CN102690170A - Method for preparing ethanol by acetic acid gas phase hydrogenation - Google Patents
Method for preparing ethanol by acetic acid gas phase hydrogenation Download PDFInfo
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- CN102690170A CN102690170A CN2011100721209A CN201110072120A CN102690170A CN 102690170 A CN102690170 A CN 102690170A CN 2011100721209 A CN2011100721209 A CN 2011100721209A CN 201110072120 A CN201110072120 A CN 201110072120A CN 102690170 A CN102690170 A CN 102690170A
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Abstract
The invention discloses a method for preparing ethanol by acetic acid gas phase hydrogenation. The method is characterized in that a reaction system comprises acetic acid, hydrogen and a catalyst; a reaction temperature is in a range of 120 to 300 DEG C; reaction pressure is in a range of 1.0 to 20.0MPa; an airspeed of an acetic acid liquid is in a range of 0.5 to 10.5h<-1>; a mole ratio of H2 to acetic acid is in a range of 1-250; the catalyst utilizes active carbon as a carrier and contains precious metal Pd and/or Pt as a main active ingredient; and one or more auxiliary agents are selected from Au, Ag, Fe, Re, Cu, Ru and their oxides. Through the catalyst, high activity and high selectivity transformation of an acetic acid and hydrogen into ethanol is realized.
Description
Technical field
The present invention relates to a kind of acetate gas phase hydrogenation and prepare the alcoholic acid method, generate alcoholic acid method with acetate for the raw material gas phase hydrogenation by a kind of being used for specifically.
Technical background
Ethanol is important solvent and industrial chemicals, or free of contamination vehicle fuel of ideal high-octane rating and additive thereof.Brazil uses ethanol to make automobile fuel or fuel dope for many years always, and China has implemented the popularization of ethanol petrol in a plurality of provinces in recent years, and effect is tangible.Along with the raising of environmental quality requirement, develop pure fuel and in gasoline, add alcohol or ether has become the main outlet of improving automobile fuel.China is populous, and cultivated area is not enough, and generally speaking grain is not abundant, and the petroleum resources relative deficiency, and coal resources are abundant relatively.Therefore; Research and development are produced the alcoholic acid technology from coal resources through synthetic gas and are substituted traditional grain fermentative routes; To the industrial consumption and alleviation petroleum resources contradiction in short supply that reduce China's grain, uplifting the people's living standard and developing national economy has the important strategic meaning.
Brazil uses ethanol to make automobile fuel or fuel dope for many years always, and China has implemented the popularization of ethanol petrol in a plurality of provinces in recent years, and effect is tangible.Along with the raising of environmental quality requirement, develop pure fuel and in gasoline, add alcohol or ether has become the main outlet of improving automobile fuel.The alcoholic acid industrial process is main with the grain fermentation method, and one ton of ethanol of the every production of grain fermentation method need consume 3.2 tons of corns.It seems that at present ethanol is one of chemical of few in number price stiffened even rises before and after financial crisis, Market Situation, it is high to remain the tight valency of goods.And substantially exceeding the present situation of ethanol price increase amplitude from present higher food prices amplitude, After-market ethanol price still has big rising space.In recent years, China's drought and waterlogging takes place again and again, makes to produce the alcoholic acid corn; Ipomoea batatas etc. are in short supply; Price increase, many producers form " cooking a meal without rice ", Shandong, Henan; The above alcohol production of the ton on ground such as Anhui factory reduce or stop production is so the practical problems that has the expert to spell out alcohol production is the tight valency height of goods of raw material (grain).Moreover, alcohol industry still is the industry that China's environmental emission organic pollutant is the highest, contaminate environment is serious, and the pollution of alcohol waste water is one of the most serious source of pollution of food and fermentation industries.China is populous, and cultivated area is not enough, and still there is 0.25～0.35 hundred million ton breach in the grain demand of current China.While China's oil relative inadequacy of resources, ethene is in short supply, and coal resources are abundant relatively.Therefore; Research and development are produced the alcoholic acid Technology from coal resources through synthetic gas; Both can save food, can make full use of the coal resources of China's abundant again, can also open up new technological approaches for China's alcohol production; Solve environmental issue, can be described as have politics, economy, the triple significances of environmental protection.
USP 4,398, and 039 and USP4,443,639 to disclose two kinds of Ru respectively catalyst based, and such catalyzer is applicable to the patent of the corresponding carbon number alcohol of hydrogenation of carboxylic acids system.USP 4,517, and 391 have reported Co-Cu-Mn-Mo sedimentation type catalyzer, can the acetate gas phase hydrogenation be converted into ethanol, and the ethanol yield is greater than 97%.USP 4,777,303 with USP 4,826,795 to have disclosed Pd-W (Mo) catalyst based, be used for C
2-C
12The carbon number hydrogenation of carboxylic acids generates the process of the alcohol of corresponding carbon number.USP 4,804,791, USP4,990,655 with USP 5,061,671 the catalyst based patent that is used for acetate and propionic acid preparation of ethanol by hydrogenating and propyl alcohol of activated carbon supported Pd-Re is disclosed.USP 4,985, and 572 have reported the patent of the Pd-Re-Ag/HSAG catalyzer that is used for acetate and the corresponding alcohols of hydrogenation of carboxylic acids system.USP 5,149, and 680 disclose the patent that load P d-Re-W (or Mo) catalyzer is used for hydrogenation of carboxylic acids system alcohols.USP 7,608, and 744 have reported and are applicable to the catalyst based patent of acetate gas phase hydrogenation alcoholic acid mineral carbon load Co.But above-mentioned technological reaction pressure and energy consumption are high, and the selectivity of ethanol product is lower.
Summary of the invention
It is that raw material fixes preparation alcoholic acid method under the reaction conditions in gas-solid two with acetate, hydrogen that the problems referred to above that the objective of the invention is to overcome prior art provide a kind of.
For realizing above-mentioned purpose, acetate gas phase hydrogenation provided by the invention prepares the alcoholic acid method, and raw acetic acid, hydrogen are fixed preparation ethanol under the reaction conditions in gas-solid two.
Reaction system of the present invention is made up of acetate, hydrogen and catalyzer; Reaction conditions is: temperature of reaction is 100～300 ℃ (preferable temperature of reaction is 130～250 ℃); Reaction pressure is that (preferable reaction pressure is 7.0～16.0MPa) to 1.0～20.0MPa, H
2The mol ratio of/acetate is 1～250 (preferable mol ratio is 10～160), and the acetic acid liquid air speed is 0.1～15.0h
-1(preferable liquid air speed is 0.3～5.0h
-1).
Said catalyzer is to be carrier with the gac, and load active component can be one or more among Pd, the Pt, and the loading of active ingredient is the 0.1-30.0% of catalyst weight; Adjuvant component be in metals such as Au, Ag, Fe, Re, Cu and Ru or the oxide compound one or more.The weight of auxiliary agent is 0.1～20.0% of catalyst weight.
Said raw acetic acid is de-iodinating and refining acetate (iodine content is less than 10ppb) or common acetate (iodine content is less than 40ppb), and hydrogen is general hydrogen or pure hydrogen (require total sulfur content to be not more than 0.1ppm, oxygen level is not more than 1ppm), and major product is an ethanol.
Catalyzer of the present invention is made up of carrier and the active ingredient that is supported on the carrier.Carrier can be a gac.Load active component can be one or more among Pd, the Pt, and the loading of active ingredient is the 0.1-30.0% of catalyst weight; Adjuvant component be in metals such as Au, Ag, Fe, Re, Cu and Ru or the oxide compound one or more.The weight of auxiliary agent is 0.1～20.0% of catalyst weight.。The catalyzer that contains said components can adopt conventional catalyst preparation method that this area is familiar with as: the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method are used in combination.
The concrete preparation process of catalyzer of the present invention is: (1) by the weight ratio of active ingredient in the said catalyzer and adjuvant component, is mixed with solution by the nitrate salt or the hydrochloride of active ingredient and adjuvant component; (2) solution with above-mentioned preparation joins in the absorbent charcoal carrier, active ingredient and adjuvant component is loaded on obtain catalyzer on the carrier.Said gac is coconut husk charcoal, peach shell charcoal or charcoal.
The present invention can significantly reduce reaction pressure and energy consumption compared with prior art, improves that acetate and hydrogen are that feedstock production is the alcoholic acid selectivity under gas phase condition.
Embodiment
The invention provides a kind of is that raw material fixes preparation alcoholic acid method under the reaction conditions in gas-solid two with acetate and hydrogen, and being about to acetate and hydrogen catalyzed conversion under gas-solid two phase reaction condition is the alcoholic acid process.Reaction system is made up of acetate, hydrogen and catalyzer.Acetate and hydrogen are being separately converted to ethanol with high reactivity, highly selective after catalyzer contacts certain hour under certain temperature and pressure in above-mentioned system.
The present invention can be directly be pumped into acetic acid liquid in the mixing tank and H
2Mix, get in the preheater, and enter into fixed-bed reactor after the preheating.
Reaction process of the present invention can adopt fixed-bed reactor, also can adopt paste state bed reactor.Preferred immobilization bed bioreactor wherein.
Catalyzer of the present invention can carry out activation through the hydrogen treat under the certain condition before using.Use the preferable condition of hydrogen deactivated catalyst to be: GHSV=500～5000h
-1, normal pressure～1.0MPa, 100～500 ℃, 2～10 hours recovery times.
Through specific embodiment the present invention is further specified below.
Embodiment 1
The catalyzer that adopts is the Pd-Re-Au/ gac.Catalyst weight consists of: Pd=1.5%, and Re=5%, Au=2%, all the other are carrier active carbon.Carrier adopts commodity coconut husk charcoal, and through conventional pickling process catalyst activity component Pd and auxiliary agent Re and Au is supported on the carrier active carbon (granularity of gac is 20～40 orders).6.8 through the hydrogen activation, activation condition is gram (about 10ml) catalyzer: GHSV=1000h before reaction
-1, normal pressure, 300 ℃, 5 hours recovery times.Select fixed-bed reactor for use.Temperature of reaction is 240 ℃, and hydrogen pressure is 8.0MPa, H
2/ acetate (purified acetic acid) mol ratio is that 20 acetic acid liquid air speeds are 0.5h
-1, the reaction times is 50h, sampling analysis.The gas phase elute adopts gc to analyze Porapark Q packed column, TCD detector; The gas chromatographic analysis of product liquid samples using, HP-15 capillary chromatographic column, fid detector.Amylalcohol is that interior mark carries out quantitative analysis.
Embodiment 2
Adopting the acetic acid liquid air speed is 0.3h
-1, other condition is identical with embodiment 1.
Embodiment 3
Adopting the acetic acid liquid air speed is 0.9h
-1, other condition is identical with embodiment 1.
Embodiment 4
Adopting the acetic acid liquid air speed is 1.3h
-1Beyond the Pd-Re-Ag/ gac, other condition is identical with embodiment 1.
Embodiment 5
Adopting the acetic acid liquid air speed is 1.8h
-1, other condition is identical with embodiment 1.
Embodiment 6
Adopting temperature of reaction is 220 ℃, and other condition is identical with embodiment 1.
Embodiment 7
Adopting temperature of reaction is 260 ℃, and other condition is identical with embodiment 1.
Embodiment 8
The employing hydrogen pressure is 7.0Mpa, and other condition is identical with embodiment 1.
Embodiment 9
The employing hydrogen pressure is 10.0Mpa, and other condition is identical with embodiment 1.
Embodiment 10
The employing hydrogen pressure is 12.0Mpa, and other condition is identical with embodiment 1.
Embodiment 11
Adopt H
2/ acetate mol ratio is 10, and other condition is identical with embodiment 1.
Embodiment 12
Adopt H
2/ acetate mol ratio is 50, and other condition is identical with embodiment 1.
Embodiment 13
Adopt H
2/ acetate mol ratio is 100, and other condition is identical with embodiment 1
Embodiment 14
Adopt H
2/ acetate mol ratio is 150, and other condition is identical with embodiment 1
Embodiment 15
Adopt 200 milliliters of stirring-type slurry attitude beds, the granularity of 16.0 gram catalyzer is that 150-200 order and 120ml acetate pump into 200ml slurry attitude bed autoclave reactor, charges into H again
2To pressure be 10.0MPa, other condition is identical with embodiment 1.
Embodiment 16
Adopt common acetate as raw material, other condition is identical with embodiment 1.
Acetate of the present invention and hydrogen are that raw material hydrogenation preparing ethanol synthesis evaluation result under gas-solid two phase reaction condition condition is summarised in the table 1.
Table 1: the acetate gas phase hydrogenation is converted into alcoholic acid condition optimizing evaluation result
Press the catalyzer of embodiment 4, reaction conditions and raw material are formed, and have carried out more than 1000 hour stability test, and acetic acid hydrogenation activity and selectivity remain unchanged basically.
The gac irregular particle that adopts 2-3mm is as carrier, and the activity of such catalysts component is identical with embodiment 4 with auxiliary agent content, has carried out the catalyzer feather weight and has amplified preparation; And at liter level single tube fixed-bed reactor (internal diameter is 25mm; Height is 3000mm, and material is 316L, and the catalyzer loading amount is 1 liter; Fill magnet ring for two sections) carried out reaction conditions and embodiment 1 identical scale-up, the result shows: activity of such catalysts and selectivity are basic identical.
Claims (8)
1. one kind prepares the alcoholic acid method by the acetate gas phase hydrogenation, and reaction system is formed product by acetate, hydrogen and catalyzer and is mainly ethanol; Reaction conditions is:
Temperature of reaction is 100～300 ℃, and reaction pressure is 1.0～20.0MPa, H
2/ acetate mol ratio=1～250, acetic acid liquid air speed are 0.5～10.5h
-1
Said catalyzer is to be carrier with the gac, and load active component can be one or more among Pd, the Pt, and the loading of active ingredient is the 0.1-30.0% of catalyst weight; Adjuvant component be in Au, Ag, Fe, Re, Cu and Ru metal or the oxide compound one or more.The weight of auxiliary agent is 0.1～20.0% of catalyst weight.
2. method according to claim 1, wherein, reaction pressure is 2.0～15.0MPa.
3. method according to claim 1, wherein, temperature of reaction is 120～280 ℃.
4. method according to claim 1, wherein, the acetic acid liquid air speed is 0.1～10.0h
-1
5. method according to claim 1, wherein, H
2/ acetate mol ratio=5～200.
6. according to any described method in the claim 1～5, said catalyzer is used H before use
2In-situ reducing is carried out activation.
7. a claim 1 is said prepares Preparation of catalysts method described in the alcoholic acid method by the acetate gas phase hydrogenation, and on carrier, concrete steps are with active constituent loading in the combination of adopting the precipitator method, pickling process, hydrothermal synthesis method or aforesaid method:
(1), is mixed with solution by the nitrate salt or the hydrochloride of active ingredient and adjuvant component by the weight ratio of active ingredient in the said catalyzer and adjuvant component;
(2) solution with above-mentioned preparation joins in the absorbent charcoal carrier, active ingredient and adjuvant component is loaded on obtain catalyzer on the carrier.
8. preparation method according to claim 7, said gac is coconut husk charcoal, peach shell charcoal or charcoal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110072120.9A CN102690170B (en) | 2011-03-22 | 2011-03-22 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
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|---|---|---|---|
| CN201110072120.9A CN102690170B (en) | 2011-03-22 | 2011-03-22 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
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| CN102690170A true CN102690170A (en) | 2012-09-26 |
| CN102690170B CN102690170B (en) | 2015-03-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861635A (en) * | 2012-12-13 | 2014-06-18 | 洛阳市科创石化科技开发有限公司 | Catalyst for ethanol preparation through direct hydrogenation of acetic acid, preparation method and application thereof |
| CN104109080A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid |
| CN105198704A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for low-energy consumption acetic acid hydrogenation production of ethanol |
| CN105198703A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid hydrogenation |
| CN106316786A (en) * | 2015-07-06 | 2017-01-11 | 唐山中溶科技有限公司 | Method for preparing ethanol through coke oven gas hydrogen extraction |
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| CN102020532A (en) * | 2010-11-11 | 2011-04-20 | 江苏索普（集团）有限公司 | Hydrogenation method for preparing alcohol by using water-solution mixture of alcohol, aldehyde, acid and ester as raw material |
| CN102085479A (en) * | 2009-12-02 | 2011-06-08 | 中国科学院大连化学物理研究所 | Catalyst for hydro-conversion of mixed aqueous solution containing alcohol, aldehyde, acid and ester into alcohols |
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| US4600571A (en) * | 1983-03-18 | 1986-07-15 | The British Petroleum Company P.L.C. | Catalysts and their use in ammonia production |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103861635A (en) * | 2012-12-13 | 2014-06-18 | 洛阳市科创石化科技开发有限公司 | Catalyst for ethanol preparation through direct hydrogenation of acetic acid, preparation method and application thereof |
| CN104109080A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for preparing ethanol through gas-phase catalysis hydrogenation of acetic acid |
| CN104109080B (en) * | 2013-04-16 | 2016-08-24 | 中国石油化工股份有限公司 | Through the method that acetic acid gas-phase catalytic hydrogenation prepares ethanol |
| CN105198704A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for low-energy consumption acetic acid hydrogenation production of ethanol |
| CN105198703A (en) * | 2014-05-29 | 2015-12-30 | 中国石油化工股份有限公司 | Method for producing ethanol by acetic acid hydrogenation |
| CN106316786A (en) * | 2015-07-06 | 2017-01-11 | 唐山中溶科技有限公司 | Method for preparing ethanol through coke oven gas hydrogen extraction |
| WO2017005110A1 (en) * | 2015-07-06 | 2017-01-12 | 唐山中溶科技有限公司 | Method for preparing ethyl alcohol by extracting hydrogen using coke gas |
| CN106316786B (en) * | 2015-07-06 | 2020-04-28 | 唐山中溶科技有限公司 | Method for preparing ethanol by extracting hydrogen from coke oven gas |
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| CN102690170B (en) | 2015-03-04 |
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