CN105289677A - SiC supported catalyst for preparing low-carbon mixed alcohol by utilizing synthesis gas, preparation method and application - Google Patents
SiC supported catalyst for preparing low-carbon mixed alcohol by utilizing synthesis gas, preparation method and application Download PDFInfo
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- CN105289677A CN105289677A CN201510764476.7A CN201510764476A CN105289677A CN 105289677 A CN105289677 A CN 105289677A CN 201510764476 A CN201510764476 A CN 201510764476A CN 105289677 A CN105289677 A CN 105289677A
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Abstract
A SiC supported catalyst for preparing low-carbon mixed alcohol by utilizing synthesis gas comprises, by weight percentage, 30-50% of SiC, 20-30% of Cu, 10-20% of Fe, 5-15% of Mn, 5-10% of Zn, 5-15% of Zr, 1-4% of Co and 0.1-5% of M, wherein M is one of alkali metals or alkaline earth metals, wherein alkali metals are Na, K, Li or Cs; and the alkaline earth metals are Mg or Ba. The SiC supported catalyst has the advantages of being good in stability, low in cost, long in service life and high in selectivity on mild reaction conditions.
Description
Technical field
The invention belongs to a kind of SiC supported catalyst of preparing low-carbon mixed alcohol by synthetic gas and method for making and application.
Background technology
MAS can be used as excellent clean vehicle fuel, because alcohol itself is containing aerobic, and the advantage such as there is sufficient combustion, efficiency high and CO, NOx and hydro carbons discharge capacity is few.Itself be also a kind of good clean fuel, the market demand increase of the higher alcohols that economical price is higher in recent years also makes the research of low-carbon alcohols receive publicity in addition.Therefore, the reaction of CO hydrogenation catalyst synthesizing low-carbon mixed alcohol has important application prospect in C1 chemical field.
Comparatively extensive by the research of the direct synthesis of low-carbon alcohol of synthesis gas, the catalyst system formed mainly contains following four kinds:
(1) modified methanol synthetic catalyst (Cu/ZnO/Al
2o
3, ZnO/Cr
2o
3): this catalyst adds appropriate alkali metal or Modified With Alkali-earth Compounds by methanol synthesis catalyst and obtains, more typical patent has EP-0034338-A2 people such as () C.E.Hofstadt and United States Patent (USP) 4513100 (Snam company subsidizes, and invention people is the people such as Fattore).Although this type of catalyst activity is higher, in product, isobutanol content is high, but shortcoming is that (pressure is 14-20MPa to severe reaction conditions, temperature is 350-450 DEG C), higher alcohol selective low (being generally less than 35%), water content high (being generally 30-50%) in product; (2) Rh catalyst based (as US4014913 and 4096164): after adding one to two kinds of transition metal or metal oxide auxiliary agent in support type Rh catalyst, have higher activity and selectivity, particularly to C to higher alcohols synthesis
2 +alcohol selective higher, product is based on ethanol.But Rh compound is expensive, catalyst is easily by CO
2poison, its activity and selectivity does not generally reach industrial requirement.(3) sulfur resistive MoS
2catalyst: being worth mentioning most is molybdenum system sulfide catalyst (main patent is shown in the USpatent4882360 of the people such as Stevens) that DOW company of the U.S. develops, this catalyst system and catalyzing not only has resistance to SO_2, product is moisture few, and higher alcohol content is higher, reach 30-70%, wherein mainly ethanol and normal propyl alcohol.The subject matter that this catalyst exists is that auxiliary element wherein very easily and between carbon monoxide forms carbonyls, causes the loss of auxiliary element, affects the activity of catalyst and selective, causes catalyst stability and life-span to be restricted.(4) Cu-Co catalyst: France Petroleum Institute (IFP) developed in the first Cu-Co co-precipitation low-carbon alcohol catalyst, only just obtain four catalyst patent (USPatent4122110 before 1985,4291126 and GBPatent2118061,2158730), the product of this catalyst synthesis is mainly C
1-C
6straight chain n-alkanol, accessory substance is mainly C
1-C
6aliphatic hydrocarbon, reaction condition gentleness (similar to low pressure methanol synthesis catalyst).The shortcoming of this catalyst is less stable.
Carborundum (SiC) is the covalent bond compound be made up of carbon and silicon, has similar adamantine tetrahedral structural unit, thus has extraordinary chemical stability, high mechanical strength and hardness, and good heat-conductivity conducting performance.In catalytic reaction process can effectively transfer reaction heat, therefore carborundum is especially suitable as catalyst carrier.The chemical stability that carborundum is good, is conducive to keeping the stable of catalyst structure, thus the extending catalyst life-span; High mechanical strength and hardness, be conducive to the intensity and the abrasion resistance properties that improve catalyst; Good heat-conductivity conducting performance, is conducive to the heat trnasfer of catalyst in course of reaction and the electron transmission between catalyst activity component and carrier.At present, both at home and abroad for being that the catalyst research of matrix is also relatively less with carborundum by preparing low-carbon mixed alcohol by synthetic gas.Chinese patent CN1736594A reports the Catalysts and its preparation method of a kind of cobalt and palladium zinc supported picotite, and this catalyst can selectively make Synthetic holography be MAS and liquid alkane mixture.This catalyst adopts simple infusion process to prepare, but catalyst activity component is cobalt and palladium, expensive, and less stable causes the commercial Application of catalyst to be restricted.
Summary of the invention
The object of this invention is to provide a kind of good stability, cost is low, and the life-span is long, under mild reaction conditions high selectivity by the Catalysts and its preparation method of preparing low-carbon mixed alcohol by synthetic gas and application.
The object of the present invention is achieved like this, use the precipitation method by FeCu catalyst cupport on SiC, there is the VIII element of stronger carbochain growing ability introducing, and transition metal, alkali metal or alkaline-earth metal, rare earth metal, thus improve the activity of CO hydrogenation reaction, improve C
2 +alcohol and C
4 +hydrocarbon selective, and suppress CO simultaneously
2with the generation of the accessory substance such as methane, SiC adds heat transfer efficiency when improving catalyst reaction, improves catalyst stability.
Catalyst weight percent prepared by the present invention consists of:
SiC:30-50%, Cu:20-30%, Fe:10-20%, Mn:5-15%, Zn:5-10%, Zr:5-15%, Co:1-4%, M:0.1-5%; Wherein M is that alkali metal or alkaline-earth metal are a kind of, and wherein alkali metal is Na, K, Li or Cs; Alkaline-earth metal is Mg or Ba etc.
SiC as above is 40-60 object β-SiC, or the β-SiC of equal proportion mixing and the mixture of α-SiC.
The preparation method of catalyst provided by the invention comprises the following steps:
Form by catalyst, SiC carrier and metal-nitrate solutions are first mixed into suspension, precipitation temperature be 60-90 DEG C with alkaline solution co-precipitation, precipitation process needs to stir, keep pH=8-9, precipitate through distilled water washing to neutrality, then dry at baking temperature is 80-120 DEG C, roasting 3h-6h at 350-400 DEG C.
When being alkali metal for M, the catalyst of preparation alkali metals modified, alkali metal can be made into soluble carbonate salt solution as precipitating reagent, is incorporated in above-mentioned coprecipitation process.
The best precipitation temperature of precipitation temperature as above is 60-90 DEG C.
Alkaline solution as above is preferably sodium carbonate, ammoniacal liquor or potash etc.
Catalyst preparing precipitation process of the present invention preferably maintains pH at 8-9.
Baking temperature as above is preferably dry at 80-110 DEG C.
Roasting as above is preferably at 350-400 DEG C of roasting temperature.
The application conditions of catalyst of the present invention is: reaction temperature is 220-280 DEG C, and pressure is 4.5-12.0MPa, and air speed is 1000-7500h
-1, H
2/ CO volume ratio=0.5-2.0.
Carry out the synthesis of low-carbon alcohols with catalyst of the present invention, CO conversion ratio 20-40%, total alcohol is selective is 40-65%, total hydrocarbon-selective 25-40%, CO
2selective 10-18%.Total alcohol space-time yield is 0.15-0.40g/h.mL.cat; Water in products content is 15-30%; C
2 +alcohol content is 40-60%, C
4 +hydrocarbon is shared percentage composition 60-70% in total hydrocarbon.
Tool of the present invention has the following advantages:
1, preparation method is simple, is easy to operation, and catalyst reaction stability, reproducible.
2, catalyst components distribution of the present invention is relatively more even, and there is strong interaction between each component, and anti-sintering property is relatively good, and cost is low, good stability, and the life-span is long.
3, catalyst of the present invention is in reduction and course of reaction, does not need to add CO
2gas, greatly reduces operating cost.
Detailed description of the invention
Embodiment 1
By account for catalyst always form the SiC of the 30wt% of quality and metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.1 be dissolved in the middle of this solution and form 80wt%SiC aaerosol solution, with the co-precipitation of 30wt% solution of potassium carbonate at 60 DEG C, precipitation process needs fully to stir, and keeps pH=8.Precipitate through distilled water washing to neutrality.After 80 DEG C of dryings under 350 DEG C of air atmospheres roasting 3h, be crushed to 40-60 order, obtain catalyst 1
#, gained catalyst respectively forms SiC:wt30%, Cu:wt20%, Fe:wt15%, Mn:wt5%, Zn:wt10%, Zr:wt15%, Co:wt4%, K:wt1%.Reaction condition is as follows: T=220 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 2
By account for catalyst always form the SiC of the 40wt% of quality and metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:0.4:0.5:0.5:0.1:0.1 be dissolved in the middle of this solution and form 70wt%SiC aaerosol solution, with the co-precipitation of 40wt% solution of potassium carbonate at 65 DEG C, precipitation process needs fully to stir, and keeps pH=8.5.Precipitate through distilled water washing to neutrality.After 90 DEG C of dryings under 380 DEG C of air atmospheres roasting 4h, be crushed to 40-60 order, obtain catalyst 2
#, gained catalyst composition SiC:wt40%, Cu:wt25%, Fe:wt10%, Mn:wt5%, Zn:wt5%, Zr:wt10%, Co:wt4%, K:1%, reaction condition is as follows: T=230 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 3
By account for catalyst always form the SiC of the 40wt% of quality and metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:0.4:0.5:0.5:0.1:0.1 be dissolved in the middle of this solution and form 75wt%SiC aaerosol solution, with the co-precipitation of 50wt% sodium carbonate liquor at 70 DEG C, precipitation process needs fully to stir, and keeps pH=9.Precipitate through distilled water washing to neutrality.After 100 DEG C of dryings under 400 DEG C of air atmospheres roasting 5h, be crushed to 40-60 order, obtain catalyst 3
#, gained catalyst composition SiC:wt40%, Cu:wt20%, Fe:wt10%, Mn:wt5%, Zn:wt10%, Zr:wt10%, Co:wt2.5%, Na:2.5%, reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 4
By account for catalyst always form the SiC of the 40wt% of quality and metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:0.4:0.5:1.0:0.1:0.1 be dissolved in the middle of this solution and form 80wt%SiC aaerosol solution, with the co-precipitation of 55wt% Lithium carbonate solution at 75 DEG C, precipitation process needs fully to stir, and keeps pH=8.5.Precipitate through distilled water washing to neutrality.After 110 DEG C of dryings under 400 DEG C of air atmospheres roasting 5h, be crushed to 40-60 order, obtain catalyst 4
#, form SiC:wt40% in gained catalyst, Cu:wt20%, Fe:wt10%, Mn:wt5%, Zn:wt10%, Zr:wt5%, Co:wt4%, Li:1%, reaction condition is as follows: T=240 DEG C, P=5.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 5
By account for catalyst always form the SiC of the 30wt% of quality and metallic atom with the form of nitrate in molar ratio Cu:Fe:Mn:Zn:Zr:Co=1.0:0.6:0.5:0.5:0.1:0.1 be dissolved in the middle of this solution and form 70wt%SiC aaerosol solution, with the co-precipitation of 45wt% cesium carbonate solution at 80 DEG C, precipitation process needs fully to stir, and keeps pH=8.5.Precipitate through distilled water washing to neutrality.Form SiC:wt30% in gained catalyst, Cu:wt20%, Fe:wt25%, Mn:wt10%, Zn:wt5%, Zr:wt5%, Co:wt1%, Cs:4%, after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst 5
#.Reaction condition is as follows: T=250 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 6
The SiC of the 35wt% of quality and metallic atom to be made into 75wt% SiC aaerosol solution with the nitrate solution of the form of nitrate Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.1 in molar ratio is always formed by accounting for catalyst, with the co-precipitation of 35wt% magnesium carbonate solution at 85 DEG C, precipitation process needs fully to stir, and keeps pH=8.Precipitate through distilled water washing to neutrality.Gained catalyst composition SiC:wt35%, Cu:wt30%, Fe:wt15%, Mnwt5%, Znwt5%, Zrwt5%, Cowt3.9%, Mg:1.1%, after 120 DEG C of dryings under 380 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst 6
#.Reaction condition is as follows: T=260 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 7
The SiC of the 35wt% of quality and metallic atom to be made into 80wt% SiC aaerosol solution with the nitrate solution of the form of nitrate Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.1 in molar ratio is always formed by accounting for catalyst, with the co-precipitation of 40wt% magnesium carbonate solution at 85 DEG C, precipitation process needs fully to stir, and keeps pH=9.Precipitate through distilled water washing to neutrality.Gained catalyst composition SiC:wt35%, Cu:wt30%, Fe:wt15%, Mnwt5%, Znwt5%, Zrwt5%, Cowt4%, Mg:1%, after 110 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst 7
#.Reaction condition is as follows: T=270 DEG C, P=7.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 8
The SiC of the 40wt% of quality and metallic atom to be made into 70wt% SiC aaerosol solution with the nitrate solution of the form of nitrate Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.02 in molar ratio is always formed by accounting for catalyst, with the co-precipitation of 50wt% brium carbonate solution at 90 DEG C, precipitation process needs fully to stir, and keeps pH=9.Precipitate through distilled water washing to neutrality.Form SiC:wt35% in gained catalyst, Cu:wt20%, Fe:wt10%, Mnwt10%, Znwt10%, Zrwt15%, Cowt1%, Ba:4%, after 120 DEG C of dryings under 350 DEG C of air atmospheres roasting 4h, be crushed to 40-60 order, obtain catalyst 8
#.Reaction condition is as follows: T=280 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 9
The SiC of the 35wt% of quality and metallic atom to be made into 75wt% SiC aaerosol solution with the nitrate solution of the form of nitrate Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.1 in molar ratio is always formed by accounting for catalyst, with the co-precipitation of 50wt% solution of potassium carbonate at 80 DEG C, precipitation process needs fully to stir, and keeps pH=8.Precipitate through distilled water washing to neutrality.Gained catalyst composition SiC:wt35%, Cu:wt25%, Fe:wt15%, Mn:wt5%, Zn:wt5%, Zr:wt10%, Co:wt4%, K:1%, after 120 DEG C of dryings under 400 DEG C of air atmospheres roasting 4h, be crushed to 40-60 order, obtain catalyst 9
#.Reaction condition is as follows: T=280 DEG C, P=6.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Embodiment 10
The SiC of the 40wt% of quality and metallic atom to be made into 80wt% SiC aaerosol solution with the nitrate solution of the form of nitrate Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.5:0.5:0.1:0.1 in molar ratio is always formed by accounting for catalyst, with the co-precipitation of 55wt% solution of potassium carbonate at 90 DEG C, precipitation process needs fully to stir, and keeps pH=9.Precipitate through distilled water washing to neutrality.Gained catalyst composition SiC:wt35%, Cu:wt20%, Fe:wt20%, Mn:wt5%, Zn:wt5%, Zr:wt5%, Co:wt4%, K:1%, after 110 DEG C of dryings under 400 DEG C of air atmospheres roasting 6h, be crushed to 40-60 order, obtain catalyst 10
#.Reaction condition is as follows: T=280 DEG C, P=7.0MPa, GHSV=7500h
-1, H
2/ CO volume ratio=2.0.Reaction result is in table 1.
Table 1 embodiment reaction result
Claims (2)
1. the percentage by weight of the SiC supported catalyst of preparing low-carbon mixed alcohol by synthetic gas consists of: a SiC:30-50%, Cu:20-30%, Fe:10-20%, Mn:5-15%, Zn:5-10%, Zr:5-15%, Co:1-4%, M:0.1-5%; Wherein M is that alkali metal or alkaline-earth metal are a kind of, and wherein alkali metal is Na, K, Li or Cs; Alkaline-earth metal is Mg or Ba.
2. the present invention has good stability, and cost is low, and the life-span is long, under mild reaction conditions the advantage of high selectivity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732645A (en) * | 2016-11-29 | 2017-05-31 | 中国科学院山西煤炭化学研究所 | The activated carbon fiber-loaded catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN109289865A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The silicon-containing catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN109289891A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The boron nitride supported catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN112495414A (en) * | 2020-11-19 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | Carbon nitride supported catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof |
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Cited By (4)
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| CN106732645A (en) * | 2016-11-29 | 2017-05-31 | 中国科学院山西煤炭化学研究所 | The activated carbon fiber-loaded catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN109289865A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The silicon-containing catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN109289891A (en) * | 2018-09-30 | 2019-02-01 | 中国科学院山西煤炭化学研究所 | The boron nitride supported catalyst and preparation method of a kind of preparing low-carbon mixed alcohol by synthetic gas and application |
| CN112495414A (en) * | 2020-11-19 | 2021-03-16 | 中国科学院山西煤炭化学研究所 | Carbon nitride supported catalyst for preparing low-carbon mixed alcohol from synthesis gas and preparation method and application thereof |
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Application publication date: 20160203 |