyst and continuous reaction for 100 hours without inactivation.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As one aspect of the invention, a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion comprises:
molybdenum-based molecular sieve catalysts and catalysts with iron oxide as a carrier;
the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10;
wherein, the active component of the molybdenum-based molecular sieve catalyst is Mo, and the mass percentage content of the active component Mo in the molybdenum-based molecular sieve catalyst is 1-10%;
in the catalyst using iron oxide as carrier, carrier Fe2O3Is in powder form, and the mass percentage content of the ferric oxide is 1 to 10 percent.
In the present invention, the term "catalytic system" means that the whole is present in the reactor as a "catalyst", which in the present invention is in the form of a mixture rather than a compound.
In certain embodiments of the present invention, the molecular sieve in the molybdenum-based molecular sieve catalyst is selected from one or more of an HZSM-5 molecular sieve, a SAPO-34 molecular sieve, an Hbeta molecular sieve, an MCM-41 molecular sieve, a Q10 molecular sieve, and an HY molecular sieve.
In certain embodiments of the invention, the molecular sieve has a molar ratio of the silicon to aluminum component of 20 to 150:1, and too low or too high acidity is detrimental to the formation of products during the reaction.
In certain embodiments of the invention, the active metal in the iron oxide supported catalyst is one or more of Pt, Pd, Ru, Ni, Mn, Cu, Co, Zr, Mg, Cr, Zn, Ce, K, Al, Ag, Rh.
As another aspect of the invention, a preparation method of a catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
preparing a molybdenum-based molecular sieve catalyst and a catalyst taking ferric oxide as a carrier by adopting an impregnation method, wherein the two catalysts are mixed according to a mass ratio of 1:1-10, fully grinding until the mixture is uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
In some embodiments of the present invention, the preparation method of the catalytic system for preparing aromatic hydrocarbons by low-temperature methane conversion comprises the following specific steps:
1) roasting the molecular sieve carrier at 400-550 ℃ for 2-12h, so that impurities possibly existing on the molecular sieve are effectively removed, and the judgment of an experimental result is not influenced;
2) preparing a molybdenum-based molecular sieve catalyst by adopting an excess impregnation method, weighing a Mo precursor and a molecular sieve carrier according to a proportion, dissolving the Mo precursor and the molecular sieve carrier in deionized water, stirring and evaporating to dryness at 55-65 ℃, then drying at 115-125 ℃ for 10-15h, and roasting at 540-560 ℃, removing impurities possibly existing in the catalyst preparation process, and stabilizing the catalyst structure to obtain the molybdenum-based molecular sieve catalyst;
3) preparing a catalyst taking iron oxide as a carrier by adopting an excess impregnation method: weighing the transition metal precursor and Fe according to the proportion2O3Dissolving the powder in a proper amount of glycol or deionized water, uniformly stirring, drying at 120-150 ℃ for 10-15h, roasting at 380-420 ℃, removing impurities possibly existing in the catalyst preparation process, and stabilizing the catalyst structure to obtain a catalyst taking iron oxide as a carrier;
4) fully grinding the molybdenum-based molecular sieve catalyst and the catalyst taking ferric oxide as a carrier according to the mass ratio until the molybdenum-based molecular sieve catalyst and the catalyst are uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
In certain embodiments of the invention, in step 1), the molecular sieve support is selected from one or more of an HZSM-5 molecular sieve, a SAPO-34 molecular sieve, an H β molecular sieve, an MCM-41 molecular sieve, a Q10 molecular sieve, an HY molecular sieve.
In certain embodiments of the invention, in step 2), the Mo precursor is ammonium molybdate tetrahydrate crystals; the amount of deionized water for dissolving the Mo precursor and the molecular sieve carrier is 2-6mL/g, and the roasting time is 2-12 h.
In certain embodiments of the present invention, in step 3), the transition metal precursor is selected from one or more of chloroplatinic acid hexahydrate crystals, dinitrosoplatinum solution, palladium chloride powder, palladium nitrate solution, ruthenium nitrate solution, nickel nitrate hexahydrate crystals; the dissolved transition metal precursor and Fe2O3The quantity of the ethylene glycol or the deionized water of the powder is 0-1mL/g, and the roasting time is 2-12 h.
In some embodiments of the present invention, in step 4), the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst using iron oxide as a carrier is 1:1-10, the ratio is too low to realize aromatization, and too high acid sites are too many to easily cause carbon deposition of the catalyst.
As another aspect of the invention, the application of the catalytic system for preparing aromatic hydrocarbon by low-temperature methane conversion of the invention comprises the following specific steps:
11) the reaction is carried out in a fixed bed reactor, and the catalyst is placed in a quartz glass tube;
12) introducing reducing gas to activate the catalyst, wherein the activation temperature is 300-500 ℃, the catalyst cannot be fully reduced when the temperature is too low, carbon deposition is easily caused by the catalytic reaction when the temperature is too high, the subsequent reaction is not facilitated, and the maintaining time is 1-10 h;
13) introducing raw material gas for reaction, wherein the raw material gas is methane gas with the concentration of 90% (10% Ar is used as internal standard gas), the reaction temperature is 350-catH, too low space velocity is not favorable for reaction, and too high space velocity is not favorable for reaction control.
Preferably, in step 12), the reducing gas is one or more of hydrogen and syngas.
Preferably, in the step 13), an auxiliary agent is added during the reaction, and the auxiliary agent is selected from one or more of benzene, toluene and xylene.
Example 1
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.15g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:3。
Filling the catalyst system into a fixed bed reactor, reducing for 3h at 400 ℃ in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 1.
Example 2
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 1.
Example 3
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.5g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:10。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 1.
Comparative example 1
0.5873g of ammonium molybdate ((NH) were weighed out4)6Mo7O24·4H2O) is dissolved in 20mL of deionized water, 5g of HZSM-5 molecular sieve powder with the silica-alumina ratio of 36 is weighed and poured into the solution, the solution is stirred and evaporated to dryness at 60 ℃ on an electromagnetic stirrer, the obtained powder is placed in a porcelain cell and dried in a baking oven at 120 ℃ for 12 hours, and the obtained precursor is baked at 550 ℃ for 2 hours to obtain the molybdenum-based molecular sieve catalyst with the load of 6 wt%, which is marked as 6 Mo/HZSM-5-36.
Subjecting the above catalyst toTabletting and granulating under 10MPa, wherein the mesh number is 20-40 meshes. 0.05g of 6Mo/HZSM-5-36 and 0.25g of SiO with the mesh number of 20-40 meshes are respectively weighed2Uniformly mixing, filling into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 1.
TABLE 1
As can be seen from the test results, when the mixing ratio of the two catalysts is changed, the reaction results are significantly changed, and the mixing ratio of the two catalysts should be appropriately adjusted when the reaction is carried out. When the mixing ratio of the two catalysts is 1:5, the conversion rate of methane is remarkably improved, the selectivity of aromatic hydrocarbon is more than 70%, and the catalysts can continuously react for 100 hours without inactivation. The methane conversion rate of the single 6Mo/HZSM-5 catalyst in the reaction is only 1.56, the selectivity of the aromatic hydrocarbon is close to 33 percent, and the reaction can only stably and continuously run for 8 hours.
Example 4
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-20 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-20＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 2.
Comparative example 2
0.5873g of ammonium molybdate ((NH) were weighed out4)6Mo7O24·4H2O) dissolved in 20mLAnd (2) weighing 5g of HZSM-5 molecular sieve powder with the silicon-aluminum ratio of 20 in deionized water, pouring the powder into the solution, stirring and evaporating the powder on an electromagnetic stirrer at 60 ℃ to dryness, placing the obtained powder in a porcelain cell, drying the powder in a drying oven at 120 ℃ for 12 hours, and roasting the obtained precursor at 550 ℃ for 2 hours to obtain the molybdenum-based molecular sieve catalyst with the load of 6 wt%, wherein the load is marked as 6 Mo/HZSM-5-20.
Tabletting and granulating the catalyst under 10MPa, wherein the mesh number is 20-40 meshes. 0.05g of 6Mo/HZSM-5-20 and 0.25g of SiO with the mesh number of 20-40 meshes are respectively weighed2Mixing uniformly, filling into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in table 2.
TABLE 2
From the test results, when the silicon-aluminum ratio of the molecular sieve is changed, the methane conversion rate and the aromatic selectivity of the mixed catalyst are higher, and the catalyst can continuously react for 100 hours without inactivation. The methane conversion rate and the aromatic hydrocarbon selectivity of the single 6Mo/HZSM-5-20 catalyst during the reaction are both low, and the reaction can only stably and continuously run for 8 hours.
Example 5
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-150 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-150＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. In the reaction processThe methane conversion and the aromatics selectivity were slightly lower than in example 4, but the catalyst was still able to react for 100 hours without deactivation.
Example 6
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 1Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：1Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 3.
Comparative example 3
0.0979g ammonium molybdate ((NH) was weighed out4)6Mo7O24·4H2O) is dissolved in 20mL of deionized water, 5g of HZSM-5 molecular sieve powder with the silica-alumina ratio of 36 is weighed and poured into the solution, the solution is stirred and evaporated to dryness at 60 ℃ on an electromagnetic stirrer, the obtained powder is placed in a porcelain cell and dried in a baking oven at 120 ℃ for 12 hours, the obtained precursor is baked at 550 ℃ for 2 hours, and the molybdenum-based molecular sieve catalyst with the load of 1 wt% is obtained and is marked as 1 Mo/HZSM-5-36.
Tabletting and granulating the catalyst under 10MPa, wherein the mesh number is 20-40 meshes. 0.05g of 1Mo/HZSM-5-36 and 0.25g of SiO with the mesh number of 20-40 meshes are respectively weighed2Mixing uniformly, filling into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 3.
TABLE 3
From the test results, when the loading amount of Mo in the molecular sieve catalyst is changed, the methane conversion rate of the mixed catalyst is maintained at 4.04%, the aromatic selectivity is maintained at more than 70%, and the catalyst is slightly coked and can continuously react for 100 hours without inactivation. The single 1Mo/HZSM-5-36 catalyst has extremely low methane conversion rate during the reaction, the aromatic selectivity does not exceed 16 percent, and the reaction can only stably and continuously run for 8 hours.
Example 7
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 10Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：10Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. From the reaction results, when the Mo loading in the molecular sieve catalyst was increased, the methane conversion and the aromatics selectivity were slightly decreased compared to example 6.
Example 8
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/H β catalyst, uniformly mixing, granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and recording the obtained mixed catalyst as 1Pt/Fe2O3：6Mo/Hβ＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4Qi ofThe volume flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 4.
Comparative example 4
0.5873g of ammonium molybdate ((NH) were weighed out4)6Mo7O24·4H2O) is dissolved in 20mL of deionized water, 5g H β molecular sieve powder is weighed and poured into the solution, the mixture is stirred and evaporated to dryness on an electromagnetic stirrer at 60 ℃, the obtained powder is placed in a porcelain cell and dried in a 120 ℃ oven for 12 hours, the obtained precursor is roasted at 550 ℃ for 2 hours, and the molybdenum-based molecular sieve catalyst with the load of 6 wt% is obtained and is marked as 6Mo/H β.
Tabletting and granulating the catalyst under 10MPa, wherein the mesh number is 20-40 meshes, and respectively weighing 0.05g of 6Mo/H β and 0.25g of SiO with the mesh number of 20-40 meshes2Mixing uniformly, filling into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 4.
TABLE 4
From the test results, when the types of the molecular sieves in the molecular sieve catalyst are changed, the methane conversion rate of the mixed catalyst is maintained at 3.73%, the aromatic selectivity is maintained at more than 50%, and the catalyst is slightly coked and can continuously react for 100 hours without inactivation. The single 6Mo/H beta catalyst has extremely low methane conversion rate in the reaction, the selectivity of aromatic hydrocarbon is close to not more than 16 percent, and the reaction can only stably and continuously run for 8 hours.
Example 9
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/SAPO-34 catalyst, uniformly mixing, granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and recording the obtained mixed catalyst as 1Pt/Fe2O3：6Mo/SAPO-34＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. From the reaction result, when the SAPO-34 molecular sieve is used as a carrier of a molecular sieve catalyst, the methane conversion rate is low, but the catalyst can still keep reacting for 100 hours without deactivation.
Example 10
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pd/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pd/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 5.
Example 11
0.05g of 1Pd/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pd/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 1h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 5.
TABLE 5
From the test results, when the reduction time of the mixed catalyst is changed, the carbon deposition of the catalyst can be effectively reduced by reducing the reduction time, the selectivity of the aromatic hydrocarbon is maintained to be more than 70%, and both reactions can continuously react for 100 hours without inactivation.
Example 12
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 3Ru/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 3Ru/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 6.
Comparative example 5
3.0927g of ruthenium nitrosylnitrate solution (HN) were weighed out4O10Ru) in a porcelain vessel, 3gFe was weighed2O3Pouring the powder into the solution, stirring until the mixture is uniformly mixed, evaporating to dryness to form paste, and placing the paste in a drying oven at 150 ℃ for drying for 12 hours to obtain the iron-based catalyst with the load of 3 wt%, which is recorded as 3Ru/Fe2O3。
Tabletting and granulating the catalyst under 10MPa, wherein the mesh number is 20-40 meshes. 0.05g of 3Ru/Fe was weighed out separately2O3With 0.25g of SiO 20-40 mesh2Mixing uniformly, filling into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 6.
TABLE 6
From the test results, it can be seen that the iron-based catalyst alone has very low methane conversion and generates substantially no aromatic hydrocarbons during the reaction. The conversion rate of the mixed catalyst is maintained at 7.08%, the selectivity of aromatic hydrocarbon exceeds 70%, and the catalyst is not deactivated after being maintained for 100 hours.
Example 13
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 10Ni/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 10Ni/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 10h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67ml/min, and the reaction space velocity is 8000ml/gcatH. The reaction results are shown in Table 7.
Example 14
0.05g of 10Ni/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 10Ni/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 10h in a hydrogen atmosphere, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 16.67ml/min, and the reaction space velocity is 20000ml/gcatH. The reaction results are shown in Table 7.
TABLE 7
The test result shows that the increase of the space velocity can slightly improve the conversion rate of the catalyst, the selectivity of the aromatic hydrocarbon of the Ni metal catalyst is slightly lower than that of the Pt metal catalyst in the reaction process, and the catalyst can maintain the reaction for 100 hours without inactivation.
Example 15
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.05g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:1。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 300 ℃ for 3h in the atmosphere of synthesis gas, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. According to the reaction result, the reduction temperature is reduced, the catalyst conversion rate is reduced, but the catalyst can still maintain the reaction for 100 hours without inactivation.
Example 16
The preparation method of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion comprises the following steps:
0.05g of 1Pt/Fe was weighed out separately2O3And 0.05g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:1。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 500 ℃ for 3h in the atmosphere of synthesis gas, then heating to 550 ℃ for reaction, wherein the pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction result shows that the reduction temperature is reduced and increased, the conversion rate of the catalyst is properly increased, the selectivity of the aromatic hydrocarbon is better, and the catalyst can keep reaction for 100 hours and is not inactivated.
Example 17
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, granulating the obtained powder, and obtaining the mixture, wherein the particle mesh number is 20-40 meshesThe synthetic catalyst is noted as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, introducing toluene steam in the reaction process, wherein the reaction pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 8000mL/gcatH. The reaction results are shown in Table 13.
Example 18
0.05g of 1Pt/Fe was weighed out separately2O3And 0.25g of 6Mo/HZSM-5-36 catalyst, uniformly mixing, then granulating the obtained powder, wherein the particle mesh number is 20-40 meshes, and the obtained mixed catalyst is marked as 1Pt/Fe2O3：6Mo/HZSM-5-36＝1:5。
Filling the catalyst into a fixed bed reactor, reducing the catalyst at 400 ℃ for 3h in a hydrogen atmosphere, heating to 550 ℃ for reaction, introducing toluene steam in the reaction process, wherein the reaction pressure is 0.1MPa, and the reaction gas is 10% Ar/CH4The gas flow is 6.67mL/min, and the reaction space velocity is 5000mL/gcatH. The reaction results are shown in Table 13.
Watch 13
From the test results, it was found that the catalyst conversion decreased slightly as the reaction space velocity decreased. In the reaction process, after the addition of the auxiliary agent, the selectivity of the aromatic hydrocarbon of the catalyst is more than 70 percent, and the catalyst can keep the reaction for 100 hours without inactivation.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (10)
1. The catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion is characterized by comprising the following components:
molybdenum-based molecular sieve catalysts and catalysts with iron oxide as a carrier;
the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10;
wherein, the active component of the molybdenum-based molecular sieve catalyst is Mo, and the mass percentage content of the active component Mo in the molybdenum-based molecular sieve catalyst is 1-10%;
in the catalyst using iron oxide as carrier, carrier Fe2O3Is in the form of powder, and the mass percentage content of the ferric oxide is 1-10%.
2. The catalytic system of claim 1, wherein: the molecular sieve in the molybdenum-based molecular sieve catalyst is selected from one or more of HZSM-5 molecular sieve, SAPO-34 molecular sieve, H beta molecular sieve, MCM-41 molecular sieve, Q10 molecular sieve and HY molecular sieve.
3. The catalytic system of claim 1, wherein: the molar ratio of the silicon-aluminum components of the molecular sieve is 20-150: 1.
4. The catalytic system of claim 1, wherein: in the catalyst taking the iron oxide as the carrier, the active metal is one or more of Pt, Pd, Ru, Ni, Mn, Cu, Co, Zr, Mg, Cr, Zn, Ce, K, Al, Ag and Rh.
5. A process for the preparation of the catalytic system according to any one of claims 1 to 4, comprising the steps of:
preparing a molybdenum-based molecular sieve catalyst and a catalyst taking ferric oxide as a carrier by adopting an impregnation method, wherein the two catalysts are mixed according to a mass ratio of 1:1-10, fully grinding until the mixture is uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
6. The process for the preparation of the catalytic system according to claim 5, characterized in that it comprises the following specific steps:
1) roasting the molecular sieve carrier at 400-550 ℃ for 2-12 h;
2) preparing a molybdenum-based molecular sieve catalyst by adopting an excess impregnation method:
weighing Mo precursor and molecular sieve carrier according to a proportion, dissolving in deionized water, stirring and evaporating at 55-65 ℃, then drying at 115-125 ℃ for 10-15h, and roasting at 540-560 ℃ to obtain the molybdenum-based molecular sieve catalyst;
3) preparing a catalyst taking iron oxide as a carrier by adopting an excess impregnation method:
weighing the transition metal precursor and Fe according to the proportion2O3Dissolving the powder in a proper amount of glycol or deionized water, uniformly stirring, drying at 120-150 ℃ for 10-15h, and roasting at 380-420 ℃ to obtain a catalyst taking iron oxide as a carrier;
4) fully grinding the molybdenum-based molecular sieve catalyst and the catalyst taking ferric oxide as a carrier according to the mass ratio until the molybdenum-based molecular sieve catalyst and the catalyst are uniformly mixed, and granulating the obtained powder to obtain the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion.
7. The method of claim 6, wherein: in the step 1), the molecular sieve carrier is selected from one or more of HZSM-5 molecular sieve, SAPO-34 molecular sieve, H beta molecular sieve, MCM-41 molecular sieve, Q10 molecular sieve and HY molecular sieve;
preferably, in the step 2), the Mo precursor is ammonium molybdate tetrahydrate crystals; the amount of the deionized water for dissolving the Mo precursor and the molecular sieve carrier is 2-6mL/g, and the roasting time is 2-12 h.
8. The method of claim 6, wherein: in the step 3), the transition metal precursor is selected from one or more of chloroplatinic acid hexahydrate crystals, dinitrosoplatinum solution, palladium chloride powder, palladium nitrate solution, ruthenium nitrate solution and nickel nitrate hexahydrate crystals; the dissolved transition metal precursor and Fe2O3Powder ofThe amount of the ethylene glycol or the deionized water is 0-1mL/g, and the roasting time is 2-12 h;
preferably, in the step 4), the mass ratio of the molybdenum-based molecular sieve catalyst to the catalyst taking iron oxide as a carrier is 1: 1-10.
9. The application of the catalytic system for preparing the aromatic hydrocarbon by low-temperature methane conversion as claimed in any one of claims 1 to 4, which is characterized by comprising the following specific steps of:
11) the reaction is carried out in a fixed bed reactor, and the catalyst is placed in a quartz glass tube;
12) introducing reducing gas to activate the catalyst, wherein the activation temperature is 300-500 ℃, and the maintaining time is 1-10 h;
13) introducing raw material gas for reaction, wherein the raw material gas is methane gas with the concentration of 90% (10% Ar is used as internal standard gas), the reaction temperature is 350-cat·h。
10. Use according to claim 9, characterized in that: in the step 12), the reducing gas is one or more of hydrogen and synthesis gas;
preferably, in the step 13), an auxiliary agent is added during the reaction, and the auxiliary agent is selected from one or more of benzene, toluene and xylene.
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