CN106807443A - A kind of copper-zinc-based catalyst and preparation method thereof - Google Patents
A kind of copper-zinc-based catalyst and preparation method thereof Download PDFInfo
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- CN106807443A CN106807443A CN201610985637.XA CN201610985637A CN106807443A CN 106807443 A CN106807443 A CN 106807443A CN 201610985637 A CN201610985637 A CN 201610985637A CN 106807443 A CN106807443 A CN 106807443A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 51
- 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 51
- 239000007787 solid Substances 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000725 suspension Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- ZDSXDABMPSGVRA-UHFFFAOYSA-N copper zinc tetranitrate Chemical compound [Cu++].[Zn++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZDSXDABMPSGVRA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MTSGLOLADCOJES-UHFFFAOYSA-J [Cu++].[Zn++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [Cu++].[Zn++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O MTSGLOLADCOJES-UHFFFAOYSA-J 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 18
- 239000000446 fuel Substances 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 241000269350 Anura Species 0.000 abstract 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000000643 oven drying Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ORIYYVFOMKXGLF-UHFFFAOYSA-L dichlorocopper zinc Chemical compound [Zn].[Cu](Cl)Cl ORIYYVFOMKXGLF-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 isohydrocarbon Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000001993 wax 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to technical field of catalytic chemistry, there is provided a kind of preparation method of copper-zinc-based catalyst for synthesis gas beam system Aviation Fuel, including：The molecular sieves of SAPO 34 and the molecular sieves of ZSM 35 are added into the metal salt solution of cupric and zinc, stir, by solvent be evaporated, solid is then dried to obtain in an oven；Solid is calcined in air atmosphere, copper-zinc-based catalyst is obtained.The present invention is unfavorable for the diffusion of reacting gas and product using copper, zinc, the molecular sieves of SAPO 3 and the molecular sieves of ZSM 35 as the active component of catalyst.Copper-zinc-based catalyst prepared by the present invention is very high in 10 16 hydrocarbon fraction selectivity for carbon number, and the content of isoparaffin is improved, it is adaptable to used as Aviation Fuel.
Description
Technical field
The present invention relates to technical field of catalytic chemistry, more particularly to a kind of copper-zinc-based catalyst and preparation method thereof.
Background technology
The energy is the basis that modern society depends on for existence and development, and the supply capacity of clean fuel is related to national economy
Sustainable development, is one of basis of national strategy safety guarantee.Aviation Fuel is not only the important fuel of engine engine,
Also there is highly important application in the field such as solvent and chemicals synthesis, the world is consumed more than 75000m3/d(LIU G,
YAN B,CHEN G.Technical review on jet fuel production.Renew.Sust.Energ.Rev.,
2013,25:59-70), its main component is normal hydrocarbon, isohydrocarbon, cycloalkane and the aromatic hydrocarbon of C8-C18 scopes.
F- T synthesis (Fischer-Tropsch Synthesis, abbreviation FTS) are by coal, natural gas and biomass ECDC
Into gas (H2+ CO) the high-quality clean fuel liquid of not sulfur-bearing, nitrogen and aromatic hydrocarbons is converted into by catalysts such as iron-based, cobalt-baseds
It is the effective way for solving petroleum resources worsening shortages and avoiding environmental pollution with the practicable techniques of high valuable chemicals.
Generally, synthesis gas beam system uses F- T synthesis route for Aviation Fuel, and its primary product is linear paraffin, is met
Anderson-Schulz-Flory (ASF) is distributed, and synthetic product is mainly the COMPLEX MIXED of the linear paraffin composition of C1-C50+
Thing, midbarrel is selectively relatively low.Copper-zinc-based catalyst is cheap, and it is high to prepare methanol selectivity for synthesis gas, and catalysis
Agent long service life.
At present, researcher is typically had long chain alkane through further cracking modification and hydroisomerizing by two step process
There is the intermediate oil of excellent combustion performance.But this process is remained high due to complex process, production cost, to a certain extent
Constrain the extensive use that coal base F- T synthesis prepare clean fuel liquid technology.Therefore, under the conditions of primary reformer, using synthesis
Gas realizes that controlled syntheses Aviation Fuel has very important significance through methyl alcohol route coupled molecule sieve catalyst.
The content of the invention
Present invention solves the technical problem that being to provide a kind of copper zinc-base catalysis for synthesis gas beam system Aviation Fuel
Agent and preparation method thereof, the copper-zinc-based catalyst is higher to Aviation Fuel cut selectivity.
In view of this, the invention provides a kind of copper-zinc-based catalyst, by weight percentage, consist of the following composition：
CuO-ZnO 10%-40%；
SAPO-34 molecular sieves 10%-30%；
ZSM-35 molecular sieve surplus.
Preferably, the silica alumina ratio of the ZSM-35 molecular sieve is 10-50：1.
Accordingly, the present invention also provides a kind of preparation method of the copper-zinc-based catalyst described in above-mentioned technical proposal, including
Following steps：SAPO-34 molecular sieves and ZSM-35 molecular sieve are added into the metal salt solution of cupric and zinc, is obtained after stirring
Suspension；Solvent in the suspension is evaporated, is then dried in an oven, obtain solid；By the solid in air gas
It is calcined under atmosphere, sintering temperature is 400-600 DEG C, obtains copper-zinc-based catalyst.
Preferably, the metal salt solution of the cupric and zinc is copper chloride zinc solution, copper nitrate zinc solution and copper acetate zinc
One or more in solution.
Preferably, the mass concentration of the metal salt solution of the cupric and zinc is 10-40%.
Preferably, the solvent in the metal salt solution of the cupric and zinc is selected from water, ethanol, normal propyl alcohol, isopropanol, positive fourth
One or more in alcohol, isobutanol.
Preferably, in the step of obtaining suspension, mixing time is 1-10h.
Preferably, in the step of obtaining solid, drying temperature is 80-120 DEG C.
Preferably, in the step of obtaining solid, drying time is 5-24h.
Preferably, in the step of obtaining copper-zinc-based catalyst, roasting time is 3-10h.
The invention provides a kind of preparation method of the copper-zinc-based catalyst for synthesis gas beam system Aviation Fuel, including
Following steps：SAPO-34 molecular sieves and ZSM-35 molecular sieve are added into the metal salt solution of cupric and zinc, is obtained after stirring
Suspension；Solvent in the suspension is evaporated, is then dried in an oven, obtain solid；By the solid in air gas
It is calcined under atmosphere, sintering temperature is 400-600 DEG C, obtains copper-zinc-based catalyst.Compared with prior art, the present invention with copper, zinc,
SAPO-3 molecular sieves and ZSM-35 molecular sieve, because molecular sieve bore diameter is smaller, are unfavorable for reaction as the active component of catalyst
The diffusion of gas and product.The copper-zinc-based catalyst of the synthesis gas beam system Aviation Fuel that the present invention is prepared, it is former for carbon
Subnumber is very high in the hydrocarbon gasoline cut selectivity of 10-16, and the content of isoparaffin is improved, it is adaptable to fired as aviation
Oil；In the absence of the wax product that carbon number is high in product, the devices such as follow-up paraffin catalytic pyrolysis can be saved, and reduce
The problems such as line clogging, so as to being effectively reduced the cost of investment and operating cost of device.Additionally, preparation method of the present invention
Simplicity, it is with low cost, adapt to large-scale industrial production.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of copper-zinc-based catalyst, by weight percentage, consist of the following composition：
CuO-ZnO 10%-40%；
SAPO-34 molecular sieves 10%-30%；
ZSM-35 molecular sieve surplus.
Metallic copper zinc and molecular sieve play the catalytic action of key as the active component of catalyst, and content is higher.Due to
Molecular sieve bore diameter is smaller, and molecular sieve plays divided active component, while playing support effect.The reaction is exothermic reaction,
The addition of molecular sieve can avoid the phenomenon of hot-spot, can also avoid the side reaction under high temperature, improve the selectivity of catalyst.
Selected molecular sieve carrier of the invention is preferably with BET specific surface area in 100-500m2The micro porous molecular sieve of/g range is
Main, larger BET specific surface area is beneficial to raising catalytic performance；And research has shown that, silica alumina ratio is higher in molecular sieve carrier, and its is resistance to
Hot acid resistance is better, therefore the present invention is sieved using the acid Series Molecules compared with high silica alumina ratio.The silicon of the SAPO-34 molecular sieves
Aluminum ratio is preferably 10-50：1, more preferably 10-30：1, more preferably 15：1.The silica alumina ratio of the ZSM-35 molecular sieve is preferably
10-50：1, more preferably 10-30：1, more preferably 15：1.
Accordingly, the present invention also provides a kind of preparation method of copper-zinc-based catalyst, comprises the following steps：Just SAPO-
34 molecular sieves and ZSM-35 molecular sieve are added into the metal salt solution of cupric and zinc, and suspension is obtained after stirring；Will be described outstanding
Solvent in turbid liquid is evaporated, and then dries in an oven, obtains solid；The solid is calcined in air atmosphere, roasting temperature
It is 400-600 DEG C to spend, and obtains copper-zinc-based catalyst.
Preferably, the metal salt solution of the cupric and zinc is preferably copper chloride zinc solution, copper nitrate zinc solution
With one or more in copper acetate zinc solution.The mass concentration of the metal salt solution of the cupric and zinc is preferably 10-40%,
More preferably 15-30%.Solvent in the metal salt solution of the cupric and zinc is preferably selected from water, ethanol, normal propyl alcohol, isopropyl
One or more in alcohol, n-butanol, isobutanol.
In the step of obtaining suspension, mixing time is preferably 1-10h, more preferably 4-10h.The step of obtaining solid
In, drying temperature is preferably 80-120 DEG C, more preferably 100-120 DEG C；Drying time is preferably 5-24h, more preferably 6-
20h.In the step of obtaining copper-zinc-based catalyst, roasting time is preferably 3-10h, more preferably 5-10h.
Metallic copper zinc and molecular sieve play the catalytic action of key as the active component of catalyst, and content is higher.Due to
Molecular sieve bore diameter is smaller, and molecular sieve plays divided active component, while playing support effect.The reaction is exothermic reaction,
The addition of molecular sieve can avoid the phenomenon of hot-spot, can also avoid the side reaction under high temperature, improve the selectivity of catalyst.
Selected molecular sieve carrier of the invention is preferably with BET specific surface area in 100-500m2The micro porous molecular sieve of/g range is
Main, larger BET specific surface area is beneficial to raising catalytic performance；And research has shown that, silica alumina ratio is higher in molecular sieve carrier, and its is resistance to
Hot acid resistance is better, therefore the present invention is sieved using the acid Series Molecules compared with high silica alumina ratio.The silicon of the SAPO-34 molecular sieves
Aluminum ratio is preferably 10-50：1, more preferably 10-30：1, more preferably 15：1.The silica alumina ratio of the ZSM-35 molecular sieve is preferably
10-50：1, more preferably 10-30：1, more preferably 15：1.
From above scheme as can be seen that the invention provides a kind of preparation side of synthesis gas beam system Aviation Fuel catalyst
Method, copper zinc catalyst is prepared using coprecipitation, prepares the direct beam system Aviation Fuel catalysts of synthesis gas, for
Carbon number is very high in the hydrocarbon gasoline cut selectivity of 10-16, rich in isoparaffin component higher.
The copper-zinc-based catalyst of synthesis gas beam system Aviation Fuel prepared by the present invention, the catalyst is for F- T synthesis
Before need to by hydrogen reduction make activation of catalyst, so can just give full play to its catalytic performance.
For a further understanding of the present invention, the technical scheme that the present invention is provided is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The raw material and chemical reagent that the embodiment of the present invention is used are purchased in market.
Embodiment 1
The preparation of 10%CuOZnO/20%SAPO-34/70%ZSM-35 catalyst：Weigh 2.09g copper nitrates and 2.14g
Zinc nitrate is added in 100mL deionized waters, and ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Weigh SAPO-34 molecular sieves
2.2g and silica alumina ratio are 15 ZSM-35 molecular sieve 7.7g, are added in above-mentioned copper nitrate zinc solution, and 4h is stirred at room temperature.Then steam
The solvent in above-mentioned suspension is done, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace
It is heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min, obtains copper-zinc-based catalyst 10%CuOZnO/
20%SAPO-34/70%ZSM-35, the wherein content of copper zinc are the 10% of catalyst carrier weight.
Embodiment 2
The preparation of 20%CuOZnO/20%SAPO-34/60%ZSM-35 catalyst：Weigh 4.70g copper nitrates and 4.81g
Zinc nitrate is added in 100mL deionized waters, and ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Weigh SAPO-34 molecular sieves
2.4g and silica alumina ratio are 15 ZSM-35 molecular sieve 7.2g, are added in above-mentioned copper nitrate zinc solution, and 4h is stirred at room temperature.Then steam
The solvent in above-mentioned suspension is done, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in Muffle furnace
It is heated to being calcined 5h under 550 DEG C, air atmosphere with the heating rate of 2 DEG C/min, obtains copper-zinc-based catalyst 10%CuOZnO/
20%SAPO-34/60%ZSM-35, the wherein content of copper zinc are the 20% of catalyst carrier weight.
Embodiment 3
The preparation of 40%CuOZnO/20%SAPO-34/40%ZSM-35 catalyst：Weigh 12.52g copper nitrates and
12.81g zinc nitrates are added in 100mL deionized waters, and ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Weigh SAPO-34
Molecular sieve 2.8g and silica alumina ratio are 15 ZSM-35 molecular sieve 5.6g, are added in above-mentioned copper nitrate zinc solution, and 4h is stirred at room temperature.
Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in horse
Not it is heated to the heating rate of 2 DEG C/min being calcined 5h under 550 DEG C, air atmosphere in stove, obtains copper-zinc-based catalyst 40%
CuOZnO/20%SAPO-34/40%ZSM-35, the wherein content of copper zinc are the 40% of catalyst carrier weight.
Embodiment 4
The preparation of 40%CuOZnO/40%SAPO-34/20%ZSM-35 catalyst：Weigh 12.52g copper nitrates and
12.81g zinc nitrates are added in 100mL deionized waters, and ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Weigh SAPO-34
Molecular sieve 5.6g and silica alumina ratio are 15 ZSM-35 molecular sieve 2.8g, are added in above-mentioned copper nitrate zinc solution, and 4h is stirred at room temperature.
Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying 6h.Dried solid is in horse
Not it is heated to the heating rate of 2 DEG C/min being calcined 5h under 550 DEG C, air atmosphere in stove, obtains copper-zinc-based catalyst 40%
CuOZnO/40%SAPO-34/20%ZSM-35, the wherein content of copper zinc are the 40% of catalyst carrier weight.
Comparative example 1
40%CuOZnO/SiO2The preparation of catalyst：Weigh 12.52g copper nitrates and 12.81g zinc nitrates add 100mL to go
In ionized water, ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Silica 8.4g is weighed, adds above-mentioned copper nitrate zinc molten
In liquid, 4h is stirred at room temperature.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120 DEG C of oven drying
6h.Dried solid is heated to being calcined 5h under 550 DEG C, air atmosphere in Muffle furnace with the heating rate of 2 DEG C/min, obtains
Copper-zinc-based catalyst 40%CuOZnO/40%SAPO-34/20%ZSM-35, the wherein content of copper zinc are catalyst carrier weight
40%.
Comparative example 2
The preparation of 40%CuOZnO/60%SAPO-34 catalyst：Weigh 12.52g copper nitrates and 12.81g zinc nitrates are added
In 100mL deionized waters, ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.SAPO-34 molecular sieve 8.4g are weighed, in addition
State in copper nitrate zinc solution, 4h is stirred at room temperature.Then the solvent in above-mentioned suspension is evaporated, the solid after being evaporated is put into 120
DEG C oven drying 6h.Dried solid is heated to 550 DEG C, air atmosphere in Muffle furnace with the heating rate of 2 DEG C/min
Lower roasting 5h, obtains copper-zinc-based catalyst 40%CuOZnO/60%SAPO-34, and the wherein content of copper zinc is catalyst carrier weight
The 40% of amount.
Comparative example 3
The preparation of 40%CuOZnO/60%ZSM-35 catalyst：Weigh 12.52g copper nitrates and 12.81g zinc nitrates are added
In 100mL deionized waters, ultrasonic dissolution obtains copper nitrate and zinc nitrate mixed solution.Weigh the ZSM-35 molecular sieve that silica alumina ratio is 15
8.4g, adds in above-mentioned copper nitrate zinc solution, and 4h is stirred at room temperature.Then the solvent in above-mentioned suspension is evaporated, after being evaporated
Solid is put into 120 DEG C of oven drying 6h.Dried solid is heated to 550 in Muffle furnace with the heating rate of 2 DEG C/min
DEG C, 5h is calcined under air atmosphere, obtain copper-zinc-based catalyst 40%CuOZnO/40%SAPO-34/20%ZSM-35, wherein copper
The content of zinc is the 40% of catalyst carrier weight.
Catalyst performance is tested
The catalyst that embodiment 1-4 and comparative example 1-3 are prepared is carried out after hydrogen reducing in fixed bed reactors
Synthesis gas beam system Aviation Fuel active testing.Test condition is：Reaction temperature is：200-350 DEG C, preferably 25 DEG C；Reaction
Pressure is：0-5MPa, preferably 3MPa；Synthesis gas air speed is 500-5000h-1, preferably 1000h-1；The body of hydrogen and carbon monoxide
Accumulating ratio is：0.5-3, preferably 2.Each reaction operating mode continues at least 10h, liquids and gases product gas chromatographic analysis, as a result
It is listed in table 1.
The performance test results of catalyst prepared by the embodiment of the present invention of table 1 and comparative example
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of copper-zinc-based catalyst, it is characterised in that by weight percentage, consist of the following composition：
CuO-ZnO 10%-40%；
SAPO-34 molecular sieves 10%-30%；
ZSM-35 molecular sieve surplus.
2. copper-zinc-based catalyst according to claim 1, it is characterised in that the silica alumina ratio of the ZSM-35 molecular sieve is
10-50：1.
3. the preparation method of the copper-zinc-based catalyst described in a kind of claim 1-2 any one, it is characterised in that including following
Step：
SAPO-34 molecular sieves and ZSM-35 molecular sieve are added into the metal salt solution of cupric and zinc, is obtained after stirring suspended
Liquid；
Solvent in the suspension is evaporated, is then dried in an oven, obtain solid；
The solid is calcined in air atmosphere, sintering temperature is 400-600 DEG C, obtains copper-zinc-based catalyst.
4. preparation method according to claim 3, it is characterised in that the metal salt solution of the cupric and zinc is copper chloride
One or more in zinc solution, copper nitrate zinc solution and copper acetate zinc solution.
5. preparation method according to claim 3, it is characterised in that the quality of the metal salt solution of the cupric and zinc is dense
It is 10-40% to spend.
6. preparation method according to claim 3, it is characterised in that the solvent in the metal salt solution of the cupric and zinc
Selected from one or more in water, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol.
7. preparation method according to claim 3, it is characterised in that in the step of obtaining suspension, mixing time is 1-
10h。
8. preparation method according to claim 3, it is characterised in that in the step of obtaining solid, drying temperature is 80-
120℃。
9. preparation method according to claim 3, it is characterised in that in the step of obtaining solid, drying time is 5-
24h。
10. preparation method according to claim 3, it is characterised in that in the step of obtaining copper-zinc-based catalyst, during roasting
Between be 3-10h.
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