CN109420521A - It is a kind of for the catalyst of Fischer-Tropsch synthesis and its preparation and application - Google Patents
It is a kind of for the catalyst of Fischer-Tropsch synthesis and its preparation and application Download PDFInfo
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- CN109420521A CN109420521A CN201710785565.9A CN201710785565A CN109420521A CN 109420521 A CN109420521 A CN 109420521A CN 201710785565 A CN201710785565 A CN 201710785565A CN 109420521 A CN109420521 A CN 109420521A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 35
- 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 33
- 238000000034 method Methods 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 33
- 229910002651 NO3 Inorganic materials 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 239000006210 lotion Substances 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 210000002268 wool Anatomy 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 6
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- -1 template Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims 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 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000009415 formwork Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- XSDOQADWZIBRFH-UHFFFAOYSA-N C(CC)Cl(CCC)(CCC)CCC Chemical compound C(CC)Cl(CCC)(CCC)CCC XSDOQADWZIBRFH-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 241001120493 Arene Species 0.000 description 3
- 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
- 239000012263 liquid product Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910015187 FePd Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical compound COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of catalyst for Fischer-Tropsch synthesis and its preparations and application.Specifically the catalyst is made of two parts, and synthesis gas prepares the ZnCrO of methanolxOxide and methanol are converted into the ZSM-5 molecular sieve of aromatic hydrocarbons.By the Cr/Zn (100-0.01) of modulation oxide and the duct acid distribution of molecular sieve, the hybrid mode of two kinds of components and mass ratio etc. can get high activity, highly selective and high stable synthesis gas prepares the catalyst of aromatic hydrocarbons.Catalyst of the present invention has the characteristics that high activity, highly selective and high stable, prepares aromatic hydrocarbons for one-step method from syngas and provides a kind of new catalyst, has a good application prospect.
Description
Technical field
The present invention relates to it is a kind of can be applied to one-step method from syngas in Fischer-Tropsch synthesis prepare aromatic hydrocarbons catalyst and its
Preparation method.
Background technique
In recent years, the rapid growth of global economy have stimulated significantly riseing to oil and natural gas consumption demand,
Workable content is increasingly reduced, and has had already appeared the insufficient phenomenon of supply.Under the energy resource structure of the few oily deficency of China's richness coal,
Developing coal-to-oil industry is a necessary selection.Other than direct coal liquefaction technology, producing synthesis gas from coal combination F- T synthesis is raw
The route of oil-producing product is also a promising important technology route.Currently, F- T synthesis and Fischer-Tropsch oil refining are technically
It has been mature technique, but in economic aspect, there are still certain disadvantages compared with oil product.In order to effectively promote Fischer-Tropsch oil refining
Economical, the exploitation high value-added product of technology, such as low-carbon alkene, aromatic hydrocarbons, have become the trend of development.
Aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene are basic organic chemical industry raw materials, are widely used in garment material, aviation boat
It, communications and transportation, decorations, the fields such as electric equipment products, mobile communication.But it is obeyed since Fischer-Tropsch synthetic is distributed
Anderson-Schulz-Flory (ASF) kinetics model, becoming the controlled syntheses of aromatic hydrocarbons is synthesis gas Study on Transformation
The ultimate challenge faced.Poplar at et al. once using nano zircite as catalyst, a step catalyzes and synthesizes gas and is converted into higher octane
It is worth hydrocarbon product.In hydrocarbon product, it is 30%-53% (Journal of that C5+, which is selectively up to arene content in 48%, C5+,
Fuel Chemistry and Technology,2016,44(7):837-844.).M Nimz et al. utilizes FePd/SiO2It urges
It is combined to gas and prepares aromatic hydrocarbons, obtain 30.5% selectivity (Catalysis Letters, 1988,1 (4): 93).Huang Xiaofan etc.
In patent CN201610550701.1, aromatized catalyst, such as Ga/Cr/ are obtained using various metals component modification molecular sieve
Co/ZSM-5 has obtained 80.8% arenes selectivity.Other than synthesis gas directly prepares aromatic hydrocarbons, scientist, which also found, utilizes conjunction
Aromatic hydrocarbons is prepared at gas two-stage method, i.e., is first converted into methanol or dimethyl ether using synthesis gas, methanol or dimethyl ether further convert
For aromatic hydrocarbons.This method can effectively improve its selectivity.In patent CN201610898431.3, author is synthesized using two-stage method
It is prepared for aromatic hydrocarbons.Zhang Qingde et al. converts synthesis gas to aromatic hydrocarbons using two isobaric series connection continuous fixed bed reactors.
First with Cu/Zn/Al2O3/γ-Al2O3For catalyst first in first stage reactor dimethyl ether synthesis, then in second-stage reaction
Aromatic hydrocarbons is synthesized using ZSM-5 as catalyst in device, arenes selectivity can be reached when CO conversion ratio is 71.9%
86.8% (Journal of Industrial and Engineering Chemistry, 2013,19 (3): 975-980.).
But in two-part method, methanol-fueled CLC is limited by thermodynamical equilibrium leads to that conversion per pass is low, recycle ratio is high, subsequent aromatisation
Etc. technical process also result in a large amount of energy dissipation, be greatly reduced economic value.If two processes are combined into one, will synthesize
The direct high selectivity aromatic hydrocarbons of gas, will embody that process is shorter, the lower advantage of energy consumption.
Packet letter and et al. by ZnCrOxIt is mixed with composite catalyst with SAPO-34, is converted into alkene for one step of synthesis gas
In the reaction of hydrocarbon, ketenes has obtained up to 80% C in the case where CO conversion ratio is 17% as intermediate species2=-C4='s
Selectivity (Science, 2016,351 (6277): 1065.).It is not unique, but has its counterpart, and Wang Ye team also utilizes catalst for synthesis of methanol Zr-
Zn oxide and methanol-to-olefin catalyst SAPO-34 are mixed to get composite catalyst, have obtained 70% C2-C4Alkene choosing
Selecting property (Angewandte Chemie, 2016,128 (15): 4803-4806.).The two belong to first by synthesis gas in a metal
It is converted into certain in the heart and recycles the acidity and shape selectivity of molecular sieve such as wax or methanol with respect to stable intermediate, it is further real
Existing C-C key formation, cracking and isomery, to breach the CH of traditional FT synthesisxChain growth mechanism, and due to the mutual rush of reaction
Into effect, the conversion ratio of CO is effectively improved.In addition to this it is possible to this method, obtain the higher vapour of added value
Oil and aromatic component.Sun Yuhan team is then by carbon dioxide-synthesized methanol catalyst In2O3The catalysis of gasoline is prepared with methanol
Agent ZSM-5 phase is compound, has obtained selectivity as 78.6% gasoline fraction (Nature Chemistry, 2017.).Currently, closing
Methanol is prepared at gas and methanol prepares aromatic hydrocarbons technology (MTA) and developed very mature, above-mentioned thought is referred from, by synthesizing methanol
Oxide and the compound preparation OX-ZEO catalyst of MTA catalyst, will effectively improve aromatic hydrocarbons while improving CO conversion ratio
Selectivity.
Since MTA reaction generally requires 350 DEG C or more, methanol selects traditional Cu-Zn-Al catalyst for methanol at high temperature
Property is extremely low, and its Zn composite oxides such as ZnZr and ZnCr can high selectivity methanol at high temperature, therefore be elected to be methanol
Catalyst carries out compound.ZSM-5 molecular sieve has the shape-selective effect in unique duct, it has also become carries out effective catalysis of synthesis aromatic hydrocarbons
Agent.The progress of the two catalyst is compound, and by the reasonable Si/Al of modulation molecular sieve, the ratio of the two forms and hybrid mode,
Gas can effectively be catalyzed and synthesized and be converted into aromatic hydrocarbons.Simultaneously as easy in inactivation, researcher are normal in the reaction for ZSM-5 catalyst
Acid and duct modulation is carried out using sodium hydroxide modified ZSM-5, to improve the stability (Applied of catalyst
Catalysis A General,2008,345(1):43-50；Journal of Materials Chemistry,1994,4
(4):605-610.).Patent of invention is consolidated using ZnCrOxCompound urge is mixed to get with the molecular sieve of sodium hydroxide modification
Agent is converted into aromatic hydrocarbons for one step of synthesis gas.The catalyst not only the catalyst have high activity with it is highly selective, but also
Possess certain stability.
Summary of the invention
The purpose of the present invention is to provide a kind of composite catalyst that aromatic hydrocarbons is prepared for one-step method from syngas, the catalyst
Has the characteristics that high activity, highly selective to the reaction.
The purpose of the present invention is to provide a kind of preparation sides of composite catalyst that aromatic hydrocarbons is prepared for one-step method from syngas
Method, this method good reliability, repeatability is strong, and universality is high.
In order to realize above-mentioned purpose of the invention, the present invention adopts the following technical scheme:
A kind of catalyst for Fischer-Tropsch synthesis.Catalyst prepares the catalyst of methanol by synthesis gas and methanol turns
The catalyst two parts mixing for turning to aromatic hydrocarbons is constituted.Synthesis gas prepares the catalyst of methanol using ZnCrOxOxide, x 1-
1.5, Zn:Cr molar ratio 1000-0.01；Methanol is converted into aromatic hydrocarbons using ZSM-5 catalyst.
A kind of preparation method of composite catalyst preparing aromatic hydrocarbons for one-step method from syngas provided by the invention is specific
Step are as follows:
1、ZnCrOxThe preparation of oxide
Weigh Al (NO3)3·9H2O, Zn (NO3)2·6H2O, Cr (NO3)3·9H2O in deionized water, Al:Zn:Cr's
1~100:1000 of molar ratio~0.01:1 stirs 0.5-6h in 50-90 DEG C of water-bath；Then dropwise into mixed solution
Precipitating reagent is added, stirs to get suspension；Suspension is filtered, is transferred at 60-120 DEG C of oven drying after washing to neutrality
Reason；Then sample is placed in Muffle furnace 300-800 DEG C of roasting 0.5-6h to get to ZnCrOxCatalyst, wherein Al is as knot
Structure auxiliary agent is present in catalyst.
2, the preparation of ZSM-5 molecular sieve
Silicon source, silicon source, alkali, template, water are uniformly mixed and obtain mixture, each substance is respectively with SiO in mixture2、
Al2O3、MxO、R、H2The molar ratio of O meter is SiO2:Al2O3:MxO:R:H2O=10-100:1:0.3-10:0.5-100:100-
10000；Wherein MxO is alkali metal, and x 1-2, R are template, and 8-24h is stirred at room temperature in said mixture；Then by it
It being transferred in the hydrothermal synthesis kettle of built-in polytetrafluoroethylene (PTFE), is placed in baking oven after sealing, crystallization temperature is 100-240 DEG C, and
Constant temperature keeps 40-360h；Obtained suspended system is centrifuged, during deionized water carrying out washing treatment 3-6 times to washing lotion is in
Property, the oven drying 5-24h by the solid sediment of collection at 60-120 DEG C；Muffle of the solid at 300-800 DEG C after drying
1-6h is roasted in furnace under air atmosphere to get ZSM-5 molecular sieve is arrived.
3, the preparation of alkali treatment modifying HZSM-5
NaOH powder is taken to prepare aqueous slkali in 50ml deionized water；Then it is heated in water-bath, weighs 0.5-3g points
Son screening, which is dispersed in aqueous slkali, stirs a period of time, then filtration washing, the oven drying by the filter cake of collection at 60-120 DEG C
5-24h；Then formulating ammonium nitrate 0.1-5mol L is weighed-1Solution, by above-mentioned filter cake dispersion wherein, stirred at 30-90 DEG C
1-12h, filtration washing, in triplicate, then by filter cake, dry 5-24h, the solid after drying exist in 60-120 DEG C of baking oven
1-8h is roasted under air atmosphere in 300-800 DEG C of Muffle furnace, the NaOH-HZSM-5 after obtaining alkali modification.
4, the mixing of two kinds of catalyst
By ZnCrO in 1xZSM-5 catalyst in catalyst and 2 or 3 is mixed, and composite catalyst is obtained.
(1) precipitating reagent used in step 1 is ammonium carbonate, ammonium hydrogen carbonate, one of sodium carbonate or two kinds or more；Step
PH should be 8-12, preferably 9-10 after precipitating reagent is added in 1；Using be added precipitating reagent after stir 1-10h, preferably 3-5h.
(2) silicon source used in step 2 is one of tetraethyl orthosilicate, silica solution, waterglass, sodium metasilicate or more
Kind；The silicon source used is one or more of sodium metaaluminate, aluminium powder, aluminum nitrate, aluminium hydroxide；Alkali is Strong oxdiative sodium, by force
One of potassium oxide or both；Organic formwork agent be tetrapropylammonium hydroxide, 4-propyl bromide, tetraethylammonium bromide,
One of tetraethyl ammonium hydroxide, 4-propyl ammonium chloride or two kinds or more.
(3) preferred 140-200 DEG C of the crystallization temperature in step 2, time preferred 48-96h；Alkaline concentration in step 3
For 0.05-5mol L-1, preferably 0.1-0.5mol L-1；Water bath temperature, that is, treatment temperature is 30-90 DEG C, preferably 60-80 DEG C；
The processing time is 15-360min, preferably 15-120min.
(4)ZnCrOxOxide and ZSM-5 molecular sieve mixing mode be silica wool isolation method, practical physical mixing method,
Polishing, any one in ball-milling method；Wherein, silica wool isolation method is that oxide and molecular sieve are isolated using silica wool
It opens, i.e. oxide-silica wool layer-molecular sieve, can be and be isolated using one layer of either multilayer silica wool (1-10)；Particle
The granular size of physical mixed method is 10-100 mesh, and preferably size is 20-60 mesh；ZnCrO in step 4xOxide and ZSM-5
The mass ratio of molecular sieve is 100-0.01, is preferably in a proportion of 5-0.2.
Composite catalyst provided by the invention is applied to catalyze and synthesize gas one-step method and prepare in the reaction of aromatic hydrocarbons: by catalyst
It is loaded in the stainless steel reaction pipe of fixed bed reaction bed and carries out reaction evaluating after the pre-treatment, unstripped gas H2And CO2Mixing
Gas, volume ratio H2:CO2=0.5:1-5:1；Volume space velocity is 300-2000h-1；Reaction temperature is 300-600 DEG C, reaction pressure
Power is 1-10MPa.Wherein pretreatment condition is atmosphere H2Environment；Volume space velocity is 500-10000h-1；Reaction temperature is
200-500 DEG C, reaction pressure is normal pressure.
Beneficial effects of the present invention:
Method for preparing catalyst provided by the present invention is reliable, is conducive to large batch of production.And by adjusting molecular sieve
Si/Al and the obtained catalyst of Strong oxdiative sodium modified condition, can effectively convert coal based synthetic gas (low hydrogen-carbon ratio) one
Step is converted into aromatic hydrocarbons, and wherein arenes selectivity may be up to 70% in hydrocarbon product, has good application value.
Detailed description of the invention
Fig. 1 is ZnCrOxThe XRD diagram of catalyst.
Fig. 2 is the XRD diagram of ZSM-5 catalyst.
Fig. 3 is the XRD diagram of the ZSM-5 catalyst of different Si/Al.
Fig. 4 is the XRD diagram of the NaOH-HZSM-5 catalyst of the modification of various concentration.
Fig. 5 is that the SEM of ZSM-5 catalyst schemes.
Fig. 6 is the SEM schematic diagram of the modified NaOH-HZSM-5 catalyst of the sodium hydroxide of various concentration
(a) the modified figure of 0.1mol L-1 (b) 0.2mol L-1 (c) 0.5mol L-1 (d) 0.1mol L-1NaOH；
Fig. 7 is the HRTEM figure of ZSM-5 catalyst and NaOH-HZSM-5 catalyst, (a) ZSM-5 and (b) 0.5NaOH-
The HRTEM schematic diagram of HZSM-5 catalyst
Fig. 8 is the activity and product distribution map that ZnCrOx catalyst is converted into methanol in synthesis gas,
(a) rate is converted for CO, (b) is distributed for selectivity of product；
Fig. 9 is the activity and selective distribution figure that ZnCrOx-ZSM-5 catalyst is converted into aromatic hydrocarbons in synthesis gas.
Figure 10 is the activity and selectivity that ZnCrOx-ZSM-5 (different Si/Al) catalyst is converted into aromatic hydrocarbons in synthesis gas
Distribution map.
Figure 11 is the activity and selective distribution that ZnCrOx-xNaOH-HZSM-5 catalyst is converted into aromatic hydrocarbons in synthesis gas
Figure.
Figure 12 is the liquid product distribution that ZnCrOx-xNaOH-HZSM-5 catalyst is converted into aromatic hydrocarbons reaction in synthesis gas
Figure.
Specific embodiment
Embodiment 1
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.By 22.42g tetraethyl orthosilicate, 0.6g sodium metaaluminate, 0.2g sodium hydroxide, 26.2g tetrapropyl hydroxide
Ammonium, 36.8g water, which are uniformly mixed, obtains mixture；It is transferred in water heating kettle, seals after 12h is stirred at room temperature in said mixture
After be placed in 180 DEG C of baking ovens constant temperature and keep 48h, be then centrifuged for washing and be in neutrality to washing lotion, the solid sediment of collection is existed
Dry 12h, 550 DEG C of roasting 4h obtain ZSM-5 molecular sieve at 110 DEG C.Two catalyst difference tablettings are granulated as 20-40 mesh
It afterwards, is that 1:1 physical mixed obtains composite catalyst ZnCrO according to mass ratiox- ZSM-5 (Si/Al=67).
Embodiment 2
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.By 11.2g tetraethyl orthosilicate, 0.25g sodium metaaluminate, 0.1g sodium hydroxide, 13.1g tetrapropyl hydroxide
Ammonium, 18.4g water, which are uniformly mixed, obtains mixture；It is transferred in water heating kettle, seals after 12h is stirred at room temperature in said mixture
After be placed in 180 DEG C of baking ovens constant temperature and keep 48h, be then centrifuged for washing and be in neutrality to washing lotion, the solid sediment of collection is existed
Dry 12h, 550 DEG C of roasting 4h obtain ZSM-5 molecular sieve at 110 DEG C.Two catalyst difference tablettings are granulated as 20-40 mesh
It afterwards, is that 1:1 physical mixed obtains composite catalyst ZnCrO according to mass ratiox- ZSM-5 (Si/Al=90).
Embodiment 3
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.By 11.2g tetraethyl orthosilicate, 0.16g sodium metaaluminate, 0.1g sodium hydroxide, 13.1g tetrapropyl hydroxide
Ammonium, 18.4g water, which are uniformly mixed, obtains mixture；It is transferred in water heating kettle, seals after 12h is stirred at room temperature in said mixture
After be placed in 180 DEG C of baking ovens constant temperature and keep 48h, be then centrifuged for washing and be in neutrality to washing lotion, the solid sediment of collection is existed
Dry 12h, 550 DEG C of roasting 4h obtain ZSM-5 molecular sieve at 110 DEG C.Two catalyst difference tablettings are granulated as 20-40 mesh
It afterwards, is that 1:1 physical mixed obtains composite catalyst ZnCrO according to mass ratiox- ZSM-5 (Si/Al=120).
Embodiment 4
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.15.2g sodium metasilicate, 0.2g aluminium powder, 0.1g sodium hydroxide, 18.2g 4-propyl bromide, 2.5g water are mixed
Uniformly obtain mixture；It is transferred in water heating kettle after 12h is stirred at room temperature in said mixture, 180 DEG C is placed in after sealing
Constant temperature keeps 48h in baking oven, is then centrifuged for washing to washing lotion and is in neutrality, and the solid sediment of collection is dry at 110 DEG C
12h, 550 DEG C of roasting 4h, obtains ZSM-5 molecular sieve.0.2g NaOH is taken to prepare 0.1mol L in 50ml deionized water-1Alkali
Solution；Then it being heated in 80 DEG C of water-baths, weighing 1g molecular sieve, which is dispersed in aqueous slkali, stirs 30min, filtration washing, and 110
DEG C dry 12h；Then 4g formulating ammonium nitrate 1mol L is weighed-1Solution 50ml, by above-mentioned filter cake dispersion wherein, stirred at 80 DEG C
2h is mixed, filtration washing, repeatedly filter cake three times, is then dried 12h by ion exchange at 110 DEG C, 4h is roasted, after obtaining alkali modification
0.1NaOH-HZSM-5.Two catalyst difference tablettings are granulated to be 1:1 physical mixed according to mass ratio after 20-40 mesh
Obtain composite catalyst ZnCrOx-0.1NaOH-HZSM-5。
Embodiment 5
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.15.2g sodium metasilicate, 0.2g aluminium powder, 0.1g sodium hydroxide, 18.2g 4-propyl bromide, 2.5g water are mixed
Uniformly obtain mixture；It is transferred in water heating kettle after 12h is stirred at room temperature in said mixture, 180 DEG C is placed in after sealing
Constant temperature keeps 48h in baking oven, is then centrifuged for washing to washing lotion and is in neutrality, and the solid sediment of collection is dry at 110 DEG C
12h, 550 DEG C of roasting 4h, obtains ZSM-5 molecular sieve.0.4g NaOH is taken to prepare 0.2mol L in 50ml deionized water-1Alkali
Solution；Then it being heated in 80 DEG C of water-baths, weighing 1g molecular sieve, which is dispersed in aqueous slkali, stirs 30min, filtration washing, and 110
DEG C dry 12h；Then 4g formulating ammonium nitrate 1mol L is weighed-1Solution 50ml, by above-mentioned filter cake dispersion wherein, stirred at 80 DEG C
2h is mixed, filtration washing, repeatedly filter cake three times, is then dried 12h by ion exchange at 110 DEG C, 4h is roasted, after obtaining alkali modification
0.1NaOH-HZSM-5.Two catalyst difference tablettings are granulated to be 1:1 physical mixed according to mass ratio after 20-40 mesh
Obtain composite catalyst ZnCrOx-0.2NaOH-HZSM-5。
Embodiment 6
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.15.2g sodium metasilicate, 0.2g aluminium powder, 0.1g sodium hydroxide, 18.2g 4-propyl bromide, 2.5g water are mixed
Uniformly obtain mixture；It is transferred in water heating kettle after 12h is stirred at room temperature in said mixture, 180 DEG C is placed in after sealing
Constant temperature keeps 48h in baking oven, is then centrifuged for washing to washing lotion and is in neutrality, and the solid sediment of collection is dry at 110 DEG C
12h, 550 DEG C of roasting 4h, obtains ZSM-5 molecular sieve.1.0g NaOH is taken to prepare 0.1mol L in 50ml deionized water-1Alkali
Solution；Then it being heated in 80 DEG C of water-baths, weighing 1g molecular sieve, which is dispersed in aqueous slkali, stirs 30min, filtration washing, and 110
DEG C dry 12h；Then 4g formulating ammonium nitrate 1mol L is weighed-1Solution 50ml, by above-mentioned filter cake dispersion wherein, stirred at 80 DEG C
2h is mixed, filtration washing, repeatedly filter cake three times, is then dried 12h by ion exchange at 110 DEG C, 4h is roasted, after obtaining alkali modification
0.1NaOH-HZSM-5.Two catalyst difference tablettings are granulated to be 1:1 physical mixed according to mass ratio after 20-40 mesh
Obtain composite catalyst ZnCrOx-0.5NaOH-HZSM-5。
Embodiment 7
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.15.2g sodium metasilicate, 0.2g aluminium powder, 0.1g sodium hydroxide, 18.2g 4-propyl bromide, 2.5g water are mixed
Uniformly obtain mixture；It is transferred in water heating kettle after 12h is stirred at room temperature in said mixture, 180 DEG C is placed in after sealing
Constant temperature keeps 48h in baking oven, is then centrifuged for washing to washing lotion and is in neutrality, and the solid sediment of collection is dry at 110 DEG C
12h, 550 DEG C of roasting 4h, obtains ZSM-5 molecular sieve.2g NaOH is taken to prepare 1mol L in 50ml deionized water-1Aqueous slkali；
Then it is heated in 80 DEG C of water-baths, weighing 1g molecular sieve, which is dispersed in aqueous slkali, stirs 30min, filtration washing, 110 DEG C of dryings
12h；Then 4g formulating ammonium nitrate 1mol L is weighed-1Solution 50ml, by above-mentioned filter cake dispersion wherein, stir 2h at 80 DEG C,
Filtration washing, repeatedly filter cake three times, is then dried 12h by ion exchange at 110 DEG C, 4h is roasted, after obtaining alkali modification
0.1NaOH-HZSM-5.Two catalyst difference tablettings are granulated to be that 1:1 physical mixed obtains according to mass ratio after 20-40 mesh
To composite catalyst ZnCrOx-1NaOH-HZSM-5。
Embodiment 8
Weigh 5.25g Al (NO3)3·9H2O, 14.56g Zn (NO3)2·6H2O, 10g Cr (NO3)3·9H2O is in 50ml
In deionized water, 0.5h is stirred in 70 DEG C of water-bath；Then 1mol L is added dropwise into mixed solution-1(NH4)2CO3
Then solution stirs 3h to PH=9；Suspension is filtered, is washed to neutrality, 80 DEG C of dry 8h, 500 DEG C of roasting 1h are obtained
ZnCrOxCatalyst.By 11.2g tetraethyl orthosilicate, 0.3g sodium metaaluminate, 0.1g sodium hydroxide, 13.1g tetrapropylammonium hydroxide,
18.4g water is uniformly mixed and obtains mixture；It is transferred in water heating kettle after 12h is stirred at room temperature in said mixture, after sealing
It is placed in constant temperature in 180 DEG C of baking ovens and keeps 48h, be then centrifuged for washing to washing lotion and be in neutrality, by the solid sediment of collection 110
Dry 12h, 550 DEG C of roasting 4h obtain ZSM-5 molecular sieve at DEG C.1g NaOH is taken to prepare 1mol L in 50ml deionized water-1
Aqueous slkali；Then it being heated in 80 DEG C of water-baths, weighing 1g molecular sieve, which is dispersed in aqueous slkali, stirs 30min, filtration washing,
110 DEG C of dry 12h；Then 4g formulating ammonium nitrate 1mol L is weighed-1Solution 50ml, by above-mentioned filter cake dispersion wherein, at 80 DEG C
Lower stirring 2h, filtration washing repeat ion exchange three times, and then by filter cake, dry 12h, roasting 4h obtain alkali and change at 110 DEG C
0.1NaOH-HZSM-5 after property.After two catalyst are mixed according to mass ratio for 1:1 powder, it is 20-40 mesh that tabletting, which is granulated,
Obtain composite catalyst ZnCrOx-0.5NaOH-HZSM-5-P。
Embodiment 9
Above-mentioned catalyst is weighed into 0.6g, is seated in fixed bed stainless steel reaction pipe and is tested for the property, device is equipped with
Cold-trap collects liquid product.Before being reacted, catalyst is activated first, atmosphere H2, volume space velocity is
1200h-1, heating rate is 5 DEG C/min, and treatment temperature is 310 DEG C, and time 2h, pressure is normal pressure.By the catalyst after activation
Fischer-Tropsch reaction is carried out, wherein unstripped gas is H2With CO (volume ratio 0.65:1, N2For Balance Air), volume space velocity 2400h-1,
Reaction pressure is 3MPa.The method for taking temperature programming is reacted, takes a temperature spot for every 20 DEG C within the scope of 320-400 DEG C, often
A temperature spot reacts 4h, and heating rate is 5 DEG C/min.Unstripped gas and gaseous product use Agilent 7890B type gas-chromatography,
It is equipped with TCD and fid detector, He gas is carrier gas, carries out on-line analysis.The liquid product being collected into uses Agilent 7890B
Type gas-chromatography HP-5 column is analyzed.
Claims (10)
1. a kind of catalyst for Fischer-Tropsch synthesis, catalyst prepares the catalyst of methanol by synthesis gas and methanol converts
Composition is mixed for catalyst two parts of aromatic hydrocarbons；Synthesis gas prepares the catalyst of methanol using ZnCrOxOxide, x 1-1.5,
The molar ratio 1000-0.01 of Zn:Cr；Methanol is converted into aromatic hydrocarbons using ZSM-5 catalyst.
2. catalyst described in accordance with the claim 1, it is characterised in that: ZnCrOxThe mass ratio of oxide and ZSM-5 molecular sieve
For 100-0.01, it is preferably in a proportion of 5-0.2.
3. a kind of preparation method of catalyst of any of claims 1 or 2, process are as follows:
1)ZnCrOxThe preparation of oxide
Weigh Al (NO3)3·9H2O, Zn (NO3)2·6H2O, Cr (NO3)3·9H2O in deionized water, mole of Al:Zn:Cr
Than 1~100:1000~0.01:1,0.5-6h is stirred in 50-90 DEG C of water-bath；Then it is added dropwise into mixed solution
Precipitating reagent stirs to get suspension；Suspension is filtered, 60-120 DEG C of oven drying processing is transferred to after washing to neutrality；
Then sample is placed in Muffle furnace 300-800 DEG C of roasting 0.5-6h to get to ZnCrOxCatalyst, wherein Al is helped as structure
Agent is present in catalyst；
2) preparation of ZSM-5 molecular sieve
Silicon source, silicon source, alkali, template, water are uniformly mixed and obtain mixture, each substance is respectively with SiO in mixture2、Al2O3、
MxO、R、H2The molar ratio of O meter is SiO2:Al2O3:MxO:R:H2O=10-100:1:0.3-10:0.5-100:100-10000；Its
Middle MxO is alkali metal, and x 1-2, R are template, and 8-24h is stirred at room temperature in said mixture；In transferring it to
It sets in the hydrothermal synthesis kettle of polytetrafluoroethylene (PTFE), is placed in baking oven after sealing, crystallization temperature is 100-240 DEG C, and constant temperature is kept
40-360h；Obtained suspended system is centrifuged, is in neutrality to washing lotion for deionized water carrying out washing treatment 3-6 times, will be collected
Oven drying 5-24h of the solid sediment at 60-120 DEG C；Solid after the drying air gas in 300-800 DEG C of Muffle furnace
1-6h is roasted under atmosphere to get ZSM-5 molecular sieve is arrived；
3) preparation of alkali treatment modifying HZSM-5
NaOH powder is taken to prepare aqueous slkali in 50ml deionized water；Then it is heated in water-bath, weighs 0.5-3g molecular sieve
It is dispersed in aqueous slkali and stirs a period of time, then filtration washing, the oven drying 5- by the filter cake of collection at 60-120 DEG C
24h；Then formulating ammonium nitrate 0.1-5mol L is weighed-1Solution, by above-mentioned filter cake dispersion wherein, stir 1- at 30-90 DEG C
12h, filtration washing, in triplicate, then by filter cake, dry 5-24h, the solid after drying exist in 60-120 DEG C of baking oven
1-8h is roasted under air atmosphere in 300-800 DEG C of Muffle furnace, the NaOH-HZSM-5 after obtaining alkali modification；
4) mixing of two kinds of catalyst
By ZnCrO in (1)xZSM-5 catalyst in catalyst and (2) or (3) is mixed, and composite catalyst is obtained.
4. the preparation method of catalyst according to claim 3, it is characterised in that: precipitating reagent used in step (1) is
Ammonium carbonate, ammonium hydrogen carbonate, one of sodium carbonate or two kinds or more；System PH is set to should be 8- after precipitating reagent is added in step (1)
12, preferably 9-10；Using be added precipitating reagent after stir 1-10h, preferably 3-5h.
5. the preparation method of catalyst according to claim 3, it is characterised in that: silicon source used in step (2) is positive
One of tetraethyl orthosilicate, silica solution, waterglass, sodium metasilicate or two kinds or more；The silicon source used is sodium metaaluminate, aluminium
One of powder, aluminum nitrate, aluminium hydroxide or two kinds or more；Alkali is one of Strong oxdiative sodium, Strong oxdiative potassium or both；
Organic formwork agent is tetrapropylammonium hydroxide, 4-propyl bromide, tetraethylammonium bromide, tetraethyl ammonium hydroxide, tetrapropyl chlorine
Change one of ammonium or two kinds or more.
6. the preparation method of catalyst according to claim 3, it is characterised in that: the crystallization temperature in step (2) is preferred
140-200 DEG C, time preferred 48-96h；Alkaline concentration in step (3) is 0.05-5mol L-1, preferably 0.1-0.5mol
L-1；Water bath temperature, that is, treatment temperature is 30-90 DEG C, preferably 60-80 DEG C；The processing time is 15-360min, preferably 15-
120min。
7. catalyst described in accordance with the claim 3, it is characterised in that: ZnCrO in step (4)xOxide and ZSM-5 molecular sieve
Mixed mode is silica wool isolation method, practical physical mixing method, polishing, any one in ball-milling method；Wherein, silica wool
Isolation method is to be kept apart oxide and molecular sieve using silica wool, i.e. oxide-silica wool layer-molecular sieve, can be use
One layer of either multilayer silica wool (1-10) is isolated；The granular size of practical physical mixing method is 10-100 mesh, preferably greatly
Small is 20-60 mesh；ZnCrO in step (4)xThe mass ratio of oxide and ZSM-5 molecular sieve is 100-0.01, preferred proportion
For 5-0.2.
8. a kind of catalyst of any of claims 1 or 2 is applied to catalyze and synthesize gas one-step method and prepare in the reaction of aromatic hydrocarbons.
9. the application of catalyst according to claim 8, it is characterised in that: catalyst is for one-step method from syngas conversion system
The reaction of standby aromatic hydrocarbons, reaction condition are as follows: Catalyst packing in the stainless steel reaction pipe of fixed bed reaction bed after the pre-treatment into
Row reaction evaluating, unstripped gas H2And CO2Gaseous mixture, volume ratio H2:CO2=0.5:1-5:1；Volume space velocity is 300-
2000h-1；Reaction temperature is 300-600 DEG C, reaction pressure 1-10MPa.
10. evaluating catalyst according to claim 9, it is characterised in that: pretreatment condition is atmosphere H2Environment；Volume
Air speed is 500-10000h-1；Reaction temperature is 200-500 DEG C, and reaction pressure is normal pressure.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170817A (en) * | 2020-01-17 | 2020-05-19 | 太原理工大学 | High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol |
| CN114733560A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by synthesis gas one-step method |
| CN115155588A (en) * | 2022-08-25 | 2022-10-11 | 南京工业大学 | Series catalyst for preparing aromatic hydrocarbon by direct hydrogenation of carbon dioxide and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003090925A1 (en) * | 2002-04-25 | 2003-11-06 | Engelhard Corporation | Fischer-tropsch catalyst |
| US20040138051A1 (en) * | 1999-09-07 | 2004-07-15 | Zhiping Shan | Novel zeolite composite, method for making and catalytic application thereof |
| CN101347744A (en) * | 2008-09-05 | 2009-01-21 | 江苏扬农化工股份有限公司 | Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof |
| CN101797516A (en) * | 2009-02-06 | 2010-08-11 | 中国石油天然气股份有限公司 | Preparation method of ZSM-5 zeolite/clay composite catalytic material |
| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
-
2017
- 2017-09-04 CN CN201710785565.9A patent/CN109420521A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040138051A1 (en) * | 1999-09-07 | 2004-07-15 | Zhiping Shan | Novel zeolite composite, method for making and catalytic application thereof |
| WO2003090925A1 (en) * | 2002-04-25 | 2003-11-06 | Engelhard Corporation | Fischer-tropsch catalyst |
| CN101347744A (en) * | 2008-09-05 | 2009-01-21 | 江苏扬农化工股份有限公司 | Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof |
| CN101797516A (en) * | 2009-02-06 | 2010-08-11 | 中国石油天然气股份有限公司 | Preparation method of ZSM-5 zeolite/clay composite catalytic material |
| CN104117380A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Process for production of hydrocarbons by synthetic gas conversion and catalysts used for process |
Non-Patent Citations (3)
| Title |
|---|
| BO ZHAO: "Direct Transformation of Syngas to Aromatics over Na-Zn-Fe5C2 and Hierarchical HZSM-5 Tandem Catalysts", 《CELL PRESS》 * |
| KANG CHENG: "Bifunctional Catalysts for One-Step Conversion of Syngas into Aromatics with Excellent Selectivity and Stabilit", 《CELL PRESS》 * |
| KANG CHENG: "Bifunctional Catalysts for One-Step Conversion of Syngas into Aromatics with Excellent Selectivity and Stability", 《CELL PRESS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170817A (en) * | 2020-01-17 | 2020-05-19 | 太原理工大学 | High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol |
| CN111170817B (en) * | 2020-01-17 | 2022-09-23 | 太原理工大学 | High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol |
| CN114733560A (en) * | 2021-01-07 | 2022-07-12 | 国家能源投资集团有限责任公司 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by synthesis gas one-step method |
| CN114733560B (en) * | 2021-01-07 | 2024-04-02 | 国家能源投资集团有限责任公司 | Composite catalyst, preparation method and application thereof, and method for preparing aromatic hydrocarbon by one-step method from synthesis gas |
| CN115155588A (en) * | 2022-08-25 | 2022-10-11 | 南京工业大学 | Series catalyst for preparing aromatic hydrocarbon by direct hydrogenation of carbon dioxide and preparation method and application thereof |
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