CN101891588B - Method for synthesizing low-carbon alcohol from synthetic gas - Google Patents
Method for synthesizing low-carbon alcohol from synthetic gas Download PDFInfo
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- CN101891588B CN101891588B CN 201010174535 CN201010174535A CN101891588B CN 101891588 B CN101891588 B CN 101891588B CN 201010174535 CN201010174535 CN 201010174535 CN 201010174535 A CN201010174535 A CN 201010174535A CN 101891588 B CN101891588 B CN 101891588B
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Abstract
The invention aims to provide a method for synthesizing low-carbon alcohol from synthetic gas with high selectivity and high efficiency. The method comprises the following steps of: 1) preparing and reducing a catalyst; 2) preheating the synthetic gas; 3) performing catalytic synthesis reaction; and 4) cooling products, and then collecting the cooled products. The method has the advantages that: because the catalyst with highly active ingredients is prepared by a soaking and subsection baking method, the selectivity of alcohols is greatly improved; the reaction gases are preheated before reaction, and quartz sand is filled in the preheating section, so that the gases can be fully heated; in order to ensure enough staying time of the gases in the catalytic section, the catalyst is filled in a reactor and the quartz sand is added simultaneously, so that the filling height of the catalyst is increased, and the reaction can be fully carried out.
Description
Technical field
The present invention relates to chemical technology field, relate in particular to a kind of method of synthesizing low-carbon alcohol from synthetic gas.
Technical background
Become gas production low-carbon alcohol (C
1-C
5Alcohol) be a breakthrough after the industrialization of synthetic gas methanol.Along with the attention to environmental requirement of energy dilemma and various countries, so that synthesizing low-carbon alcohol from synthetic gas is subject to people's attention more.The application of low-carbon alcohol mainly contains following several respects:
Liquid fuel main application take low-carbon alcohol as representative is that (low-carbon alcohol that define here is as take ethanol as main as the clean gasoline additive, the C2+ alcohol that comprises part), this mainly is because contain a certain amount of C2+ alcohol in the alcohol mixture, good stability to water, the solvation effect also compares better, and can obviously improve gasoline octane rating, strengthens its anti-seismic performance, in this respect, low-carbon alcohol is expected to replace with serious pollution methyl tertiary butyl ether (MTBE); Secondly, low-carbon alcohol can be used alone as the oligosaprobic clean fuel of engine a new generation by petroleum replacing, and can be in the situation that do not change the available engine structure and use.Coal-based alcohol ether (comprises methyl alcohol, low-carbon alcohol and dme) fuel is based on the chemistry of fuel product with strategic importance of derived energy chemical diversification of feedstock, low-carbon alcohol has been proved to be high-octane rating, oligosaprobic vehicle fuel additive, can mix with gasoline and be made into alcohol-oil hybrid fuel, also can directly use separately, in recent years owing to the reason of environmental protection aspect, methyl tertiary butyl ether (MTBE) is disabled at some countries and regions (such as California, USA) as oil dope, so that low-carbon alcohol is as the practical value multiplication of oil dope. and also someone uses the straight-chain low-carbon alcohol mixture to prepare diesel product.In addition, low-carbon alcohol can also be as new industrial chemicals.At present, no matter be energy industry or the basic raw material of chemical industry, all mainly from oil, in order to change this situation, the basic chemical industry raw material that development and production derives from beyond the oil is significant, and synthesis of low-carbon alcohol is of great value approach wherein.Therefore, from the favor of the extremely many national chemists of new catalyst system of the direct synthesis of low-carbon alcohol of synthetic gas.Up to the present, a large amount of work is being done by various countries aspect the research of synthesizing low-carbon alcohol from synthetic gas technique, and the low-carbon alcohol synthetic catalyst is conducted extensive research, and has developed the catalyzer synthesis technique system of multiple synthesis of low-carbon alcohol.
The utilization with alcohol fuel is the most extensive in the low-carbon alcohol at present.Alcohol fuel also claims biofuel, fuel alcohol, gasohol, ethanol vapor wet goods, and it is to add the formed modified version propellant combination of a certain proportion of ethanol in gasoline or diesel oil, is a kind of economical and practical clean fuel.When the ethanol mix ratio was in 25%, fuel can keep its original dynamic property.The more important thing is, ethanol is a kind of manifestation of sun power, and in the large system of whole nature, the production and consumption process of ethanol can form free of contamination closed cycle, and eternal regeneration is never exhausted.Alcohol fuel also is present most widely used biofuel, is used widely in some countries and regions.Simultaneously, because prospective oil is not enough, the interdependency of its import is larger, still think to have the alcohol fuel of better substitution effect, its development space is with increasing.
But the existing synthesizing low-carbon alcohol from synthetic gas catalyst system low problem (＜30%) of selectivity that all has C2+ alcohol on the whole, therefore, the novel process system of synthesis of low-carbon alcohol receives much attention recently.
Summary of the invention
The method that the purpose of this invention is to provide a kind of highly selective, high efficiency synthesizing low-carbon alcohol from synthetic gas.
In order to reach above purpose, the present invention has taked following technical scheme:
As shown in Figure 1, the inventive method may further comprise the steps:
1) catalyzer preparation and reduction;
2) synthetic gas preheating;
3) catalytic synthesis;
4) the product cooling is collected.
The expression formula of catalyzer of the present invention is in the step 1): CuFeCoM
AM
B/ SiO
2, M wherein
AThe combination of one or more elements in the transition metals such as Zn, Cr, Zr, Mn, Ni, M
BBe a kind of of basic metal, alkaline-earth metal or rare earth element, comprise: Li, Na, K, Ca etc.
Catalyzer employing segmentation pickling process and baking inphases legal system are standby.
The catalyzer drying that makes is ground in (preferably to 80-100 orders), is filled in the reactor, reduce under atmosphere of hydrogen, and slow cooling is to room temperature.
During reduction preferred parameter be temperature between the 300-400 degree, 8 hours recovery times.
Step 2) synthetic gas passes into reaction system by gas tank through reducing valve in, and pressure-controlling at 4 ~ 9MPa, and is controlled its flow by under meter, makes H
2/ CO mol ratio reaches between 1 ~ 3, controls simultaneously air speed at 3000 ~ 8000h
-1Between; In order to make the synthetic gas preheating abundant, fill quartz sand at preheating section, gas fully is heated.
Gas is heated and reaches 250 degree for good.
The synthetic gas of process preheating in the step 3), when carrying out catalyzed reaction by catalyzer, temperature is controlled between 300 ~ 450 ° of C, in order to make gas abundant in the catalytic section residence time, in reactor, mix quartz sand in the catalyst filling, to improve the packing height of catalyzer, react fully and carry out.
Gas in the step 4) after the process catalyzed reaction is through cooling by water to 20 ~ 40 ° C, and collection tail gas.
The major advantage of the inventive method is: the catalyzer that gets high-activity component with dipping and baking inphases legal system; For reactant gases provides preheating, fill quartz sand at preheating section before the reaction, gas fully is heated; In order to make gas abundant in the catalytic section residence time, in reactor, mix quartz sand in the catalyst filling, to improve the packing height of catalyzer, react fully and carry out; Under this operational path, the selectivity of alcohols, particularly the selectivity of C2+ alcohol improves greatly.
Description of drawings
Fig. 1 is the inventive method process flow sheet
Embodiment
Do the present invention is further described below in conjunction with concrete application implementation of the present invention.
Embodiment 1
Press activity component load quantity wt% (weight percent, lower same) expression formula Cu (25) Fe (15) Co (20) M
A(15) M
B(5) (each component that marks is the per-cent of active ingredient, and rest part is the content of carrier, i.e. SiO
2) Kaolinite Preparation of Catalyst, M
ABe Zn, M
BBe K
2CO
3By methods such as dipping and baking inphases, make synthetic catalyst, prepared catalyzer is moved in the reactor, in reactor, use H
2400 ℃ of lower reducing catalysts 8 hours, slowly then airborne absolutely temperature switched to synthetic gas at pressure 5.0～6.0MPa, 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 is as follows:
Table 1
Embodiment 2
Pressure 5.0MPa, 350 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2, all the other are with embodiment 1.Acquired results is as follows:
Table 2
Embodiment 3
Pressure 5.0～6.0MPa, 350 ℃ of temperature, air speed 5000h
-1, H
2/ CO=2, all the other are with embodiment 1.Acquired results is as follows:
Table 3
Embodiment 4
Pressure 5.0～6.0MPa, 400 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2, all the other are with embodiment 1.Acquired results is as follows:
Table 4
Embodiment 5
Catalyzer consists of by charge capacity: Cu (25) Fe (25) Co (25) MA (10) MB (3), MA are Mn, and MB is Ca (OH) 2, and all the other are with embodiment 1.Pressure 5.O～6.OMPa, 300 ℃ of temperature, air speed 6000h
-1, H
2/ CO=2, acquired results is as follows:
Table 5
Embodiment 6
Catalyzer consists of by charge capacity: Cu (25) Fe (10) Co (15) MA (15) MB (10), MA are Ni, and MB is Na2CO3, and all the other are with embodiment 1.Pressure 5.0～6.OMPa, 300 ℃ of temperature, air speed 10000h-1, H
2/ CO=2, acquired results is as follows:
Table 6
Embodiment 7
Catalyzer consists of by charge capacity: Cu (30) Fe (15) Co (30) MA (15) MB (5), MA are Zr, and all the other are with embodiment 1.Pressure 6.OMPa, 300～350 ℃ of temperature, air speed 6000h-1, H
2/ CO=2, acquired results is as follows:
Table 7
Claims (1)
1. the method for a synthesizing low-carbon alcohol from synthetic gas, described low-carbon alcohol comprises the C of part for take ethanol as main
2 +Alcohol is characterized in that may further comprise the steps:
1) catalyzer preparation and reduction: the expression formula of catalyzer is: CuFeCoM
AM
B/ SiO
2, M wherein
ABe selected from a kind of among Cr, Zr, the Ni, M
BBe selected from a kind of among Li, Na, the Ca; The catalyzer drying that makes is ground, and is filled in the reactor, reduce under atmosphere of hydrogen, and slow cooling is to room temperature;
2) synthetic gas preheating: synthetic gas passes into reaction system by gas tank through reducing valve, and pressure-controlling at 4～9M Pa, and is controlled its flow by under meter, makes H
2/ CO mol ratio reaches between 1～3, controls simultaneously air speed at 3000～8000h
?1Between; In order to make the synthetic gas preheating abundant, fill quartz sand at preheating section, gas fully is heated;
3) catalytic synthesis: the synthetic gas of process preheating is when carrying out catalyzed reaction by catalyzer, temperature is controlled between 300～450 ° of C, in order to make gas abundant in the catalytic section residence time, in reactor, mix quartz sand in the catalyst filling, to improve the packing height of catalyzer, react fully and carry out;
4) the product cooling is collected.
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| CN102247852B (en) * | 2011-05-18 | 2013-04-24 | 中国科学院广州能源研究所 | 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 |
| CN102872882B (en) * | 2012-09-17 | 2014-11-26 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst for preparing low carbon alcohol, as well as preparation method and application of copper-based catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110357A2 (en) * | 1982-11-29 | 1984-06-13 | Research Association For Petroleum Alternatives Development | Process for the production of mixed alcohols |
| CN1481934A (en) * | 2003-02-26 | 2004-03-17 | 郑州大学 | Synthetic low carbon alcohol catalyst and method for making the same |
| CN101327434A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Catalyst for jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and production method and use |
-
2010
- 2010-05-10 CN CN 201010174535 patent/CN101891588B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110357A2 (en) * | 1982-11-29 | 1984-06-13 | Research Association For Petroleum Alternatives Development | Process for the production of mixed alcohols |
| CN1481934A (en) * | 2003-02-26 | 2004-03-17 | 郑州大学 | Synthetic low carbon alcohol catalyst and method for making the same |
| CN101327434A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Catalyst for jointly producing low carbon mixed alcohol and gasoline fraction from synthesis gas and production method and use |
Non-Patent Citations (4)
| Title |
|---|
| CO hydrogenation to mixed alcohols over co-precipitated Cu–Fe catalysts;Minggui Lin等;《Catalysis Communications》;20080318;第9卷(第9期);第1869-1873页 * |
| Minggui Lin等.CO hydrogenation to mixed alcohols over co-precipitated Cu–Fe catalysts.《Catalysis Communications》.2008,第9卷(第9期),第1869-1873页. |
| Su Yunlai等.Synthesis of Ketones and Alcohols via Syngas on Fe-Cu Based Catalysts.《Chinese Journal of Catalysis》.2004,第25卷(第9期),第683-684页. |
| Synthesis of Ketones and Alcohols via Syngas on Fe-Cu Based Catalysts;Su Yunlai等;《Chinese Journal of Catalysis》;20040930;第25卷(第9期);第683-684页 * |
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