CN102247852B - Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas - Google Patents
Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas Download PDFInfo
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- CN102247852B CN102247852B CN2011101294263A CN201110129426A CN102247852B CN 102247852 B CN102247852 B CN 102247852B CN 2011101294263 A CN2011101294263 A CN 2011101294263A CN 201110129426 A CN201110129426 A CN 201110129426A CN 102247852 B CN102247852 B CN 102247852B
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Abstract
The invention provides a Cu-Fe-Co base catalyst which has higher C2<+> alcohol selectivity and is used for synthesizing low carbon alcohol by utilizing synthesis gas and a preparation method thereof. The expression of the catalyst is CuaFebCocMd/SiO2, or CuaFebCocMd/Al2O3 or CuaFebCocMd/(SiO2+Al2O3), wherein M is one or a combination of more than one of transitional metal element, alkali metal, alkaline earth metal and rare-earth element, and a catalyst carrier is SiO2 or Al2O3 or a mixture of SiO2 and Al2O3; and loaded active components Cu, Fe, Co and M in the catalyst respectively account for a, b, c and d of the total weight of the catalyst (wt%), a is 10-35%, b is 10-35%, c is 1-10%, d is 0-5%, and the catalyst carrier accounts for 15-79%. The catalyst is prepared by adopting the steps of impregnation and substep reduction. The Cu-Fe-Co base catalyst provided by the invention can be applied to the low carbon alcohol process by virtue of the synthesis gas. The catalyst provided by the invention has low cost, a simple preparation method and stable performance, and the industrial amplification production is easy to realize; and compared with similar catalysts, the catalyst provided by the invention has mild reaction conditions and low reaction equipment requirements when being used for synthesizing the low carbon alcohol by utilizing the synthesis gas.
Description
[technical field]
The present invention relates to chemical technology field, specifically, relate to a kind of synthesis gas and prepare the Cu-Fe-Co of low-carbon alcohols catalyst based and preparation method and its application in synthesizing low-carbon alcohol from synthetic gas technique.
[technical background]
Synthesis gas production low-carbon alcohols (C
1-C
5Alcohol) be a breakthrough after the industrialization of synthesis gas methanol.Along with the attention to environmental requirement of energy crisis and various countries, so that synthesizing low-carbon alcohol from synthetic gas is subject to people's attention more.The application of low-carbon alcohols mainly contains following several respects:
At first can be used as the high-quality power fuel, although the calorific value of low-carbon alcohols a little less than vapour, diesel oil because the existence of oxygen in the alcohol, its ratio of combustion vapour, diesel oil are abundant, harmful substance is less in the exhaust emissions, is environmentally friendly fuel.The Another Application of low-carbon alcohols is clean gasoline additive.Since MTBE puts on market as gasoline additive, with the good miscibility of itself and gasoline and high octane number.But there are some problems in the use of the discovery of research in recent years MTBE, leak as being easy in storage, transportation and the use procedure, cause drinking water pollution, human health is existed threaten.California, USA has confirmed that by zoopery MTBE has carcinogenesis to human body, is decided by before 2003 its forbidding, and Environmental Protection Agency also is defined in the U.S. and completely forbids and use MTBE.Performance indications can substitute MTBE and low-carbon alcohols is so that its high-octane rating, explosion-proof anti-seismic performance be superior etc.Simultaneously, low-carbon alcohols or basic organic chemical industry raw material.
The technology of synthesizing low-carbon alcohol from synthetic gas mainly contains both at home and abroad at present:
Alkali metals modified Cu-Zn-Al catalyst system and catalyzing (the Octamix technique of Germany Lurgi company exploitation, EP0034338-A2), Zn-Cr-K catalyst system and catalyzing (the MAS technique of Italy Snam company and the exploitation of Denmark Topse company, GB2076423, EP0768290A1), the MoS of U.S. DOW chemical company and Unide Carbon cooperative development
2Catalyst system and catalyzing (Sygmol technique, US4752622, US4675344).Domestic patent has the Zr-Cu-Ni-Mn catalyst system and catalyzing (CN1428192A) of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences, the rhodium base catalyst system and catalyzing (CN1179993A) of Xiamen University, the Cu/Ce of the electroless plating method preparation of Tsing-Hua University
0.5Zr
0.5O
2Catalyst system and catalyzing (CN101259415A) etc.
Research finds that Cu is the active component of synthesizing methanol in each component of modification F-T synthetic catalyst, is conducive to the non-Dissociative of CO, and is favourable to synthol; Cobalt or iron component are conducive to the Dissociative of CO, impel single intermediate carbon CH
x +Formation, and highly active single intermediate carbon mutually combines, and forms the C-C key, realizes carbon chain growth.Wherein Co CO hydrogenation activity is high, and F-T chain growth ability is strong, and water gas shift reaction is insensitive, be difficult for carbon distribution and poisoning under the hot conditions, but price is high, and reserves are limited; And Fe chain growth ability is slightly poor than Co, and responsive to water gas shift reaction, the catalyst based activity of independent Cu-Fe is relatively poor, C
2+Pure is selectively low, but its reserves are abundant, cheap, can be used as low-cost main active component, and can selectively obtain low-carbon alkene by height, is easy to occur carbongl group synthesis reaction and generates low-carbon alcohols.
The industrial production cost compare is low in order to develop, specific activity better, C
2+The selectivity ratios of alcohol is higher, is badly in need of a kind of new catalyst system of exploitation, the demand of satisfying the market.
All there is C in existing synthesizing low-carbon alcohol from synthetic gas catalyst system and catalyzing on the whole
2+The high problem of selectively low, production cost of alcohol, therefore, the new catalyst system and catalyzing of synthesis of low-carbon alcohol receives much attention recently.
[summary of the invention]
The object of the invention is to overcome the deficiency of existing catalyst system and catalyzing, a kind of higher C that has is provided
2+The Cu-Fe-Co of alcohol selectivity of synthesis gas synthesis of low-carbon alcohol is catalyst based and preparation method thereof, in order to reduce the Catalyst Production cost.
Another object of the present invention provides the catalyst based application in the low-carbon alcohols synthesis technique of above-mentioned Cu-Fe-Co.
For further improving C
2+The content of alcohol reduces the Catalyst Production cost, the invention provides a kind of catalyst take Cu-Fe-Co as main component with catalysis CO hydrogenation synthesizing low carbon alcohol, and wherein Fe is as the active component of main carbon chain growth, and Co modifies catalyst as auxiliary agent.
The catalyst based expression formula of Cu-Fe-Co of the present invention is: Cu
aFe
bCo
cM
d/ SiO
2Or Cu
aFe
bCo
cM
d/ Al
2O
3, or Cu
aFe
bCo
cM
d/ (SiO
2+ Al
2O
3); Wherein M is the combination of one or more elements in transition metal, alkali metal, alkaline-earth metal or the rare earth element, and catalyst carrier is SiO
2, or Al
2O
3, or SiO
2And Al
2O
3Mix; Calculate by percentage to the quality, the active component Cu of load, Fe, Co and M account for the catalyst total amount and are respectively a, b, c and d in the described catalyst, and a=10～35%, b=10～35%, and c=1～10%, d=0～5%, catalyst carrier is 15～79%.
Described M is selected from the combination of one or more elements among Cr, Zr, Mn, Mo, Ni, V, Rb, Cs, Li, Na, K, Ca, Mg, Ba, the Ce.
When catalyst carrier is SiO
2And Al
2O
3During mixture, SiO
2And Al
2O
3Can mix with arbitrary proportion.
The preparation method of the catalyst based employing step impregnation of Cu-Fe-Co of the present invention or a step dipping, step-by-step reduction.May further comprise the steps:
Nitrate or acetate or oxalates or the citrate aqueous solution with Cu, Fe, Co, M, or contain ethanol below 30% or the mixed aqueous solution of acetone or ethylene glycol and above-mentioned substance, behind the impregnation catalyst agent carrier 0.5～12 hour, oven dry, then the speed with 1.0～10 ℃/min rises to 250～500 ℃ of roastings 3～12 hours, then naturally cools to room temperature.
Impregnation method can step impregnation or a step dipping.
Cu-Fe-Co of the present invention is catalyst based to be can be used in the synthesizing low-carbon alcohol from synthetic gas technique, and its application conditions is: pressure 1.5～10.0MPa, 210～450 ℃ of temperature, air speed 500～14000h
-1, H
2/ CO=0.5～3.
The catalyst based advantage of Cu-Fe-Co of the present invention is:
(1) this catalyst cost is low, and the preparation method is simple, and stable performance is easy to industry's enlarging production;
(2) employing step impregnation or goes on foot the preparation method of dipping, step-by-step reduction, can make the catalyst of high-activity component, is conducive to improve the selective of alcohols;
(3) compare with catalyst of the same type, this catalyst is gentle for the synthesis of the reaction condition of gas synthesis of low-carbon alcohol, and is less demanding to consersion unit.
[specific embodiment]
It is following that the present invention is described in detail by embodiment.
Embodiment 1
By expression formula Cu
25Fe
15Co
5K
2/ (SiO
2)
58Kaolinite Preparation of Catalyst is got 10.0g 30～100 order microsphere silica gels, and by the nitrate aqueous solution (with incipient impregnation) of above-mentioned expression formula proportional arrangement Cu, Fe, Co, K, dipping is after 4 hours, in 200 ℃ of lower oven dry under the room temperature.Then the speed with 1.0 ℃/min is warming up to 400 ℃ of roastings 8 hours, then naturally cools to room temperature.
Prepared catalyst is moved in the reactor, use H
2400 ℃ of lower reduction 8 hours, then switch to synthesis gas at pressure 1.5～10.0MPa, 300 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2 collects liquid product with ice-water bath, the gas chromatographic analysis product composition, and acquired results such as table 1:
Table 1
Embodiment 2
By expression formula Cu
20Fe
20Co
5Ce
2/ (SiO
2)
53Kaolinite Preparation of Catalyst is got 10.0g 30～100 order microsphere silica gels, contains the aqueous solution (with incipient impregnation) of ethanol 10% by the oxalates of above-mentioned expression formula proportional arrangement Cu, Fe, Co, Ce, and all the other are with embodiment 1.Pressure 5.5MPa, temperature 210-450 ℃, air speed 6000h
-1, H
2/ CO=2, acquired results such as table 2:
Table 2
Embodiment 3
By expression formula Cu
25Fe
25Co
3Mn
2/ (SiO
2)
45Kaolinite Preparation of Catalyst is got 10.0g 30～100 order microsphere silica gels, contains the aqueous solution (with incipient impregnation) of 30% acetone by the acetate of above-mentioned expression formula proportional arrangement Cu, Fe, Co, Mn, and all the other are with embodiment 1.Pressure 5.5MPa, 350 ℃ of temperature, air speed 500～14000h
-1, H
2/ CO=2, acquired results is as follows:
Table 3
Embodiment 4
By expression formula Cu
25Fe
20Co
5K
2/ (SiO)
48Kaolinite Preparation of Catalyst uses the citrate of Cu, Fe, Co, K to contain the aqueous solution (with incipient impregnation) of ethylene glycol 10%, and all the other are with embodiment 1.Pressure 5.5MPa, 350 ℃ of temperature, air speed 6000h
-1, H
2/ CO=0.5～3, acquired results is as follows:
Table 4
Embodiment 5
Take the identical preparation process of embodiment 1, according to catalyst expression formula Kaolinite Preparation of Catalyst as shown in table 5, pressure 5.5MPa, 350 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2, all the other are with embodiment 1, and acquired results is as follows:
Table 5
Claims (6)
1. the Cu-Fe-Co of a synthesizing low-carbon alcohol from synthetic gas is catalyst based, it is characterized in that: the catalyst based expression formula of described Cu-Fe-Co is: Cu
aFe
bCo
cM
d/ SiO
2, or Cu
aFe
bCo
cM
d/ Al
2O
3, or Cu
aFe
bCo
cM
d/ (SiO
2+ Al
2O
3); Wherein M is a kind of in transition metal, alkali metal, alkaline-earth metal or the rare earth element, and catalyst carrier is SiO
2, or Al
2O
3, or SiO
2And Al
2O
3Mix; Calculate by percentage to the quality, the active component Cu of load, Fe, Co and M account for the catalyst total amount and are respectively a, b, c and d in the described catalyst, and a=10～35%, b=10～35%, and c=1～10%, d=0～5%, catalyst carrier is 15～79%.
2. Cu-Fe-Co as claimed in claim 1 is catalyst based, it is characterized in that: described M is selected from a kind of among Cr, Zr, Mn, Mo, Ni, V, Rb, Cs, Li, Na, K, Ca, Mg, Ba, the Ce.
3. Cu-Fe-Co as claimed in claim 1 is catalyst based, it is characterized in that described catalyst carrier is SiO
2Or Al
2O
3Or SiO
2And Al
2O
3Mixture; When catalyst carrier is SiO
2And Al
2O
3During mixture, SiO
2And Al
2O
3Can mix with arbitrary proportion.
4. the catalyst based preparation method of Cu-Fe-Co claimed in claim 1, it is characterized in that comprising the steps: with Cu, Fe, the nitrate of Co, M or the aqueous solution of acetate or oxalates or citrate, or contain ethanol below 30% or the mixed aqueous solution of acetone or ethylene glycol and above-mentioned substance, impregnation catalyst agent carrier 0.5～12 hour, the dipping post-drying, then the speed with 1.0～10 ℃/min rises to 300～500 ℃ of roastings 3～12 hours, then naturally cools to room temperature.
5. Cu-Fe-Co claimed in claim 1 is catalyst based prepares application in the low-carbon alcohols technique at synthesis gas.
6. the catalyst based application in synthesizing low-carbon alcohol from synthetic gas technique of Cu-Fe-Co as claimed in claim 5, it is characterized in that: the catalyst based condition for the synthesis of the gas synthesis of low-carbon alcohol of described Cu-Fe-Co is: pressure 1.5～10.0MPa, 210～450 ℃ of temperature, air speed 500～14000h
-1, H
2/ CO=0.5～3.
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| CN102319575B (en) * | 2011-06-03 | 2012-12-26 | 中国科学院广州能源研究所 | Application of Cu-Fe-based catalyst in synthesis of higher alcohol with synthetic gas |
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| CN101327433A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Nano metallic carbide catalyst and preparation and use |
| CN101891588B (en) * | 2010-05-10 | 2013-10-23 | 中国科学院广州能源研究所 | Method for synthesizing low-carbon alcohol from synthetic gas |
| CN101804354B (en) * | 2010-05-12 | 2013-08-28 | 新奥新能(北京)科技有限公司 | Low-carbon alcohol catalyst prepared from synthetic gas as well as preparation method and application thereof |
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