CN102247852A - 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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- CN102247852A CN102247852A CN2011101294263A CN201110129426A CN102247852A CN 102247852 A CN102247852 A CN 102247852A CN 2011101294263 A CN2011101294263 A CN 2011101294263A CN 201110129426 A CN201110129426 A CN 201110129426A CN 102247852 A CN102247852 A CN 102247852A
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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 Cu-Fe-Co catalyst based and preparation method and its application in synthesizing low-carbon alcohol from synthetic gas technology of a kind of synthesis gas preparation low-carbon alcohols.
[technical background]
Synthesis gas production low-carbon alcohols (C
1-C
5Alcohol) be a breakthrough after the synthesis gas production methanol industryization.Along with energy crisis and various countries to the attention of environmental requirement, make synthesizing low-carbon alcohol from synthetic gas be 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, though 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 a clean gasoline additive.Since MTBE puts on market as gasoline additive, with good miscibility of itself and gasoline and high octane number.But there are some problems in the use of discovering MTBE in recent years, leak, cause drinking water pollution, human health is existed threaten as being easy in storage, transportation and the use.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 still is basic Organic Chemicals.
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 technology of Germany Lurgi company exploitation, EP0034338-A2), Zn-Cr-K catalyst system and catalyzing (the MAS technology 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 technology, 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.
Discover that Cu is the active component of synthesizing methanol in each component of modification F-T synthetic catalyst, help the non-absorption of dissociating of CO, favourable to synthol; The absorption of dissociating that cobalt or iron component help CO impels single intermediate carbon CH
x +Formation, and highly active single intermediate carbon mutually combines, and forms the C-C key, realizes that carbochain increases.Co CO hydrogenation activity height wherein, F-T chain growth ability is strong, and water gas shift reaction is insensitive, is difficult for carbon distribution and poisoning under the hot conditions, but the price height, reserves are limited; And Fe chain growth ability is poor slightly than Co, and to the water gas shift reaction sensitivity, the catalyst based activity of independent Cu-Fe is relatively poor, C
2+The selectivity of alcohol is 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 take place carbongl group synthesis reaction and generates low-carbon alcohols.
The industrial production cost is lower 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, satisfies the demand in market.
All there is C in existing on the whole synthesizing low-carbon alcohol from synthetic gas catalyst system and catalyzing
2+The problem that selectivity is low, production cost is high of alcohol, therefore, the new catalyst system and catalyzing of synthesis of low-carbon alcohol receives much attention recently.
[summary of the invention]
The objective 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, so that 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 with Cu-Fe-Co be the catalyst of main component with catalysis CO hydrogenation synthesizing low carbon alcohol, the active component that increases as main carbochain of Fe wherein, 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 a 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 the oxalates or the citrate aqueous solution with Cu, Fe, Co, M, or contain the 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, speed with 1.0～10 ℃/min rises to 250～500 ℃ of roastings 3～12 hours then, then naturally cools to room temperature.
Impregnation method can a 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 technology, 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, helps improving the selectivity of alcohols;
(3) compare with catalyst of the same type, it is gentle that this catalyst is used for the reaction condition of synthesizing low-carbon alcohol from synthetic gas, less demanding to consersion unit.
[specific embodiment]
Followingly the present invention is done detailed explanation by embodiment.
Embodiment 1
By expression formula Cu
25Fe
15Co
5K
2/ (SiO
2)
58The preparation 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 oven dry down under the room temperature.Speed with 1.0 ℃/min is warming up to 400 ℃ of roastings 8 hours then, then naturally cools to room temperature.
Prepared catalyst is moved in the reactor, use H
2Reduced 8 hours down at 400 ℃, switch to synthesis gas then at pressure 1.5～10.0MPa, 300 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2 collects liquid product with ice-water bath, and the gas chromatographic analysis product is formed, gained result such as table 1:
Table 1
Embodiment 2
By expression formula Cu
20Fe
20Co
5Ce
2/ (SiO
2)
53The preparation 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, gained result such as table 2:
Table 2
Embodiment 3
By expression formula Cu
25Fe
25Co
3Mn
2/ (SiO
2)
45The preparation 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, the gained result is as follows:
Table 3
Embodiment 4
By expression formula Cu
25Fe
20Co
5K
2/ (SiO)
48The preparation 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, the gained result is as follows:
Table 4
Embodiment 5
Take the identical preparation process of embodiment 1, prepare catalyst, pressure 5.5MPa, 350 ℃ of temperature, air speed 6000h according to catalyst expression formula as shown in table 5
-1, H
2/ CO=2, all the other are with embodiment 1, and the gained result 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 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%.
2. Cu-Fe-Co as claimed in claim 1 is catalyst based, it is characterized in that: 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.
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 the described Cu-Fe-Co of 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 the 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 oven dry of dipping back, speed with 1.0～10 ℃/min rises to 300～500 ℃ of roastings 3～12 hours then, then naturally cools to room temperature.
5. the catalyst based application in synthesis gas preparation low-carbon alcohols technology of the described Cu-Fe-Co of claim 1.
6. the catalyst based application in synthesizing low-carbon alcohol from synthetic gas technology of Cu-Fe-Co as claimed in claim 5, it is characterized in that: the catalyst based condition that is used for synthesizing low-carbon alcohol from synthetic gas 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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| CN102319575A (en) * | 2011-06-03 | 2012-01-18 | 中国科学院广州能源研究所 | Cu-Fe-based catalyst used in synthesis of higher alcohol with synthetic gas, preparation method thereof and application thereof to process for synthesizing higher alcohol with synthetic gas |
| CN103613483A (en) * | 2013-11-14 | 2014-03-05 | 中国科学院广州能源研究所 | Application of layered loading catalyst in preparation of lower alcohol by using synthesis gas |
| CN103831112A (en) * | 2014-03-20 | 2014-06-04 | 太原理工大学 | Catalyst for preparing low alcohol from synthesis gases as well as preparation method and application of catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101804354A (en) * | 2010-05-12 | 2010-08-18 | 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 |
| CN101891588A (en) * | 2010-05-10 | 2010-11-24 | 中国科学院广州能源研究所 | Method for synthesizing low-carbon alcohol from synthetic gas |
-
2011
- 2011-05-18 CN CN2011101294263A patent/CN102247852B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101891588A (en) * | 2010-05-10 | 2010-11-24 | 中国科学院广州能源研究所 | Method for synthesizing low-carbon alcohol from synthetic gas |
| CN101804354A (en) * | 2010-05-12 | 2010-08-18 | 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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