CN101830776A - Method for synthesizing ethanol - Google Patents
Method for synthesizing ethanol Download PDFInfo
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- CN101830776A CN101830776A CN201010177750A CN201010177750A CN101830776A CN 101830776 A CN101830776 A CN 101830776A CN 201010177750 A CN201010177750 A CN 201010177750A CN 201010177750 A CN201010177750 A CN 201010177750A CN 101830776 A CN101830776 A CN 101830776A
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- ethanol
- synthesizing alcohol
- carbon monoxide
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Abstract
The invention discloses a method for synthesizing ethanol, which comprises the following steps of: 1, preparing oxalic acid diester through coupling reaction of carbon monoxide and nitrite under the catalysis of an alumina-supported palladium catalyst; 2, pre-heating and vaporizing the oxalic acid diester and mixing with hydrogen; carrying out catalytic hydrogenation reaction on the mixed gas on a silicon dioxide-supported copper catalyst, and then cooling and distilling the reaction product to obtain ethanol. The preparation method of the invention realizes over 80% of selectivity and high yield of ethanol, and the gas used in synthesis process can be completely converted through circulation, thereby establishing a good foundation for research on the industry of synthesizing ethanol from biomass.
Description
Technical field
The invention belongs to technical field of organic synthesis, refer more particularly to a kind of method of synthesizing alcohol.
Background technology
Ethanol is commonly called as alcohol, is a kind of clean fuel.Oil substitutes such as exploitation fuel alcohol, taking measures to save petroleum resources is one of emphasis of the Tenth Five-Year Plan (2001-2005) outline.Vehicle-use alcohol gasoline is a kind of new automobile fuel that denatured fuel ethanol and gasoline are mixed by a certain percentage and form.It can effectively improve the performance and the quality of oil product, reduces the discharging of principal pollutant such as carbon monoxide, hydrocarbon polymer and does not influence the rideability of automobile.Ethanol petrol is the present development priority of renewable energy source in the world as a kind of novel clean fuel, meets China's energy substitution strategy and renewable energy source developing direction.Ethanol also is a kind of important chemical material, can be as the raw material of industrial chemical and polymkeric substance.
At present, industrial production alcoholic acid method mainly is the direct aquation method of fermentation method and ethene.Fermentation legal system ethanol is to grow up on the basis of wine brewing, in the quite long period of history, once is to produce the unique commercial run of alcoholic acid.The massfraction of ethanol in fermented liquid is about 6%-10%, and contains some other organic impurity, can obtain 95% industrial alcohol through rectifying.Yet at present fermentation method alcoholic acid raw material still comes from cereal grain fermentation method and can only utilize 6-carbon sugar in the biomass, and can't utilize 5-carbon sugar and xylogen in the biomass.In addition, fermentation method alcoholic acid raw material mainly still comes from cereal grain (stalk cellulose disassociation fermentation conversion rate is also too low) at present, and cereal grain fermentative production of ethanol and people strive grain, and grain price goes up thereupon, and restriction cereal grain fermentative production of ethanol is give stricted orders by country at present.The direct aquation method of ethene is exactly under the condition that heating, pressurization and catalyzer exist, and ethene and water direct reaction are produced ethanol.Ethene obtains from petroleum cracking, thereby its production cost and throughput seriously depend on petroleum industry.
Synthetic gas is to be main ingredient with carbon monoxide and hydrogen, as a kind of unstripped gas of industrial chemicals.Synthetic gas can derive from the partial oxidation of gasifying biomass, coal gasification and Sweet natural gas and reform, thereby the advantage of aboundresources and Sustainable development is arranged from the synthetic gas synthesizing alcohol.Experience a nearly century though direct method is produced alcoholic acid research, still be faced with stern challenge.Though the homogeneous catalysis process can obtain higher ethanol selectivity, owing to use expensive catalysts, higher working pressure and loaded down with trivial details catalyst separating and removal process have limited the practical application of this technology.For heterogeneous catalysis process,, cause alcoholic acid selectivity and yield all lower because the carbochain that the formation of C-C key is subjected to dynamic (dynamical) restriction and contains the intermediate of two carbon atoms increases fast.Thereby seek one efficiently the operational path of synthesizing alcohol have important practical significance.
Summary of the invention
The invention provides the method that a kind of selectivity is good, yield is high and be easy to realize industrialized synthesizing alcohol.
A kind of method of synthesizing alcohol comprises:
(1) carbon monoxide and nitrous acid ester carry out linked reaction under the catalysis of alumina load palladium catalyst, prepare oxalate diester;
(2) mix with oxalate diester heating vaporization and with hydrogen, mixed gas carries out catalytic hydrogenation reaction on silicon dioxide carried copper catalyst, and reaction product obtains ethanol through cooling, distillation.
It is palladium that carbon monoxide and nitrous acid ester carry out linked reaction catalyst system therefor activeconstituents, and carrier is the α-Al with vesicular structure
2O
3, specific surface area is 3～30m
2/ g, catalyzer are that the pickling process by routine obtains.Catalyzer needs reduction activation before use, to guarantee the catalytic activity of catalyzer.
The used nitrous acid ester of linked reaction can be methyl nitrite or ethyl nitrite, can be selected from the commercially available prod, also can be prepared by Sodium Nitrite, sulfuric acid and alcohol according to method well known in the art; Perhaps, generated by nitrogen protoxide, oxygen and alcohol reaction, described alcohol is methyl alcohol or ethanol.Of the present invention is to be the feedstock production nitrous acid ester with nitrogen protoxide, oxygen and alcohol, concrete operations step reference literature US 4353843.
Oxalate diester is dimethyl oxalate or oxalic acid diethyl ester, is prepared by corresponding methyl nitrite or ethyl nitrite respectively.
Linked reaction is carried out in fixed-bed reactor, and the product oxalate diester that generates after the condensation is collected from the bottom of reactor, if the preparation oxalic acid diethyl ester, its cooling back is a liquid, directly collects; If dimethyl oxalate, because its cooling back is a solid, so, can adopt C for follow-up reinforced convenience
1～C
4Alkyl alcohol collect, collection method can be with reference to patent documentation EP 0046983, what obtain is the alcoholic solution of dimethyl oxalate, can handle and directly use in the catalytic hydrogenation reaction; Selected alcohol has solvability preferably to dimethyl oxalate, and can not react with dimethyl oxalate, can not participate in follow-up catalytic hydrogenation reaction.The by product nitrogen protoxide that reaction generates can further change into nitrous acid ester and recycle; Linked reaction is carried out under normal pressure, and temperature of reaction is 100～150 ℃; Carbon monoxide: the volume ratio of methyl nitrite is: 1.1～2: 1, and the total gas volume air speed of carbon monoxide and nitrous acid ester is 900～4500h
-1
Barkite catalytic hydrogenation reaction catalyst system therefor active ingredient is a copper, and carrier is unbodied silicon-dioxide.Catalyzer obtains by the Preparation by Uniform Precipitation of routine, adopts to make precipitation agent with ammoniacal liquor or urea, and in-situ deposition is on the nano SiO 2 particle that silicon sol forms or be deposited on the silicon-dioxide for preparing in advance.The specific surface area of catalyzer is 150～400m
2/ g.Catalyzer needs reduction activation before use, to guarantee the catalytic activity of catalyzer.
Catalytic hydrogenation reaction also is to carry out in fixed-bed reactor, mix with oxalate diester preheating vaporization and with hydrogen, gas mixture feeds in the fixed-bed reactor and carry out catalytic hydrogenation reaction on silicon dioxide carried copper catalyst, temperature of reaction is 220～300 ℃, reaction pressure is 0.5～6MPa, the mol ratio of oxalate diester and hydrogen is 1: 10～500, (be meant that it is 101.325 kPas with pressure that temperature is 0 ℃) under the normal conditions, the residence time of oxalate diester on catalyzer is 0.5～20s, and reaction product obtains ethanol after condensation and distillation.
The main component that main raw material carbon monoxide that the present invention is used and hydrogen are synthetic gas can derive from the gas that number of ways such as gasifying biomass, gasification and gas by partial oxidation of natural reformation produce.Can be pure carbon monoxide and hydrogen, also can be the hydrogen that contains the carbon monoxide of small quantity of hydrogen and contain a small amount of carbon monoxide, can also contain the rare gas element of picture nitrogen and carbonic acid gas etc. in the gas.
The beneficial effect that the present invention has is embodied in: method synthetic ethanol provided by the invention, and selectivity and yield are higher; The industry that can be the biomass synthesizing alcohol is established good research basis.
Embodiment
Embodiment 1
(1) preparation alumina load palladium catalyst: take by weighing 5g α-Al
2O
3, be that 0.5% charge capacity takes by weighing 0.063g Pd (NO by weight percentage
3)
22H
2O is mixed with steeping fluid, and solvent is a deionized water, is 15m with specific surface area then
2Carrier α-Al of/g
2O
3Soak 10h in steeping fluid, 80 ℃ of following transpiring moistures obtain solid, again the gained solid are dried 12h down at 120 ℃, and 400 ℃ of following roasting 2h promptly get alumina load palladium catalyst (Pd/ α-Al
2O
3).
(2) preparation dimethyl oxalate: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 2ml, and catalyzer is used 50ml/min CO reductase 12 h under 350 ℃ of conditions before use.Unstripped gas carbon monoxide and methyl nitrite (wherein, methyl nitrite is to prepare according to document US 4353843) are from top to bottom by reactor (volume ratio of carbon monoxide and methyl nitrite is 1.4: 1), and the volume space velocity of unstripped gas is 2500h
-1, product is collected product gas chromatogram on-line analysis with the methyl alcohol of 0.46ml/min 40 ℃ of following condensations.Be reflected under the normal pressure and carry out, temperature of reaction is 120 ℃, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 20%.
(3) prepare silicon dioxide carried copper catalyst: take by weighing 15.25g Cu (NO
3)
23H
2The O solid, be that 30% charge capacity prepares copper catalyst by mass percentage, the steps include: under agitation, the cupric nitrate solid that takes by weighing is dissolved in the 200ml deionized water, and the adding strong aqua reaches 10 up to the pH value of solution, take by weighing the alkaline silica sol of 37.4g 25%, then above-mentioned two kinds of liquid are added drop-wise in the flask that fills 50ml distilled water simultaneously, the pH value of control solution is 9.Add the back and continue to stir 4h, heating makes pH value reach 6-7 under 90 ℃ of conditions then.Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h promptly get described copper catalyst, and specific surface area is 294m
2/ g.
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 250 ℃, and reaction pressure is 2MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, and the mol ratio of hydrogen and dimethyl oxalate is 100, the residence time is 8.6s (under the normal conditions).The transformation efficiency 100% of dimethyl oxalate, alcoholic acid selectivity are 65%, and the selectivity of n-propyl alcohol is 9%, and the selectivity of Virahol is 8%.
Embodiment 2
Prepare alumina load palladium catalyst, dimethyl oxalate and silicon dioxide carried copper catalyst according to embodiment 1;
Temperature of reaction is 280 ℃ in the preparation ethanol step, the mol ratio of hydrogen and dimethyl oxalate is 350, the residence time is 5.7s (under the normal conditions), other conditions are with embodiment 1, the transformation efficiency 100% of dimethyl oxalate, the alcoholic acid selectivity is 83%, and the selectivity of n-propyl alcohol is 12%, and the selectivity of Virahol is 1%.
Embodiment 3
Prepare alumina load palladium catalyst, dimethyl oxalate and silicon dioxide carried copper catalyst according to embodiment 1;
Temperature of reaction is 290 ℃ in the preparation ethanol step, and the residence time is 3s (under the normal conditions), and other conditions are with embodiment 2, the transformation efficiency 100% of dimethyl oxalate, and the alcoholic acid selectivity is 75%, and the selectivity of n-propyl alcohol is 7%, and the selectivity of Virahol is 5%.
Embodiment 4
(1) prepares the alumina load palladium catalyst according to embodiment 1 same method;
(2) prepare the reaction product that the methyl alcohol of using 0.21ml/min in the dimethyl oxalate step instead is collected condensation, other conditions are with embodiment 1, and the mass percent concentration of the product mesoxalic acid dimethyl ester of collection is 35%;
(3) prepare silicon dioxide carried copper catalyst: take by weighing 14.26g Cu (NO
3)
23H
2The O solid is that 40% charge capacity prepares copper catalyst by mass percentage, the steps include: under agitation, and cupric nitrate solid and the 10.63g urea that is taken by weighing is dissolved in the 300ml deionized water, drips the acidic silicasol of 22.5g 25% then.After adding, continue to stir 3h.Under 90 ℃, make hydrolysis of urea reach 7 then until pH value.Filter, wash 5 times, 120 ℃ of oven dry, 450 ℃ of roasting 4h promptly get described copper catalyst, and specific surface area is 319m
2/ g.
(4) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The methanol solution of the intermediate product dimethyl oxalate that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 230 ℃, and reaction pressure is 3MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, the mol ratio of hydrogen and dimethyl oxalate is 400, the residence time is 4.8s (under the normal conditions), the transformation efficiency 100% of dimethyl oxalate, the alcoholic acid selectivity is 58%, and the selectivity of n-propyl alcohol is 12%, and the selectivity of Virahol is 12%.
Embodiment 5
Prepare according to embodiment 1 and to prepare dimethyl oxalate and silicon dioxide carried copper catalyst among alumina load palladium catalyst and the embodiment 4;
Temperature of reaction is 270 ℃ in the preparation ethanol step, and reaction pressure is 4MPa, and the residence time is 4.3s (under the normal conditions), other conditions are with embodiment 4, the transformation efficiency 100% of dimethyl oxalate, and the alcoholic acid selectivity is 85%, the selectivity of n-propyl alcohol is 9%, and the selectivity of Virahol is 2%.
Embodiment 6
(1) prepares the alumina load palladium catalyst according to embodiment 1 same method and prepare silicon dioxide carried copper catalyst with embodiment 4 identical methods;
(2) preparation oxalic acid diethyl ester: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of alumina load palladium catalyst is 1.5ml, and catalyzer is used 50ml/min CO reductase 12 h under 350 ℃ of conditions before use.Unstripped gas carbon monoxide and ethyl nitrite (wherein, ethyl nitrite is to prepare according to document US 4353843) are from top to bottom by reactor (carbon monoxide and ethyl nitrite volume ratio are 1.8: 1), and the volume space velocity of unstripped gas is 3100h
-1, product is collected after condensation, product gas chromatogram on-line analysis.Be reflected under the normal pressure and carry out, temperature of reaction is 135 ℃, and the mass percent concentration of the product mesoxalic acid diethyl ester of collection is 96%.
(3) preparation ethanol: the internal diameter of stainless steel fixed-bed reactor is 8mm, and the consumption of copper catalyst is 3ml, and catalyzer is used 50ml/min H before use
2Under 350 ℃ of conditions, reduce 4h.The intermediate product oxalic acid diethyl ester that obtains in the step (2) is through vaporization and and H
2Mix back feeding fixed-bed reactor and react, temperature of reaction is 280 ℃, and reaction pressure is 3MPa.Condensed product liquid is the certain hour sampling analysis at interval, the chromatogram on-line analysis of uncooled gas, the mol ratio of hydrogen and oxalic acid diethyl ester are 150, and the residence time is 18s (under the normal conditions), the transformation efficiency 98% of oxalic acid diethyl ester, alcoholic acid selectivity are 78%.
Embodiment 7
According to embodiment 1 prepare the alumina load palladium catalyst, embodiment 4 prepares silicon dioxide carried copper catalyst and embodiment 6 prepares oxalic acid diethyl ester;
The mol ratio of hydrogen and oxalic acid diethyl ester is 300 in the preparation ethanol step, and other conditions are with embodiment 6, the transformation efficiency 100% of oxalic acid diethyl ester, and the alcoholic acid selectivity is 83%.
Claims (7)
1. the method for a synthesizing alcohol comprises:
(1) carbon monoxide and nitrous acid ester carry out linked reaction under the catalysis of alumina load palladium catalyst, prepare oxalate diester;
(2) mix with oxalate diester heating vaporization and with hydrogen, mixed gas carries out catalytic hydrogenation reaction on silicon dioxide carried copper catalyst, and reaction product obtains ethanol through cooling, distillation.
2. the method for synthesizing alcohol according to claim 1 is characterized in that, described linked reaction is to carry out under normal pressure, and temperature of reaction is 100～150 ℃.
3. the method for synthesizing alcohol according to claim 1 is characterized in that, in the described linked reaction, carbon monoxide: the volume ratio of nitrous acid ester is: 1.1～2: 1, and the total gas volume air speed of carbon monoxide and nitrous acid ester is: 900～4500h
-1
4. the method for synthesizing alcohol according to claim 1 is characterized in that, the temperature of reaction of described catalytic hydrogenation reaction is 220～300 ℃, and reaction pressure is 0.5～6MPa.
5. the method for synthesizing alcohol according to claim 1 is characterized in that, the specific surface area of described silicon dioxide carried copper catalyst is 150～400m
2/ g.
6. the method for synthesizing alcohol according to claim 1 is characterized in that, in the described catalytic hydrogenation reaction, the mol ratio of oxalate diester and hydrogen is 1: 10～500; Under the normal conditions, the residence time of described oxalate diester on catalyzer is 0.5～20 second.
7. the method for synthesizing alcohol according to claim 1 is characterized in that, described linked reaction and catalytic hydrogenation reaction all are to carry out in fixed-bed reactor.
Priority Applications (1)
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|---|---|---|---|
| CN 201010177750 CN101830776B (en) | 2010-05-20 | 2010-05-20 | Method for synthesizing ethanol |
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|---|---|---|---|
| CN 201010177750 CN101830776B (en) | 2010-05-20 | 2010-05-20 | Method for synthesizing ethanol |
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| CN101830776B CN101830776B (en) | 2013-09-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125843A (en) * | 2010-12-07 | 2011-07-20 | 浙江大学 | Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| CN105085167A (en) * | 2015-08-28 | 2015-11-25 | 天津大学 | Two-section method process for preparing alcohol by oxalic ester hydrogenation |
| CN106378128A (en) * | 2016-09-30 | 2017-02-08 | 中国科学院福建物质结构研究所 | Preparation method of Pd/Al2O3 catalyst for synthesis of oxalate by CO |
| CN111344413A (en) * | 2017-07-01 | 2020-06-26 | 艾尔控股公司 | System and method for on-site generation of liquid alcohol from carbon dioxide |
-
2010
- 2010-05-20 CN CN 201010177750 patent/CN101830776B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| YING-YING ZHU, ET AL: "The Influence of Copper Particle Dispersion in Cu/SiO2 Catalysts on the Hydrogenation Synthesis of Ethylene Glycol", 《CATAL LETT》 * |
| 李竹霞等: "Cu/SiO2催化剂上草酸二甲酯加氢反应的研究", 《化学反应工程与工艺》 * |
| 陈庚申等: "一氧化碳和亚硝酸酯合成草酸酯和草酸", 《天然气化工》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125843A (en) * | 2010-12-07 | 2011-07-20 | 浙江大学 | Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product |
| CN102125843B (en) * | 2010-12-07 | 2013-04-10 | 浙江大学 | Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product |
| CN102350358A (en) * | 2011-08-10 | 2012-02-15 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| WO2013020399A1 (en) | 2011-08-10 | 2013-02-14 | 天津大学 | Catalyst for ethanol production via hydrogenation of oxalate and preparation method and use thereof |
| CN102350358B (en) * | 2011-08-10 | 2013-08-21 | 天津大学 | Preparation method and application of catalyst for preparing ethanol by oxalate hydrogenation |
| EP2636448B1 (en) * | 2011-08-10 | 2016-09-14 | Tianjin University | Catalyst for ethanol production via hydrogenation of oxalate esters and preparation method and use thereof |
| CN105085167A (en) * | 2015-08-28 | 2015-11-25 | 天津大学 | Two-section method process for preparing alcohol by oxalic ester hydrogenation |
| CN106378128A (en) * | 2016-09-30 | 2017-02-08 | 中国科学院福建物质结构研究所 | Preparation method of Pd/Al2O3 catalyst for synthesis of oxalate by CO |
| CN106378128B (en) * | 2016-09-30 | 2018-12-21 | 中国科学院福建物质结构研究所 | A kind of CO synthesis of oxalate Pd/Al2O3The preparation method of catalyst |
| CN111344413A (en) * | 2017-07-01 | 2020-06-26 | 艾尔控股公司 | System and method for on-site generation of liquid alcohol from carbon dioxide |
| US11919841B2 (en) | 2017-07-01 | 2024-03-05 | Air Company Holdings, Inc. | Systems and methods for on-site liquid alcohol production from carbon dioxide |
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|---|---|
| CN101830776B (en) | 2013-09-25 |
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