CN101428229B - Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof - Google Patents
Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof Download PDFInfo
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- CN101428229B CN101428229B CN2007100478776A CN200710047877A CN101428229B CN 101428229 B CN101428229 B CN 101428229B CN 2007100478776 A CN2007100478776 A CN 2007100478776A CN 200710047877 A CN200710047877 A CN 200710047877A CN 101428229 B CN101428229 B CN 101428229B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst for synthesis of low-carbon mixed alcohol from syngas and a preparation method thereof, and mainly solves the problems of low cost, low catalytic activity and low selectivity of low-carbon alcohol (particularly ethanol) in the product in the prior art. The catalyst contains the following components in weight percentages: a) 25% to 45% of Mo, b) 5% to 15% of Co, c)10% to 25% of K, d) 1% to 15% of a rare-earth metal, and e) S in balance amount. With the technical scheme, the catalyst overcomes the problems in the prior art and is applied to the industrial production of low-carbon mixed alcohol from syngas.
Description
Technical field
The present invention relates to a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas and preparation method thereof.
Background technology
By synthesis gas system oxygenatedchemicals is one of effective rational method that utilizes of natural gas.The oxygenatedchemicals that makes can be used as gasoline additive, in order to improve octane number, replaces with serious pollution methyl tertiary butyl ether(MTBE) (MTBE); Secondly their also alternative oil are used alone as the oligosaprobic clean fuel of engine a new generation.Wherein, owing to contain the above oxygenatedchemicals of two carbon, therefore to the good stability of water, the solvation effect is excellent than methyl alcohol, gasoline additive that is considered to be more suitable for and clean fuel in low-carbon alcohols technology and the ethanol product.
The above oxygenatedchemicals of two carbon such as ethanol is large industrial chemicals.If can directly make c_2-oxygen compounds such as ethanol from natural gas, then both can save food, reduce environmental pollution, can make full use of the coal and the natural gas resource of China's abundant again, thereby alleviate the excessive pressure of China's grain industrial consumption.Combine with ethanol dehydration (ETO) technology as synthesis gas system ethanol (GTE), can directly generate ethene, substitute existing petrochemical industry route to a certain extent, thereby solve China's oil resource problem in short supply day by day, it is huge therefore to carry out this Research Significance.
The existing at present report of producing ethanol in a large number by the co hydrogenation selectivity.U.S. Pat 4235801 discloses from synthesis gas, uses the catalyst producing and ethanol in next life of a kind of main rhodium-containing and iron.U.S. union carbide corporation patent US4377643 adopts Rh/SiO
2Catalyst is selected c_2-oxygen compounds such as synthesizing alcohol, acetaldehyde and acetic acid by synthesis gas, but its active low also rich a large amount of methane that produce.Improve the purpose product selectivity in order to improve catalyst performance, studied influence such as metal such as various auxiliary agents such as Fe, Ir, Ti, Mn, Sc, Zr and alkali metal K, Na etc. catalytic performance.Even so, it is still very difficult to improve the ethanol selectivity separately.R.Burch (J.Catal., 1997,165:249～261) etc. adopt 2%Rh-10%Fe/Al
2O
3Catalyst, under 1MPa pressure, by the synthetic ethanol of synthesis gas selectivity, selectivity is up to 50%.Patent of invention CN 1225852A such as Luo Hongyuan provide c_2-oxygen compound catalyst such as synthesis gas system ethanol, acetic acid, acetaldehyde, the selectivity about 40% of its ethanol.Molybdenum that what deserves to be mentioned is most U.S. DOW company exploitation is sulfide catalyst (main patent is seen people's such as Stevens people's such as US4882360, Cochran EP0119609A).This new catalyst is the MoS that is mixed by alkali
2Form, have unique sulfur resistance, and do not tie charcoal, can be than high sulfur content (20～100mg/m
3) and low H
2Use under the unstripped gas condition of/CO than (0.7～1).Thereby the harsh conditions that the unstripped gas deep desulfurization process brought and the problem of expensive cost have been avoided.Simultaneously, product is moisture few in this catalyst system, and higher alcohol content is higher, wherein mainly is ethanol and normal propyl alcohol.Above reason makes the dark audient's multi-expert of this catalyst system and catalyzing scholar's favor, is considered to be expected to most one of catalyst system of realizing commercial Application.In recent years, the Shanxi coalification of the domestic Chinese Academy of Sciences be that the sulfide catalyst system has also been done comparatively deep research to molybdenum, and applied for relevant patent, see CN1631527A, CN1663683A, CN1431049A etc.From present pertinent literature patent report, the catalyst based raw materials used cost height of Rh, preparation technology's relative complex, and catalyst is easily by CO
2Poison; MoS
2Matrix is that catalytic activity is lower, and especially the selectivity of ethanol is lower for low-carbon alcohols in the product, has hindered the industrialization of such catalyst to a certain extent.
Summary of the invention
One of technical problem to be solved by this invention is to have catalyst for preparing low-carbon mixed alcohol by synthetic gas cost of material height in the prior art, catalytic activity is low, the low-carbon alcohols low problem of selectivity of ethanol especially provides a kind of new catalyst for preparing low-carbon mixed alcohol by synthetic gas in the product.This catalyst is used for preparing low-carbon mixed alcohol by synthetic gas, has active height, and low-carbon alcohols is ethanol selectivity height particularly, and hydrogen-carbon ratio regulation and control degree is big, the characteristics that reaction pressure is low.Two of technical problem to be solved by this invention provides preparation method a kind of and one of technical solution problem corresponding catalyst for preparing low-carbon mixed alcohol by synthetic gas.This method has that cost of material is low, the characteristics that preparation is simple.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for preparing low-carbon mixed alcohol by synthetic gas comprises following component by weight percentage:
A) 25～45% Mo;
B) 5～15% Co;
C) 10～25% K;
D) 1～15% rare earth metal;
E) S of surplus.
In the technique scheme, the consumption preferable range of Mo is 35～45% by weight percentage, and the consumption preferable range of Co is 10～15%, and the consumption preferable range of K is 10～15%, and the consumption preferable range of rare earth metal is 5～15%.Described rare earth metal preferred version is to be selected from least a among Ce, La or the Y.Each metal preferred version is for to exist with sulphided form in the catalyst.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of catalyst for preparing low-carbon mixed alcohol by synthetic gas may further comprise the steps:
A) be with ammonium molybdate and the mixed ammonium thiomolybdate that gets of ammonium sulfide solution under 6.5～9.0 conditions in the pH value;
B) cobalt salt and rare earth metal salt are dissolved in the ethanol, at 50～70 ℃ of following ultrasonic reactions after 0.5～5 hour, add the ammonium thiomolybdate that a) step makes, obtain mixture;
C) with b) mixture that makes of step is 50～70 ℃ of following ultrasonic reactions 0.5～5 hour, forms homogeneous precipitation, is cooled to room temperature, aging 12～48 hours then, obtains sediment;
D) with c) step gained sediment washs, mix with sylvite dry back, and 400～550 ℃ of roastings promptly got required catalyst in 1～8 hour under inert atmosphere.
In the technique scheme, a) the pH value preferable range of solution is 6.5～8.0 in the step.The cobalt salt preferred version is for being selected from cobalt acetate, and the rare earth metal salt preferred version is for being selected from rare-earth metal nitrate, and the sylvite preferred version is for being selected from potash.D) preferred version of inert atmosphere described in the step is for being selected from nitrogen or argon gas.
The examination condition of catalyst of the present invention: temperature is 290～350 ℃, and reaction pressure is 2～5MPa, unstripped gas H
2/ CO ratio is 1～3.
Add rare earth metal such as lanthanum, cerium or yttrium in the molybdenum cobalt-based sulfide catalyst of the present invention as auxiliary agent, can improve the especially selectivity of ethanol of activity of such catalysts and MAS.Catalyst of the present invention can use higher H
2The unstripped gas of/CO, and under relatively low pressure condition, obtain comparatively ideal catalytic activity and selectivity, reaction condition gentleness.The present invention introduces rare earth metal in the preparation process of molybdenum cobalt-based sulfide catalyst, and in the ethanol non-aqueous media, adopt ultrasonic method to prepare, can avoid the formation of independent metal sulfide phase, each uniform component distribution, help forming strong interaction between auxiliary agent and the host, prevent that auxiliary agent runs off, and improves the stability and the life-span of catalyst.Adopt technical scheme of the present invention, C in the low-carbon alcohols product
2 +Alcohol content 〉=43%, the selectivity of ethanol 〉=55%, C
2 +Alcohol space-time yield 〉=0.10 Grams Per Hour milliliter catalyst has obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Add 10 gram ammonium molybdates after 96.7 grams, 8 weight % (in S) ammonium sulfide solutions are heated to 65 ℃, stirring reaction is used the pH=7 of acetic acid regulator solution after 2 hours, continue stirring reaction after 4 hours, be cooled to room temperature, 0 ℃ was worn out 20 hours, filtered, and washed with ethanol, vacuum drying makes the ammonium thiomolybdate solid.
1.26 gram cobalt acetates and 0.31 gram lanthanum nitrate are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 60 ℃ ultrasonic 0.5 hour; Add 3.3 gram ammonium thiomolybdate solids again, continued ultrasonic 3 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 24 hours down, filter, with the ethanol washing, 120 ℃ of dryings 15 hours; The black solid of oven dry evenly mixes with potash, feeds nitrogen then, in 500 ℃ of following roastings 4 hours, obtains catalyst A, and its component and percentage by weight composition see Table 1.
[embodiment 2]
1.26 gram cobalt acetates and 1.08 gram cerous nitrates are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 65 ℃ ultrasonic 0.5 hour; Add 3.1 gram ammonium thiomolybdate solids again, continued ultrasonic 2.5 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 20 hours down, filter, with the ethanol washing, 120 ℃ of dryings 15 hours; The black solid of oven dry evenly mixes with potash, feeds argon gas then, in 550 ℃ of following roastings 2 hours, obtains catalyst B, and its component and percentage by weight composition see Table 1.
[embodiment 3]
1.90 gram cobalt acetates and 1.72 gram yttrium nitrates are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 55 ℃ ultrasonic 4 hours; Add 4.1 gram ammonium thiomolybdate solids again, continued ultrasonic 3.5 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 30 hours down, filter, with the ethanol washing, 110 ℃ of dryings 20 hours; The black solid of oven dry evenly mixes with potash, feeds argon gas then, in 450 ℃ of following roastings 6 hours, obtains catalyst C, and its component and percentage by weight composition see Table 1.
[embodiment 4]
2.10 gram cobalt acetates and 0.38 gram lanthanum nitrate, 0.31 gram cerous nitrate are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 55 ℃ ultrasonic 4 hours; Add 4.9 gram ammonium thiomolybdate solids again, continued ultrasonic 3.5 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 30 hours down, filter, with the ethanol washing, 110 ℃ of dryings 20 hours; The black solid of oven dry evenly mixes with potash, feeds argon gas then, in 450 ℃ of following roastings 6 hours, obtains catalyst D, and its component and percentage by weight composition see Table 1.
[embodiment 5]
1.58 gram cobalt acetates and 0.77 gram lanthanum nitrate, 0.23 gram praseodymium nitrate are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 55 ℃ ultrasonic 4 hours; Add 2.8 gram ammonium thiomolybdate solids again, continued ultrasonic 3.5 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 30 hours down, filter, with the ethanol washing, 110 ℃ of dryings 20 hours; The black solid of oven dry evenly mixes with potash, feeds argon gas then, in 450 ℃ of following roastings 6 hours, obtains catalyst E, and its component and percentage by weight composition see Table 1.
[Comparative Examples 1]
1.37 gram cobalt acetates and 0.55 gram manganese nitrate are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 60 ℃ ultrasonic 0.5 hour; Add 2.6 gram ammonium thiomolybdate solids again, continued ultrasonic 3 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 12 hours down, filter, with the ethanol washing, 120 ℃ of dryings 12 hours; The black solid of oven dry evenly mixes with potash, feeds nitrogen then, in 550 ℃ of following roastings 2.5 hours, obtains catalyst D1, and its component and percentage by weight composition see Table 1.
[Comparative Examples 2]
1.37 gram cobalt acetates and 0.43 gram copper nitrate are dissolved in 40 milliliters of ethanol and are mixed with mixed solution, and 60 ℃ ultrasonic 0.5 hour; Add 2.6 gram ammonium thiomolybdate solids again, continued ultrasonic 3 hours, to forming black precipitate; Naturally cool to room temperature, in 0 ℃ aging 12 hours down, filter, with the ethanol washing, 120 ℃ of dryings 12 hours; The black solid of oven dry evenly mixes with potash, feeds nitrogen then, in 550 ℃ of following roastings 2.5 hours, obtains catalyst D2, and its component and percentage by weight composition see Table 1.
[embodiment 6]
With carrying out the preparing low-carbon mixed alcohol by synthetic gas reaction under catalyst A～E reaction condition below, the results are shown in Table 1.
Reactor: internal diameter is the stainless steel fixed bed reactors of 6mm
330 ℃ of reaction temperatures
Reaction pressure 3.0MPa
0.8 milliliter of loaded catalyst
Air speed 2225 hours
-1
Raw material proportioning (mole) H
2/ CO=2
[Comparative Examples 3]
Catalyst D1, D2 are carried out the preparing low-carbon mixed alcohol by synthetic gas reaction under [embodiment 6] reaction condition, the results are shown in Table 1.
Claims (7)
1. catalyst for preparing low-carbon mixed alcohol by synthetic gas, composed of the following components by weight percentage:
A) 25～45% Mo;
B) 5～15% Co;
C) 10～25% K;
D) 1～15% rare earth metal;
E) S of surplus;
The preparation method of described catalyst for preparing low-carbon mixed alcohol by synthetic gas may further comprise the steps:
A) be with ammonium molybdate and the mixed ammonium thiomolybdate that gets of ammonium sulfide solution under 6.5～9.0 conditions in the pH value;
B) cobalt salt and rare earth metal salt are dissolved in the ethanol, at 50～70 ℃ of following ultrasonic reactions after 0.5～5 hour, add the ammonium thiomolybdate that a) step makes, obtain mixture;
C) with b) mixture that makes of step is 50～70 ℃ of following ultrasonic reactions 0.5～5 hour, forms homogeneous precipitation, is cooled to room temperature, aging 12～48 hours then, obtains sediment;
D) with c) step gained sediment washs, mix with sylvite dry back, and 400～550 ℃ of roastings promptly got required catalyst in 1～8 hour under inert atmosphere.
2. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that the consumption of Mo is 35～45% by weight percentage, the consumption of Co is 10～15%, and the consumption of K is 10～15%, and the consumption of rare earth metal is 5～15%.
3. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that described rare earth metal is selected from least a among Ce, La or the Y.
4. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that each metal exists with sulphided form in the described catalyst.
5. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that the pH value of solution in a) step is 6.5～8.0.
6. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that described cobalt salt is a cobalt acetate, described rare earth metal salt is a rare-earth metal nitrate, and described sylvite is potash.
7. according to the described catalyst for preparing low-carbon mixed alcohol by synthetic gas of claim 1, it is characterized in that d) inert atmosphere described in the step is nitrogen or argon gas.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8383691B2 (en) * | 2009-06-30 | 2013-02-26 | Albemarle Corporation | Methods of making improved cobalt-molybdenum-sulfide catalyst compositions for higher alcohol synthesis |
| CN102008963B (en) * | 2010-10-22 | 2012-05-16 | 清华大学 | Method for preparing low-carbon mixed alcohol catalyst from synthesis gas |
| CN103143374B (en) * | 2013-02-22 | 2015-12-23 | 厦门大学 | For the synthesis of gas modification molybdenum phosphide catalyst preparing low-carbon alcohols and preparation method thereof |
| 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 |
| CN114471650A (en) * | 2020-11-13 | 2022-05-13 | 国家能源投资集团有限责任公司 | Supported catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof |
| CN114797903B (en) * | 2021-01-21 | 2024-04-02 | 国家能源投资集团有限责任公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof |
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| US4831060A (en) * | 1984-07-30 | 1989-05-16 | The Dow Chemical Company | Mixed alcohols production from syngas |
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| CN1207957A (en) * | 1998-09-10 | 1999-02-17 | 厦门大学 | Catalyst for synthesizing methyl mercaptan from synthesized gas contg. hydrogen sulfide |
| US6605647B2 (en) * | 2000-07-04 | 2003-08-12 | President Of Tohoku University | Hydrogenation of carbon monoxide using sulfide catalysts |
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