CN106140192A - One improves the selective catalyst of synthesis gas converted product and preparation method thereof and application - Google Patents
One improves the selective catalyst of synthesis gas converted product and preparation method thereof and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract 8
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 45
- 238000005470 impregnation Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract 1
- BJLLEZDLIAARQJ-UHFFFAOYSA-N cobalt copper manganese Chemical compound [Mn][Cu][Co] BJLLEZDLIAARQJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910002520 CoCu Inorganic materials 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017816 Cu—Co Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021213 Co2C Inorganic materials 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 1
- YOPUATYREUZXIO-UHFFFAOYSA-N copper;methanol Chemical compound [Cu].OC YOPUATYREUZXIO-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One improves the selective catalyst of synthesis gas converted product and preparation method thereof and application, relates to a kind of cobalt-copper-manganese catalyst with activated carbon as carrier, belongs to chemical technology field.Catalyst uses co-impregnation to prepare, and uses pre reduction activation.In catalyst, each weight percentages of components consists of: carrier active carbon (AC): 76%～83%；Activity component metal cobalt (Co): 6.3%～12.5%, activity component metal copper (Cu): 3.3%～6.3%；Auxiliary agent manganese oxide (MnO): 1%～8.2%.Under proper condition, synthesis gas can be made to generate, and methanol content is low and alcohol distribution concentrates on C for this catalyst2-C5Between linear alcohol mixture.It is simple that the present invention has preparation simultaneously, it is easy to operation, advantage with low cost, has obvious economic benefit.
Description
Technical field
The present invention relates to a kind of catalyzed conversion synthesis gas preparing liquid fuel or the technology of chemical products, belong to derived energy chemical field.Particularly to syngas catalytic conversion mixed alcohol and liquid hydrocarbon catalyst and preparation method thereof.
Background technology
MAS (abbreviation low-carbon alcohols) refers to by C1-C6The liquid mixture of straight chain alcohol composition, can be used as alternative fuel, clean gasoline additive or chemicals and industrial chemicals.The research being directly synthesized low-carbon alcohols by synthesis gas starts from the twenties in 19th century.The impact of twice oil crisis of the seventies in last century and the enhancing of people's environmental consciousness, make with coal, natural gas or biomass that to be raw material produce the research topic of low-carbon alcohols through synthesis gas receives people and greatly pay attention to.
Since at the beginning of last century, researcher have developed multiple different formate low-carbon alcohol catalyst system, and the most representative have a following four: (1) modified high temperature (high pressure) methanol synthesis catalyst.By ZnO/Cr2O3Add alkaline assistant (such as Cs, K) modification and obtain.Such catalyst primary product is methanol and side chain isobutanol, and reaction condition is more harsh (pressure 14-20MPa, temperature 350-450 DEG C).(2) modified low temperature (low pressure) methanol synthesis catalyst.At low-temp synthesis of methanol copper-based catalysts (Cu/ZnO/Al2O3Or Cu/ZnO/Cr2O3The selectivity of low-carbon alcohols in alkaline assistant such as (such as Cs, K) modified equally raising product is added in).Such catalyst reaction mild condition, but active component Cu easy-sintering, and in product, methanol content is high.Above two classes see Patents EP-0034338-A2, US Patent 4513100 etc..(3) Cu-Co catalyst.IFP (IFP) developed in the first Cu-Co and is co-precipitated low-carbon alcohol catalyst, having obtained multiple patent (US Patent 4122110,4291126) at present, such catalyst operating condition is gentleer, primary product is straight chain n-alkanol, reactivity and C2+The selectivity of alcohol is higher, but total alcohol selectivity is relatively low and water in products is more.(4) catalyst with base of molybdenum.US Patent 4882360 seen from typical catalyst with base of molybdenum.Catalyst with base of molybdenum typically has the sulfur resistance of uniqueness and is difficult to carbon distribution, and product water content is few, can add alkali metal promoter and other metal components are optimized, can make the C of alcohol2+/C1Ratio is relatively reasonable, but this catalyst system and catalyzing is harsh to synthesis gas proportion requirement, and auxiliary agent cobalt easily causes cobalt to run off with carbon monoxide formation carbonyl cobalt.
Due to higher alcohols (monohydric alcohol more than 6 carbon atoms, can be used for synthesizing plasticizer, detergent, surface activity and other fine chemicals) added value high, and the reaction scheme of directly being prepared higher alcohols by synthesis gas is short, occur the catalyst directly being prepared higher alcohols by synthesis gas the most in recent years.Domestic patent CN101310856A was once reported with activated carbon as carrier, Co and Co2C is catalyst of synthesizing bigh carbon alcohol of active component and preparation method thereof, can one-step synthesis C1-C18Straight chain higher alcohol, wherein total alcohol selectivity is 38.3%.United States Patent (USP) US Patent 4504600 reports the ferrum-based catalyst of a kind of thallium auxiliary agent, synthesis gas can obtain C in the hydrocarbon product synthesized6-C12Higher alcohols, weight accounts for the 5-10% of THC.Chinese patent CN103433046A reports a kind of " CoCuM " catalyst system using coprecipitation to prepare, wherein M is one or more auxiliary agents, total alcohol Mass Selective of this system is up to 64.3%, and wherein methanol content in total alcohol is 18.4-64.3%, C6+Alcohol accounts for 13.2-31.5% in total alcohol.
In each patent reported above, the total alcohol selectivity having is high, but methanol proportion in total alcohol is bigger；The total alcohol selectivity having is preferable, and methanol content is low, but the distribution width of alcohol, and main alkoxide component does not highlights.Due to activated carbon supported cobalt-base catalyst have methanol content low feature, and " CoCu " base catalyst has the high selective feature of total alcohol, and both catalyst systems the most easily use auxiliary agent modulation, therefore the present invention is combined and uses Mn species modulation by activated carbon supported Co catalysts and " CoCu " base catalyst, obtain activated carbon supported " CoCuMn " catalyst, compared with above catalyst system, the activity that the present invention has catalyst is higher, the selectivity of total alcohol is preferable, methanol constituent content is low, low-carbon alcohols component (C2-C5) feature that content is high.
Summary of the invention
It is the highest that the purpose of the present invention is primarily directed to activated carbon supported cobalt-base catalyst total alcohol selectivity, and the problem that the distribution of alcohol is not concentrated, and " CoCu " though the total alcohol selectivity of catalyst is high the problem that methanol constituent content is too high, a kind of catalyst with unique texture and its preparation method and application is provided, obtain high total alcohol selectivity simultaneously, low methanol content, and the alkoxide component of relatively integrated distribution.Such catalyst preparation process is simple, with low cost, has excellent synthol selectivity and higher C2+Alkoxide component content, has obvious using value.
The invention mainly comprises active component, auxiliary agent, load and catalyst reaction condition.
The preparation of catalyst
With cocoanut active charcoal as carrier, it is made into the activated carbon granule of 80-100 mesh, washes away the floating ash in surface initially with tap water, then adopt and be washed with deionized water 10 times.
Use co-impregnation to be impregnated into by the mixed aqueous solution of cobalt nitrate, copper nitrate and manganese nitrate on activated carbon AC carrier, keep 1h, afterwards by sample 60 DEG C of drying 12h in air；Under an inert atmosphere in 350 DEG C of roastings, obtain the presoma of catalyst.
By 4mL catalyst precursor as in reactor, being passed through the pure hydrogen that pressure is 0.1MPa, air speed is 1000h-1, it is warming up to 430 DEG C with the heating rate of 5 DEG C/min, keeps 4h, reduction to cool to room temperature after terminating；Then H is cut2Being the mixed gas of 2 with CO volume ratio, boost to 3MPa, air speed is 500h-1, it is warming up to 220 DEG C with 1 DEG C/min, after stable reaction 24h, interval 24h sampling.
Air speed of the present invention is to be passed through the volume of gas and the ratio of catalyst volume in the unit time.
Advantages of the present invention
(1) with cheap cobalt nitrate, copper nitrate, manganese nitrate is raw material.
(2) catalyst synthesized has: the selectivity of total alcohol is higher, and methanol constituent content is low, C2+The constituent content of alcohol is high, and alcohol integrated distribution is at C2-C5Between alcohol.
Accompanying drawing explanation
Fig. 1 be embodiment 1 preparation catalyst reacted after XRD figure；
Fig. 2 be embodiment 2 preparation catalyst reacted after XRD figure；
Fig. 3 be embodiment 3 preparation catalyst reacted after XRD figure；
Fig. 4 be embodiment 4 preparation catalyst reacted after XRD figure；
Fig. 5 be embodiment 2 preparation catalyst reacted after high-resolution-ration transmission electric-lens (TEM) figure；
Fig. 6 be embodiment 3 preparation catalyst reacted after high-resolution-ration transmission electric-lens (TEM) figure；
Fig. 7 be embodiment 4 preparation catalyst reacted after high-resolution-ration transmission electric-lens (TEM) figure.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, and the present invention includes but not limited to the following examples
Embodiment 1
Weigh 3.704g cobalt nitrate (Co (NO3)2·6H2O) with 0.755g copper nitrate (Cu (NO3)·3H2O), putting in the 50mL beaker filling 5mL aqueous solution, stir and be completely dissolved with copper nitrate to cobalt nitrate, the manganese nitrate solution adding 0.324g 50% is miscible.Take 5gAC carrier, by carrier impregnation in the impregnation liquid containing active component, static 1h, make its active component and help active component to be carried on carrier by capillarity, 12h is dried again in 60 DEG C of air, gained sample in 350 DEG C of constant temperature calcining 4h, is then cooled to room temperature, obtains black sample in an ar atmosphere.The named A of above catalyst, catalyst composition is listed in table 1.The physical property characterization result of catalyst is listed in table 2.
Taking the above-mentioned catalyst of 4mL and carry out reduction treatment, institute's employing condition with step is: be passed through the pure hydrogen that pressure is 0.1MPa, and air speed is 1000h-1, it is warmed up to 430 DEG C with 5 DEG C/min, keeps 4h, reduction to cool to room temperature after terminating.Then the catalyst after reduction being carried out reaction evaluating, institute's employing condition with step is: incision H2Being the mixed gas of 2 with CO volume ratio, corresponding air speed is 500h-1, react after 24h is stably, then through 24h sample analysis.Reaction result is listed in table 3.From XRD spectra it can be seen that course of reaction occurs in that the diffraction maximum of metallic cobalt and metallic copper.
Embodiment 2
Weigh 3.704g cobalt nitrate (Co (NO3)2·6H2O) with 0.755g copper nitrate (Cu (NO3)·3H2O), putting in the 50mL beaker filling 5mL aqueous solution, stir and be completely dissolved with copper nitrate to cobalt nitrate, the manganese nitrate solution adding 1.302g 50% is miscible.Take 5g AC carrier, by carrier impregnation in the impregnation liquid containing active component, static 1 hour, make its active component and help active component to be carried on carrier by capillarity, 12h is dried again in 60 DEG C of air, gained sample in 350 DEG C of constant temperature calcining 4h, is then cooled to room temperature, obtains black sample in an ar atmosphere.The named B of above catalyst, catalyst composition is listed in table 1.The physical property characterization result of catalyst is listed in table 2.
Taking the above-mentioned catalyst of 4mL and carry out reduction treatment, institute's employing condition with step is: be passed through the pure hydrogen that pressure is 0.1MPa, and air speed is 1000h-1, it is warmed up to 430 DEG C with 5 DEG C/min, keeps 4h, reduction to cool to room temperature after terminating.Then the catalyst after reduction being carried out reaction evaluating, institute's employing condition with step is: incision H2Being the mixed gas of 2 with CO volume ratio, corresponding air speed is 500h-1, react after 24h is stably, then through 24h sample analysis.Reaction result is listed in table 3.From XRD spectra it can be seen that course of reaction occurs in that the diffraction maximum of metallic cobalt and metallic copper.From TEM spectrogram it can be seen that less circular metal cobalt granule is in close contact with metallic copper particle.
Embodiment 3
Weigh 3.704g cobalt nitrate (Co (NO3)2·6H2O) with 1.51g copper nitrate (Cu (NO3)·3H2O), putting in the 50mL beaker filling 5mL aqueous solution, stir and be completely dissolved with copper nitrate to cobalt nitrate, the manganese nitrate solution adding 2.605g 50% is miscible.Take 5g AC carrier, by carrier impregnation in the impregnation liquid containing active component, static 1 hour, make its active component and help active component to be carried on carrier by capillarity, 12h is dried again in 60 DEG C of air, gained sample in 350 DEG C of constant temperature calcining 4h, is then cooled to room temperature, obtains black sample in an ar atmosphere.The named C of above catalyst, catalyst composition is listed in table 1.The physical property characterization result of catalyst is listed in table 2.
Taking the above-mentioned catalyst of 4mL and carry out reduction treatment, institute's employing condition with step is: be passed through the pure hydrogen that pressure is 0.1MPa, and air speed is 1000h-1, it is warmed up to 430 DEG C with 5 DEG C/min, keeps 4h, reduction to cool to room temperature after terminating.Then the catalyst after reduction being carried out reaction evaluating, institute's employing condition with step is: incision H2Being the mixed gas of 2 with CO volume ratio, corresponding air speed is 500h-1, react after 24h is stably, then through 24h sample analysis.Reaction result is listed in table 3.From XRD spectra it can be seen that course of reaction occurs in that the diffraction maximum of metallic cobalt and metallic copper.From TEM spectrogram it can be seen that less circular metal cobalt granule is in close contact with metallic copper particle.
Embodiment 4
Weigh 1.975g cobalt nitrate (Co (NO3)2·6H2O) with 1.51g copper nitrate (Cu (NO3)·3H2O), putting in the 50mL beaker filling 5mL aqueous solution, stir and be completely dissolved with copper nitrate to cobalt nitrate, the manganese nitrate solution adding 2.605g 50% is miscible.Take 5gAC carrier, by carrier impregnation in the impregnation liquid containing active component, static 1 hour, make its active component and help active component to be carried on carrier by capillarity, dry 12 hours in 60 DEG C of air again, gained sample in 350 DEG C of constant temperature calcining 4h, is then cooled to room temperature, obtains black sample in an ar atmosphere.The named D of above catalyst, catalyst composition is listed in table 1.The physical property characterization result of catalyst is listed in table 2.
Taking the above-mentioned catalyst of 4mL and carry out reduction treatment, institute's employing condition with step is: be passed through the pure hydrogen that pressure is 0.1MPa, and air speed is 1000h-1, it is warmed up to 430 DEG C with 5 DEG C/min, keeps 4h, reduction to cool to room temperature after terminating.Then the catalyst after reduction being carried out reaction evaluating, institute's employing condition with step is: incision H2Being the mixed gas of 2 with CO volume ratio, corresponding air speed is 500h-1, react after 24h is stably, then through 24h sample analysis.Reaction result is listed in table 3.From XRD spectra it can be seen that course of reaction occurs in that the diffraction maximum of metallic cobalt and metallic copper.From TEM spectrogram it can be seen that less circular metal cobalt granule is in close contact with metallic copper particle.
Analysis test method used by the present invention: 1) obtained through conversion by each constituent content of interpolation in preparation process forming of catalyst；2) specific surface area of catalyst, pore volume and pore-size distribution measure and use Merck & Co., Inc of U.S. ASAP 2020 low temperature liquid nitrogen absorption method, and specific surface area is BET specific surface area；3) the thing phase of the D8Advance X-ray powder diffractometer analysis of catalyst of Brooks Co., Ltd of Germany (Bruker) is used；4) structure of the high power tem study catalyst of the C/M300 of PHILIPS Co. is used；5) 7890 gas chromatographic analysis product compositions of Agilent company of the U.S. are used.
Table 1 catalyst forms
| Catalyst is numbered | A | B | C | D |
| AC content, % | 83.2 | 80.8 | 76.1 | 80.4 |
| Co content, % | 12.5 | 12.1 | 11.4 | 6.4 |
| Cu content, % | 3.3 | 3.2 | 6.1 | 6.4 |
| MnO content, % | 1.0 | 3.9 | 6.4 | 6.8 |
The performance indications of table 2 catalyst
| Catalyst | BET specific surface area (m2/g) | Pore volume (ml/g) | Average pore size (nm) |
| Absorbent charcoal carrier | 774.1 | 0.44 | 2.3 |
| A | 646.5 | 0.32 | 2.5 |
| B | 656.2 | 0.32 | 2.6 |
| C | 568.1 | 0.28 | 2.4 |
| D | 706.1 | 0.34 | 2.3 |
Table 3 evaluating catalyst result
| Catalyst is numbered | A | B | C | D |
| CO conversion ratio, % | 38.6 | 52.2 | 56.0 | 58.3 |
| Methane selectively, % | 30.8 | 14.1 | 8.9 | 7.7 |
| C2-C4Hydrocarbon selective, % | 37.6 | 22.0 | 26.1 | 22.5 |
| CO2Selectivity, % | 6.3 | 3.8 | 5.9 | 5.2 |
| C5+Selectivity, % | 16.2 | 36.6 | 34.1 | 24.5 |
| Total alcohol selectivity, % | 9.1 | 23.5 | 25.0 | 40.1 |
| Methanol/total alcohol, % | 4.0 | 6.6 | 3.1 | 2.7 |
| C2-C5Alcohol/total alcohol, % | 69.5 | 54.2 | 68.5 | 80.0 |
| C6-C14Alcohol/total alcohol, % | 26.5 | 39.2 | 28.4 | 17.3 |
Note: selectivity is each component selectivity (in terms of carbon number) in organic product.
From data above, catalyst has more rational specific surface area, pore volume and pore-size distribution；It is little granule Co and the oarse-grained Cu being in close contact that catalyst generates the active sites of alcohol；Catalyst under the above-described reaction conditions, has higher reactivity and good selectivity in fixed bed reactors, and in gained alcohol, methanol content is low, and alcohol integrated distribution is at C2-C5Between alcohol.
Claims (5)
1. one kind is improved synthesis gas (carbon monoxide and the gaseous mixture of hydrogen) the selective catalyst of converted product, it is characterised in that catalyst
Composition: catalyst by mass percentage, consisting of: carrier active carbon (AC): 76%～83%；Activity component metal
Cobalt (Co): 6.3%～12.5%, activity component metal copper (Cu): 3.3%～6.3%；Auxiliary agent manganese oxide (MnO): 1%～8.2%.
Method the most according to claim 1, it is characterised in that the preparation method of catalyst: cobalt nitrate and copper nitrate are dissolved in from
In sub-water, then mix with 50% manganese nitrate solution, be then impregnated on absorbent charcoal carrier, stand 1 hour；Afterwards by sample
12h is dried for 60 DEG C in air；Gained sample, in argon gas atmosphere, in 350 DEG C of constant temperature calcining 4h, is then cooled to room temperature,
Obtain activated carbon supported " CoCuMn " catalyst.
Method the most according to claim 1, it is characterised in that the reducing condition of catalyst: use pure H2Reduction, reduction temperature is
430 DEG C, air speed is 1000h-1, pressure is 0.1MPa, and the recovery time is 4h.
4. according to method described in claim 1, it is characterised in that generate the active sites structure of alcohol on catalyst: less spherical metal
Co granule and bigger Ni metal granule keep being in close contact.
Method the most according to claim 1, it is characterised in that the reaction condition of catalyst: in fixed bed reactors device, reaction
Gas is synthesis gas, H in synthesis gas2Being 2 with the volume ratio of CO, air speed is 500h-1, reaction temperature is 220 DEG C, pressure
Power is 3MPa.
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| CN112742397A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Synthetic alcohol catalyst and preparation method and application thereof |
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