CN116408138A - Catalyst for synthesizing aromatic hydrocarbon and preparation method and application thereof - Google Patents
Catalyst for synthesizing aromatic hydrocarbon and preparation method and application thereof Download PDFInfo
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- CN116408138A CN116408138A CN202111678550.5A CN202111678550A CN116408138A CN 116408138 A CN116408138 A CN 116408138A CN 202111678550 A CN202111678550 A CN 202111678550A CN 116408138 A CN116408138 A CN 116408138A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 19
- 239000011257 shell material Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 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 67
- 239000011162 core material Substances 0.000 claims abstract description 66
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
- 239000000843 powder Substances 0.000 claims abstract description 65
- 238000001035 drying Methods 0.000 claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 21
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 11
- 239000010431 corundum Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000003786 synthesis reaction Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 241000219782 Sesbania Species 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 102220043159 rs587780996 Human genes 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- -1 air Chemical compound 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- 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 provides a catalyst for synthesizing aromatic hydrocarbon, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a metal oxide, a metal modified HZSM-5 molecular sieve, a binder and a solvent, uniformly stirring, and drying to obtain a core material; mixing shell raw materials containing kaolin, corundum powder and pseudo-boehmite, and preparing shell material powder with the average particle size smaller than 100 mu m; mixing the inner core material, the shell material powder, inorganic acid and water, granulating to enable the shell material powder to exist on the surface of the inner core material, and preparing a catalyst precursor; and drying and roasting the catalyst precursor to obtain the catalyst. The catalyst of the invention has high catalytic activity and low attrition index, and can synthesize aromatic hydrocarbon in one step.
Description
Technical Field
The invention belongs to the technical field of synthesis gas conversion, and particularly relates to a catalyst for synthesizing aromatic hydrocarbon, a preparation method and application thereof.
Background
Heavy aromatic hydrocarbon is mixed aromatic hydrocarbon with carbon nine aromatic hydrocarbon as main component, and at present, the production of aromatic hydrocarbon raw material mainly adopts petroleum refining, but at present, the heavy aromatic hydrocarbon of China is large in use amount, and especially uses durene, and these components are all very precious organic chemical raw materials, so that the development of novel synthetic aromatic hydrocarbon production technology has great significance.
At present, synthesis gas is used as a raw material for preparing hydrocarbon products, the content of the synthesized hydrocarbon products is often low, so that the development of a novel catalyst system has important significance for improving the conversion rate and selectivity in the conversion process of the synthesis gas, for example, patent document CN106607083A provides a catalyst for preparing aromatic hydrocarbon from the synthesis gas and a use method thereof, a physical mixing and tabletting method is adopted to obtain a ferrite catalyst for loading ZSM-5, the catalyst is applied to industrial production of preparing aromatic hydrocarbon from the synthesis gas, and the ferrite catalyst has the problems of activity reduction, easy abrasion and the like under high-temperature and high-pressure reaction conditions. And only the synthesis of light aromatics is studied in this document and the synthesis of heavy aromatics is not involved.
Generally, an aromatic hydrocarbon is prepared by a two-step method, for example, patent document CN110002932a provides a method and an apparatus for preparing aromatic hydrocarbon by using synthesis gas, wherein the aromatic hydrocarbon is prepared by a two-stage reactor, and a catalyst is filled in a first-stage reaction zone to convert the synthesis gas into hydrocarbons mainly comprising olefins; filling another catalyst in the second stage reaction zone, introducing benzene or toluene, and adding a large quantity of hydrogen and CO 2 In the presence, olefins are converted to aromatics by alkylation. In order to improve the reaction efficiency, a catalyst for synthesizing aromatic hydrocarbon in one step needs to be developed, and the catalytic activity, the wear resistance and the applicability of the catalyst are required to be higher by adopting a one-step method for preparing the aromatic hydrocarbon.
Disclosure of Invention
The catalyst prepared by the preparation method has high catalytic activity and low attrition index, can synthesize aromatic hydrocarbon in one step, and effectively overcomes the defects in the prior art.
In one aspect of the present invention, there is provided a method for preparing a catalyst for synthesizing aromatic hydrocarbons, comprising the steps of: mixing a metal oxide, a metal modified HZSM-5 molecular sieve, a binder and a solvent, uniformly stirring, and drying to obtain a core material; mixing shell raw materials containing kaolin, corundum powder and pseudo-boehmite, and preparing shell material powder with the average particle size smaller than 100 mu m; mixing the inner core material, the shell material powder, inorganic acid and water, granulating to enable the shell material powder to exist on the surface of the inner core material, and preparing a catalyst precursor; and drying and roasting the catalyst precursor to obtain the catalyst.
According to an embodiment of the present invention, the mass ratio of the core material and the catalyst precursor is (30 to 95): 100; and/or, the process of mixing the core material, the shell material powder, the inorganic acid and the water comprises the following steps: dissolving inorganic acid in water to prepare an inorganic acid aqueous solution; wherein the mass concentration of the inorganic acid in the inorganic acid aqueous solution is 1% -3%; mixing an aqueous solution of inorganic acid with powders of a core material and a shell material, wherein the mass ratio of the core material to the aqueous solution of inorganic acid is (1:15): 1.
according to one embodiment of the invention, the mass ratio of the kaolin, the corundum powder and the pseudo-boehmite in the shell raw material is 1: (0.5-5): (0.05-0.5).
According to an embodiment of the invention, the shell material further comprises an auxiliary agent; the mass ratio of the kaolin to the auxiliary agent is 1: (0.02-0.1); the auxiliary agent comprises at least one of silicon carbide, silicon oxide and potassium oxide.
According to an embodiment of the present invention, the shell material further comprises sesbania powder; the mass ratio of the kaolin to the sesbania powder is 1: (0.01-0.05).
According to one embodiment of the invention, the mass ratio of the metal oxide to the metal modified HZSM-5 molecular sieve is 5: (1-25); and/or the metal in the metal oxide comprises at least one of copper, aluminum, zinc; and/or the metal in the metal modified HZSM-5 molecular sieve comprises at least one of zinc, molybdenum, cobalt, niobium, and nickel.
According to an embodiment of the present invention, the metal oxide has a copper molar content of 30% to 60%, a zinc molar content of 30% to 60%, and an aluminum molar mass of 10% to 15%.
According to one embodiment of the invention, the roasting adopts a sectional roasting treatment, and the process of the sectional roasting treatment comprises the following steps: carrying out first roasting treatment on the dried catalyst precursor in inert atmosphere, and then carrying out second roasting treatment in oxygen-containing gas; wherein the reaction conditions of the first roasting treatment are as follows: the temperature is 200-400 ℃, the time is 1-8 h, and the reaction conditions of the second roasting treatment are as follows: the temperature is 450-600 ℃ and the time is 3-8 h.
In a second aspect of the invention, there is provided a catalyst for the synthesis of aromatic hydrocarbons, obtainable by the process as described above.
In a third aspect of the present invention, there is provided a process for the preparation of an aromatic hydrocarbon comprising reacting a feedstock comprising hydrogen and carbon monoxide over a catalyst to produce an aromatic hydrocarbon product; wherein the catalyst comprises the catalyst.
The implementation of the invention has at least the following beneficial effects:
the preparation method of the catalyst for synthesizing aromatic hydrocarbon provided by the invention can be used for preparing a double-structure catalyst with a core and a shell, wherein the catalyst comprises a core material and a shell material existing on the surface of the core material, and the core material containing metal oxide and metal modified HZSM-5 molecular sieve can be used as an active component of the catalyst; the shell material prepared from the raw materials contains a large amount of alumina, so that the mechanical strength of the catalyst can be improved, the prepared catalyst has high catalytic activity, can be used for synthesizing aromatic hydrocarbon, especially for synthesizing C9+ heavy aromatic hydrocarbon, improves the aromatic hydrocarbon yield, has good wear resistance (the wear index is not higher than 5.1 percent), is beneficial to use, and has long service life; meanwhile, the catalyst can also be used for synthesizing heavy aromatic hydrocarbon by a one-step method, so that the synthesis process of the heavy aromatic hydrocarbon is simplified.
In addition, the preparation method of the catalyst for synthesizing aromatic hydrocarbon provided by the invention has the advantages of simple preparation process, controllable process conditions, easiness in operation and the like, and is beneficial to industrial production and application.
Detailed Description
The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the catalyst for synthesizing aromatic hydrocarbon provided by the invention comprises the following steps: mixing a metal oxide, a metal modified HZSM-5 molecular sieve, a binder and a solvent, uniformly stirring, and drying to obtain a core material; mixing shell raw materials containing kaolin, corundum powder and pseudo-boehmite, and preparing shell material powder with the average particle size smaller than 100 mu m; mixing the inner core material, the shell material powder, inorganic acid and water, granulating to enable the shell material powder to exist on the surface of the inner core material, and preparing a catalyst precursor; and drying and roasting the catalyst precursor to obtain the catalyst.
Through the process, the performances of the prepared catalyst such as catalytic activity, stability and mechanical strength can be improved, and the inventor considers through research and analysis that in the preparation process, firstly, a metal oxide and a metal modified HZSM-5 molecular sieve are compounded to be used as active components of the catalyst together; secondly, mixing shell raw materials containing an alumina component, enhancing the mechanical strength of the shell, and enabling the average particle size of powder of the shell material to be smaller than 100 mu m, so that the shell material can uniformly exist on the surface of the inner core, loosening of powder of the shell material caused by overlarge particle size is prevented, and the shell material cannot be molded on the surface of the inner core, thereby influencing the stability and mechanical strength of the catalyst; in addition, the shell material is stably present on the surface of the inner core by adding the binder such as inorganic acid, and the shell material and the inner core are matched together to show good synergistic effect. By the above process, it is also advantageous to obtain a catalyst in which the components are uniformly distributed. Therefore, through the preparation process, the catalyst with the advantages of good catalytic activity, high mechanical strength, good stability and the like can be prepared.
Specifically, mixing a metal oxide, a metal modified HZSM-5 molecular sieve, a binder and a solvent, uniformly stirring, uniformly compounding the metal oxide and the metal modified HZSM-5 molecular sieve together under the action of the binder in the uniform stirring process, and filtering, washing and drying to obtain a core material; wherein, before mixing, the metal oxide and the metal modified HZSM-5 molecular sieve are crushed and ground to the particle size of below 200 meshes; in some embodiments, the metal oxide, metal modified HZSM-5 molecular sieve has a mass ratio of 5: (1 to 25), for example, 5: 1. 5: 3. 1: 1. 1: 2. 1: 3. 1: 4. 1:5 or any two thereof. Wherein the binder comprises silica gel, and in the specific implementation process, the silica gel is mixed with water to form a silica gel solution, and the concentration of the silica gel solution is 15% -30%, for example, 15%, 20%, 25%, 30% or a range formed by any two of the silica gel solutions. The conditions of the drying process are: the drying temperature is in the range of 90 ℃ to 120 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃ or any two of them, and the drying time is in the range of 9h to 15h, such as 9h, 10h, 11h, 12h, 15h or any two of them.
In the invention, the core material obtained by compounding the metal oxide and the metal modified HZSM-5 molecular sieve is an active component of the catalyst, and the core material has the catalytic activity of the metal oxide and the metal modified HZSM-5 molecular sieve by adjusting the mass ratio of the metal oxide to the metal modified HZSM-5 molecular sieve in the core material, so that the active component with high catalytic activity can be obtained, and the stability of the catalyst is improved.
In some embodiments, the metal in the metal oxide comprises at least one of copper, aluminum, zinc, i.e., at least one of copper oxide, aluminum oxide, zinc oxide.
In the present invention, the metal oxide is an oxide containing at least copper, preferably a mixed oxide containing copper, aluminum, or zinc. In some embodiments, the molar content of copper in the metal oxide is in the range of 30% -60%, e.g., 30%, 35%, 40%, 45%, 50%, 55%, 60%, or any two of these; the molar content of zinc is in the range of 30% to 60%, such as 30%, 35%, 37.5%, 40%, 45%, 50%, 55%, 60% or any two thereof; the molar mass of aluminum is in the range of 10% to 15%, for example 10%, 11%, 12.5%, 13%, 14%, 15% or any two thereof.
Specifically, the metal oxide may be purchased or obtained by conventional methods, for example, by the following preparation processes: mixing metal salt and water to obtain a metal salt solution; dropwise adding ammonia water into the metal salt solution until the pH reaches 8.0-8.1 to obtain a metal precipitate; and drying and roasting the metal precipitate to obtain the metal oxide. Wherein the metal salt comprises at least one of copper salt, aluminum salt and zinc salt, further comprises at least one of copper nitrate, aluminum nitrate and zinc nitrate, preferably a mixed metal salt of copper nitrate, aluminum nitrate and zinc nitrate, and the water can be deionized water, and oxides containing copper, aluminum and zinc are obtained through the preparation process.
In the specific implementation process of the invention, the mixed solution can be acidified by adding nitric acid solution into the metal salt solution, the metal salt can be completely dissolved in water to form uniform metal salt solution by heating and stirring, the heating temperature is 60-80 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any two of the two ranges, and the heating and stirring time is 0.5h; dropwise adding ammonia water with the concentration of 1mol/L into the mixed solution until the pH reaches 8.0-8.1, precipitating metal ions in the mixed solution in a precipitation mode under the condition of constant-temperature water bath, aging the precipitate for 1-1.5 h, filtering and washing the precipitate to obtain a metal precipitate, drying the metal precipitate to remove excessive water, obtaining a metal oxide precursor, and roasting the metal oxide precursor to obtain the metal oxide. Wherein the dropping of ammonia water is accompanied by continuous stirring to uniformly mix the solution, the dropping amount of ammonia water is determined according to pH, the filtration can be performed by a conventional filtration method such as suction filtration to filter out the precipitated product, and the filtered product is washed with distilled water to remove unreacted salts on the surface of the filtered product, the washing is performed at least once, wherein the washing process comprises washing three times with 800mL of distilled water; the conditions of the drying treatment are as follows: the drying temperature is 90-120 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃ or a range composed of any two of them, and the drying time is 9-15 h, such as 9h, 10h, 11h, 12h, 15h or a range composed of any two of them; the conditions of the roasting treatment are as follows: the firing temperature is 300 to 500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or a range composed of any two of them, and the firing time is 2 to 6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or a range composed of any two of them.
Further, the metal modified HZSM-5 molecular sieve is a HZSM-5 molecular sieve loaded with modified metal, and in the metal modified HZSM-5 molecular sieve, the mass ratio of the metal to the HZSM-5 molecular sieve is 3-6: 100, for example 3: 100. 4: 100. 5: 100. 6:100 or any two of them to ensure that the molecular sieve in the inner core has complete crystal form and uniform grain distribution. In the metal modified HZSM-5 molecular sieve, the HZSM-5 molecular sieve is provided with hollow particles and contains a plurality of pore channels with uniform pore diameters, the metal is loaded on the surface of a molecular sieve framework or is embedded into the molecular sieve framework, the metal modified HZSM-5 molecular sieve has better catalytic performance by introducing modified metal, and the stability of the structure of the metal modified HZSM-5 molecular sieve is further enhanced by controlling the mass ratio of the modified metal to the HZSM-5 molecular sieve, so that the catalytic performance of an active component is improved. In some embodiments, the metal in the metal-modified HZSM-5 molecular sieve comprises at least one of zinc, molybdenum, cobalt, niobium, and nickel, preferably at least one of zinc and nickel, to further reduce the cost of the catalyst, e.g., the metal-modified HZSM-5 molecular sieve may be a zinc-modified HZSM-5 molecular sieve, may be a nickel-modified HZSM-5 molecular sieve, and may be a zinc and nickel-modified HZSM-5 molecular sieve.
In the invention, a conventional method is adopted to prepare the metal modified HZSM-5 molecular sieve, which comprises the following steps: mixing an HZSM-5 molecular sieve, metal salt and water, and standing to obtain a modified mixture; drying and roasting the mixture to obtain a metal modified HZSM-5 molecular sieve, wherein the mixing and standing are performed to allow metal salt to enter pore channels of a molecular sieve framework so as to reach molecular sieve adsorption saturation; the purpose of the drying process is to remove the moisture from the mixture to obtain a modified molecular sieve precursor, the drying process conditions being: the drying temperature is 90-120 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃ or a range composed of any two of them, and the drying time is 9-15 h, such as 9h, 10h, 11h, 12h, 15h or a range composed of any two of them; the metal is loaded on the surface of the molecular sieve framework or embedded into the molecular sieve framework through roasting treatment, and the conditions of the roasting treatment are as follows: the firing temperature is 300 to 500 ℃, such as 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃ or a range composed of any two of them, and the firing time is 2 to 6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours, 6 hours or a range composed of any two of them.
Specifically, the process of mixing the HZSM-5 molecular sieve, the metal salt and water and then standing the mixture comprises the steps of firstly mixing the metal salt and water to form a solution containing the metal salt at room temperature, then slowly dripping the solution containing the metal salt into the HZSM-5 molecular sieve to enable the metal salt to be adsorbed in the molecular sieve, and then standing the mixture for 9-15 hours to obtain a modified mixture, for example, 9 hours, 10 hours, 11 hours, 12 hours, 15 hours or a range formed by any two of the metal salt and the water.
In the practice of the present invention, the metal modified HZSM-5 molecular sieves include HZSM-5 molecular sieves modified with at least two metals, and the particular preparation process includes, for example: mixing an HZSM-5 molecular sieve, a first metal salt and water, and standing to obtain a first modified mixture; drying and roasting the first modified mixture to obtain a first metal modified HZSM-5 molecular sieve; then mixing the first metal modified HZSM-5 molecular sieve, second metal salt and water, and standing to obtain a second modified mixture; and drying and roasting the second modified mixture to obtain the first metal and second metal modified HZSM-5 molecular sieve.
In the present invention, the shell material contains alumina, and the alumina component can enhance the mechanical strength of the shell material, further enhance the mechanical strength of the catalyst, and in order to enhance the adhesion between the alumina component and the core material, in some embodiments, the shell material powder is prepared by using a shell raw material containing kaolin, corundum powder and pseudo-boehmite.
In general, the shell material is ground to obtain a shell material powder, and the average particle diameter (or D50) of the shell material powder is set to be less than 100. Mu.m, preferably 30 μm to 80. Mu.m, more preferably 40 μm to 70. Mu.m, for example, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm or any two of the above ranges, and the powder particle diameter in the above range can prevent the loosening of the shell material due to the excessive particle diameter of the powder, thereby affecting the mechanical strength of the catalyst; meanwhile, the particle size of the powder is prevented from being too small, so that the densification degree of the shell material formed by the powder is too high, and the catalytic activity of the inner core is influenced. Among them, the submerged treatment adopts a conventional grinding method, for example, grinding the shell raw material using a planetary ball mill.
In some embodiments, the mass ratio of kaolin to corundum powder is 1: (0.5 to 5), for example, 1:0.5, 1: 1. 1: 3. 1:5 or any two thereof; the mass ratio of the kaolin to the pseudo-boehmite is 1: (0.05 to 0.5), for example, 1:0.05, 1:0.1, 1:0.3, 1:0.5 or any two thereof.
In order to further improve the comprehensive performance of the shell material, the shell raw material also comprises an auxiliary agent; the mass ratio of the kaolin to the auxiliary agent is 1: (0.02 to 0.1), for example, 1:0.02, 1:0.08, 1:0.1 or any two thereof; the auxiliary agent comprises at least one of silicon carbide, silicon oxide and potassium oxide. Wherein silicon carbide and silicon oxide can further enhance the wear resistance of the shell material, and potassium oxide can improve the specific surface area of the shell material, increase the contact area between the catalyst and the reaction gas, and further improve the catalytic activity.
In the present invention, in order to further improve the adhesion between the shell material powder and the core material, in some embodiments, the shell material further includes sesbania powder; the sesbania powder can increase the adhesion capability of the shell material powder, so that the shell material powder can stably exist on the surface of the inner core, and the mass ratio of the kaolin to the sesbania powder is 1: (0.01 to 0.05), for example, 1:0.01, 1:0.02, 1:0.04, 1:0.05 or any two thereof.
In the invention, the inner core material, the shell material powder, the inorganic acid and the water which meet the requirements are mixed and then granulated, so that the shell material powder exists on the surface of the inner core material to prepare the catalyst precursor; wherein the granulation process may be performed in a centrifugal granulator, the granulation process comprising: placing the core material on a rotary table of a centrifugal granulator, and coating the surface of the core material with shell material powder by taking inorganic acid as a binder, wherein the operation conditions of the centrifugal granulator are as follows: the turntable has a diameter of 45cm and a rotational speed of the turntable in the range of 100 revolutions per minute to 200 revolutions per minute (rpm), such as 100rpm, 150rpm, 200rpm or any two thereof; the catalyst precursor may be of any shape, for example, it may be in the form of a sphere having a diameter of 30mm to 35 mm.
In some embodiments, the mass ratio of the core material to the catalyst precursor is (30-95): 100, i.e., the mass content of the core material in the catalyst precursor is in the range of 30% to 95%, e.g., 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 80%, 88%, 95% or any two thereof.
In the invention, the process of mixing the core material, the shell material powder, the inorganic acid and the water comprises the following steps: dissolving inorganic acid in water to prepare an inorganic acid aqueous solution; the inorganic acid aqueous solution is mixed with the powder of the core material and the shell material. The inorganic acid aqueous solution is an adhesive between the shell material powder and the core material, so that the adhesiveness between the shell material powder and the core material is ensured, and the phenomenon that the shell material powder collapses during subsequent roasting due to the inorganic acid aqueous solution with excessive mass is prevented, and in some embodiments, the mass ratio of the core material to the inorganic acid aqueous solution is (1:15): 1, for example 1: 1. 3: 1. 5: 1. 10: 1. 15:1 or any two thereof; wherein the mass concentration of the inorganic acid in the aqueous solution of the inorganic acid is 1% to 3%, for example, 1%, 1.5%, 2%, 2.5%, 3% or any two thereof.
In the present invention, the catalyst precursor is dried and calcined to obtain a catalyst, wherein the drying includes at least one of an air-flow spray drying method, a centrifugal spray drying method, and an evaporation drying method, for example, the catalyst precursor is evaporated and dried in a forced air drying oven at a drying temperature of 120 to 240 ℃, for example, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 240 ℃, or any two thereof, and a drying time of 1 to 8 hours, for example, 1 hour, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, or any two thereof.
In some embodiments, the firing employs a staged firing process, the staged firing process comprising: carrying out first roasting treatment on the dried catalyst precursor in inert atmosphere, and then carrying out second roasting treatment in oxygen-containing gas; the inert atmosphere is an atmosphere containing an inert gas including nitrogen; the oxygen-containing gas is an atmosphere containing oxygen, such as air, an oxidizing atmosphere; the reaction conditions of the first roasting treatment are as follows: the temperature is 200-400 ℃, such as 200 ℃, 250 ℃, 300 ℃, 330 ℃, 380 ℃, 400 ℃ or any two of them, the time is 1-8 h, such as 1h, 2h, 4h, 6h, 8h or any two of them, and the reaction conditions of the second roasting treatment are: the temperature is in the range of 450 ℃ to 600 ℃, such as 450 ℃, 500 ℃, 550 ℃, 600 ℃ or any two thereof, the time is in the range of 3 hours to 8 hours, such as 3 hours, 5 hours, 6 hours, 8 hours or any two thereof, the first roasting and the second roasting can be performed in a tube furnace, such as at a temperature rising rate of 3 ℃/min to 6 ℃/min, such as 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min or any two thereof.
The catalyst for synthesizing aromatic hydrocarbon provided by the invention is prepared by adopting the preparation method. The catalyst for synthesizing the aromatic hydrocarbon has a double-structure catalyst taking a molecular sieve as an inner core, wherein the inner core of the catalyst not only has a pore channel structure of an HZSM-5 molecular sieve, but also has the stability of metal oxide and the capability of catalyzing and synthesizing the aromatic hydrocarbon; the shell of the catalyst has high mechanical strength on the premise of not affecting the catalytic activity of the inner core, and the two materials are compounded together by utilizing the different advantages of the inner core and the outer shell, so that the catalyst has good catalytic activity and mechanical strength, and is favorable for the reaction of synthesizing aromatic hydrocarbon by a one-step method.
The aromatic hydrocarbon preparation method provided by the invention comprises the steps of reacting raw materials containing hydrogen and carbon monoxide under the action of the catalyst to generate an aromatic hydrocarbon product; the specific process comprises the following steps: loading the catalyst into a reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction to obtain aromatic hydrocarbon; wherein the synthesis gas comprises hydrogen (H) 2 ) Carbon monoxide (CO), wherein the volume ratio of the hydrogen to the carbon monoxide is (0.5-3): 1, for example 0.5: 1. 1: 1. 2: 1. 3:1 or any two thereof. The reaction conditions in the reactor are as follows: the reaction temperature is 300 to 500 ℃, for example 300 to 330 ℃, 400 ℃, 500 ℃ or any two of them, and the pressure is 0.4 to 4MPa, for example 0.4MPa, 0.8MPa, 1MPa, 2MPa, 4MPa or any two of them.
The catalyst has excellent structural stability and wide application range, and is used in the preparation of aromatic hydrocarbonThe catalyst can be used in both tubular reactors and fluidized bed reactors. For example, the volume space velocity of CO gas in the tubular reactor is 600h -1 ～1000h -1 For example 600h -1 、800h -1 、1000h -1 Or any two of them, the reaction time is 1 h-12 h, for example 1h, 5h, 10h, 12h or any two of them; the gas velocity in the fluidized bed reactor is in the range of 0.25m/s to 1m/s, for example 0.25m/s, 0.5m/s, 0.75m/s, 1m/s or any two of these.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, metal oxides and metal modified HZSM-5 molecular sieves were prepared as follows:
preparation of metal oxide:
dissolving 4mol of copper nitrate trihydrate, 3mol of zinc nitrate hexahydrate and 1mol of aluminum nitrate nonahydrate in 1960mL of deionized water to form a mixed solution, adding 40mL of nitric acid into the mixed solution for acidification, and stirring at 70 ℃ for 0.5h to form a uniform metal salt solution; slowly dripping 1mol/L ammonia water solution into the mixed solution under the condition of constant-temperature water bath at 70 ℃ and continuously stirring until the pH value reaches 8.0 to obtain a precipitate, and aging the precipitate for 1.5h; filtering and separating the obtained precipitate, and washing the separated precipitate with 800mL of distilled water for three times; drying the washed precipitate at 110 ℃ for 12 hours, and roasting at 300 ℃ for 3 hours to obtain the metal oxide.
Preparation of metal modified HZSM-5 molecular sieves:
dissolving 54.1g of nickel nitrate hexahydrate in 100mL of deionized water to form a nickel nitrate solution, slowly dripping the nickel nitrate solution into 20g of HZSM-5 molecular sieve until adsorption is saturated, and standing for 12h at room temperature to obtain a nickel modified mixture;
drying the nickel modified mixture at 110 ℃ for 12 hours in sequence, and roasting for 4 hours at 500 ℃ to obtain a nickel modified HZSM-5 molecular sieve;
dissolving 49.6g of zinc nitrate hexahydrate in 100mL of deionized water to form a zinc nitrate solution, slowly dripping the obtained zinc nitrate solution into 20g of nickel modified HZSM-5 molecular sieve until adsorption is saturated, standing for 12h at room temperature, sequentially drying the obtained product at 110 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain zinc and nickel modified HZSM-5 molecular sieve; wherein, in the zinc and nickel modified HZSM-5 molecular sieve, the mass of the modified metal zinc is 3% of the mass of the HZSM-5 molecular sieve, and the mass of the modified metal nickel is 3% of the mass of the HZSM-5 molecular sieve.
Example 1
Preparation of the catalyst
Crushing 19g of metal oxide and 19g of zinc and nickel modified HZSM-5 molecular sieve to below 200 meshes, adding 15% of silica gel solution into the crushed powder, stirring the mixture for 20 minutes to uniformly mix the mixture, filtering and washing the mixture, and drying the mixture at 110 ℃ for 12 hours to obtain a core material;
mixing shell raw materials containing 25g of kaolin (wherein the alumina content in the kaolin is 45.7 wt% and the water content is 0.4 wt%, respectively), 75g of corundum powder, 5g of pseudo-boehmite, 2g of silicon carbide and 1.25g of sesbania powder, and grinding the shell raw materials by using a planetary ball mill to obtain shell material powder with D50=70 mu m;
placing the inner core material into a centrifugal granulator with the diameter of a rotary disc of 45cm and the rotating speed of 200rpm, taking nitric acid with the mass concentration of 3% as a binder, and coating shell material powder on the surface of the inner core material to obtain a catalyst precursor with the diameter of about 35 mm; wherein the mass ratio of the core material to the nitric acid aqueous solution is 10:1, the mass content of the core material in the catalyst precursor is 35%;
drying the catalyst precursor in a forced air drying oven at 120 ℃ for 5 hours by adopting an evaporation drying method, performing first roasting on the dried catalyst in a nitrogen atmosphere, and performing second roasting in an oxidizing atmosphere to finally obtain the catalyst; wherein the first roasting temperature is 380 ℃, the time is 4 hours, the second roasting temperature is 550 ℃, the time is 8 hours, and the heating rates of the first roasting and the second roasting are 4 ℃/min;
preparation of aromatic hydrocarbons
Loading the catalyst 4g into a fixed bed tubular reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction, wherein H in the synthesis gas 2 The volume ratio of the catalyst to CO is 2, the reaction temperature is 330 ℃, the pressure is 4MPa, and the space velocity of the reaction gas is 600h -1 The reaction time was 12 hours, and the reaction results are shown in Table 1.
The catalyst of example 1 was analyzed to have a mass content of 78% alumina.
Example 2
Preparation of the catalyst
Crushing 25g of metal oxide and 25g of zinc and nickel modified HZSM-5 molecular sieve to below 200 meshes, adding 20% of silica gel solution into the crushed mixture, stirring the mixture for 30min to uniformly mix the mixture, filtering and washing the mixture, and drying the mixture at 110 ℃ for 10h to obtain a core material;
mixing shell raw materials containing 25g of kaolin (wherein the alumina content in the kaolin is 45.7 wt% and the water content is 0.4 wt%, respectively), 25g of corundum powder, 7.5g of pseudo-boehmite, 0.5g of silicon carbide and 1g of sesbania powder, and grinding the shell raw materials by using a planetary ball mill to obtain a shell material powder with D50=40 mu m;
placing the inner core material into a centrifugal granulator with the diameter of a rotary disc of 45cm and the rotating speed of 100rpm, taking nitric acid with the mass concentration of 2% as a binder, and coating shell material powder on the surface of the inner core material to obtain a catalyst precursor with the diameter of about 30 mm; wherein the mass ratio of the core material to the nitric acid aqueous solution is 5:1, the mass content of the core material in the catalyst precursor is 88%;
drying the catalyst precursor for 1 hour at 180 ℃ by adopting airflow spraying, performing first roasting on the dried catalyst in a nitrogen atmosphere, and performing second roasting in an oxidizing atmosphere to finally obtain the catalyst; wherein the first roasting temperature is 300 ℃, the time is 6 hours, the second roasting temperature is 500 ℃, the time is 6 hours, and the heating rates of the first roasting and the second roasting are 4 ℃/min;
preparation of aromatic hydrocarbons
Loading the catalyst 4g into a fixed bed tubular reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction, wherein H in the synthesis gas 2 The volume ratio of the catalyst to CO is 2, the reaction temperature is 330 ℃, the pressure is 4MPa, and the space velocity of the reaction gas is 1000h -1 The reaction time was 12 hours, and the reaction results are shown in Table 1.
The mass content of alumina in the catalyst of example 2 was analyzed to be 72%.
Example 3
Preparation of the catalyst
Crushing 50g of metal oxide and 50g of zinc and nickel modified HZSM-5 molecular sieve to below 200 meshes, adding 25% of silica gel solution into the crushed mixture, stirring the mixture for 40 minutes to uniformly mix the mixture, filtering and washing the mixture, and drying the mixture at 120 ℃ for 10 hours to obtain a core material;
mixing shell raw materials containing 50g of kaolin (wherein the alumina content in the kaolin is 45.7 wt% and the water content is 0.4 wt%, respectively), 100g of corundum powder, 5g of pseudo-boehmite, 5g of silicon carbide and 1g of sesbania powder, and grinding the shell raw materials by using a planetary ball mill to obtain shell material powder with D50=60 mu m;
placing the inner core material into a centrifugal granulator with the diameter of a rotary disc of 45cm and the rotating speed of 150rpm, taking nitric acid with the mass concentration of 1% as a binder, and coating shell material powder on the surface of the inner core material to obtain a catalyst precursor with the diameter of about 35 mm; wherein the mass ratio of the core material to the nitric acid aqueous solution is 3:1, the mass content of the core material in the catalyst precursor is 65%;
drying the catalyst precursor for 6 hours at 150 ℃ by adopting a centrifugal spraying method, performing first roasting on the dried catalyst in a nitrogen atmosphere, and performing second roasting in an oxidizing atmosphere to finally obtain the catalyst; wherein the first roasting temperature is 400 ℃, the time is 4 hours, the second roasting temperature is 550 ℃, the time is 8 hours, and the heating rates of the first roasting and the second roasting are 6 ℃/min;
preparation of aromatic hydrocarbons
Loading the catalyst 40g into a fluidized bed reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction, wherein H in the synthesis gas 2 The volume ratio to CO was 2, the reaction temperature was 330℃and the pressure was 4MPa, the gas flow rate of the fluidized bed was 0.25m/s, the reaction time was 1h, and the reaction results are shown in Table 1.
The mass content of alumina in the catalyst of example 3 was analyzed to be 70%.
Comparative example 1
Preparation of the catalyst
Crushing 50g of metal oxide and 50g of zinc and nickel modified HZSM-5 molecular sieve to below 200 meshes, filtering, washing, and drying at 120 ℃ for 10 hours to obtain a catalyst precursor; roasting the catalyst precursor for 8 hours under the condition of 500 ℃ in nitrogen atmosphere, wherein the roasting heating rate is 3 ℃/min, and finally obtaining the catalyst;
preparation of aromatic hydrocarbons
Loading the 40g catalyst into a fixed bed reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction, wherein H in the synthesis gas 2 The volume ratio of the catalyst to CO is 2, the reaction temperature is 330 ℃, the pressure is 4MPa, and the space velocity of the reaction gas is 1000h -1 The reaction time was 12 hours, and the reaction results are shown in Table 1.
Comparative example 2
Preparation of the catalyst
Crushing 50g of metal oxide and 50g of zinc and nickel modified HZSM-5 molecular sieve to below 200 meshes, filtering, washing, and drying at 120 ℃ for 10 hours to obtain a catalyst precursor; roasting the catalyst precursor for 10 hours under the nitrogen atmosphere at the temperature of 600 ℃ at the roasting heating rate of 3 ℃/min to finally obtain a catalyst;
preparation of aromatic hydrocarbons
Loading the 40g catalyst into a fixed fluidized bed reactor, and introducing synthesis gas into the reactor to carry out synthesis reaction, wherein H in the synthesis gas 2 The volume ratio to CO was 2, the reaction temperature was 330℃and the pressure was 0.4MPa, the gas flow rate of the fluidized bed was 0.25m/s, the reaction time was 1h, and the reaction results are shown in Table 1.
In the present invention, the conversion (%) means the conversion of the synthesis gas into a product, and the conversion is calculated from the conversion (%) = (mole number of CO reacted)/(mole number of CO supplied) ×100%; the selectivity was calculated as selectivity (%) = (moles of product produced)/(moles of CO reacted) ×100%; analyzing the reacted product on line by adopting gas chromatography and calculating to obtain the conversion rate and selectivity of the corresponding product; the abrasion performance of the catalyst is measured by adopting a high-speed air injection method, and the specific process comprises the following steps: placing a catalyst sample in an experimental device, suspending the catalyst by utilizing the action of flowing fluid to form fluidization, abrading the catalyst under the erosion action of the fluid, weighing the mass of the catalyst every one hour, calculating according to the ratio of the mass difference before and after the abrasion of the catalyst to the original mass of the catalyst to obtain an abrasion index, and summarizing to obtain a table 1:
TABLE 1
As can be seen from Table 1, the catalysts of comparative examples 1-2, which had no shell structure, were placed in a fluidized bed reactor, and the catalyst of comparative example 2 was not maintained in a stable fluidized state, resulting in powder blocking portions formed by attrition of the catalyst after the reaction, analyzing the sample inlet, and affecting the progress of the reaction. The catalyst for synthesizing aromatic hydrocarbon has the advantages of simple preparation method, high wear resistance, mechanical strength and far lower wear index than that of a comparative example, and good reaction activity during synthesizing aromatic hydrocarbon, especially durene (the durene selectivity is higher than 18.99 percent), and wide application range, and can be applied to a fixed bed reactor and a fluidized bed reactor.
Preferred embodiments of the present invention and experimental verification are described in detail above. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. A method for preparing a catalyst for synthesizing aromatic hydrocarbons, comprising the steps of:
mixing a metal oxide, a metal modified HZSM-5 molecular sieve, a binder and a solvent, uniformly stirring, and drying to obtain a core material;
mixing shell raw materials containing kaolin, corundum powder and pseudo-boehmite, and preparing shell material powder with the average particle size smaller than 100 mu m;
mixing the inner core material, the shell material powder, inorganic acid and water, granulating to enable the shell material powder to exist on the surface of the inner core material, and preparing a catalyst precursor;
and drying and roasting the catalyst precursor to obtain the catalyst.
2. The preparation method according to claim 1, wherein the mass ratio of the core material to the catalyst precursor is (30 to 95): 100; and/or the number of the groups of groups,
the process of mixing the kernel material, the shell material powder, the inorganic acid and the water comprises the following steps:
dissolving the inorganic acid in water to prepare an inorganic acid aqueous solution; wherein the mass concentration of the inorganic acid in the inorganic acid aqueous solution is 1% -3%;
mixing the inorganic acid aqueous solution with the core material and the shell material powder, wherein the mass ratio of the core material to the inorganic acid aqueous solution is (1:15): 1.
3. the preparation method according to claim 1, wherein the mass ratio of the kaolin, the corundum powder and the pseudo-boehmite in the shell raw material is 1: (0.5-5): (0.05-0.5).
4. A method of preparation according to any one of claims 1 to 3 wherein the shell material further comprises an auxiliary agent; the mass ratio of the kaolin to the auxiliary agent is 1: (0.02-0.1); the auxiliary agent comprises at least one of silicon carbide, silicon oxide and potassium oxide.
5. The method according to claim 4, wherein the shell material further comprises sesbania powder; the mass ratio of the kaolin to the sesbania powder is 1: (0.01-0.05).
6. The preparation method according to claim 1, wherein the mass ratio of the metal oxide to the metal modified HZSM-5 molecular sieve is 5: (1-25); and/or the number of the groups of groups,
the metal in the metal oxide comprises at least one of copper, aluminum and zinc; and/or the number of the groups of groups,
the metal in the metal modified HZSM-5 molecular sieve comprises at least one of zinc, molybdenum, cobalt, niobium and nickel.
7. The method according to claim 1 or 6, wherein the metal oxide has a copper molar content of 30 to 60%, a zinc molar content of 30 to 60%, and an aluminum molar mass of 10 to 15%.
8. The method of claim 1, wherein the firing employs a staged firing process, the staged firing process comprising: carrying out first roasting treatment on the dried catalyst precursor in inert atmosphere, and then carrying out second roasting treatment in oxygen-containing gas; wherein the reaction conditions of the first roasting treatment are as follows: the temperature is 200-400 ℃, the time is 1-8 h, and the reaction conditions of the second roasting treatment are as follows: the temperature is 450-600 ℃ and the time is 3-8 h.
9. A catalyst for the synthesis of aromatic hydrocarbons, characterized in that it is obtainable by the process according to any one of claims 1 to 8.
10. A method for preparing aromatic hydrocarbon is characterized by comprising the steps of reacting raw materials containing hydrogen and carbon monoxide under the action of a catalyst to generate an aromatic hydrocarbon product; wherein the catalyst comprises the catalyst of claim 9.
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