CN102688758A - Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof Download PDFInfo
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- CN102688758A CN102688758A CN2011100721285A CN201110072128A CN102688758A CN 102688758 A CN102688758 A CN 102688758A CN 2011100721285 A CN2011100721285 A CN 2011100721285A CN 201110072128 A CN201110072128 A CN 201110072128A CN 102688758 A CN102688758 A CN 102688758A
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Abstract
The invention discloses a catalyst for preparing ethanol by acetic acid gas phase hydrogenation and a preparation method thereof. The catalyst for preparing ethanol by acetic acid gas phase hydrogenation comprises one or more main active components, one or more auxiliary agents and a carrier. The one or more main active components are precious metal Pd or/and Pt. The one or more auxiliary agents are selected from Au, Ag, Fe, Re, Cu, Ru and their oxides. The carrier is active carbon, graphite or multi-walled carbon nanotube. In a fixed bed reactor, at a certain temperature, under the action of hydrogen pressure and the catalyst, the high activity and high selectivity transformation of acetic acid into products comprising ethanol as a main product is realized.
Description
Technical field
The present invention relates to a kind of catalyst of acetate gas phase hydrogenation ethanol production, relate at length that a kind of to be used under the gas-phase reaction condition that acetate and hydrogen reaction is converted into ethanol be the catalyst of primary product.
Technical background
Ethanol is important solvent and industrial chemicals, still desirable free of contamination vehicle fuel of high-octane rating and additive thereof.Brazil uses ethanol to make motor vehicle fuel or fuel additive 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 motor vehicle 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; The technology that research and development are produced ethanol from coal resources through synthesis gas substitutes 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 motor vehicle fuel or fuel additive 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 motor vehicle fuel.The industrial process of ethanol 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 chemicals 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 rise in price 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 the corn of producing ethanol; Ipomoea batatas etc. are in short supply; Rise in price, 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 problem 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 pollution is the highest, contaminated environment is serious, and the pollution of alcohol waste water is one of the most serious pollution sources 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; The technology of ethanol is produced in research and development through synthesis gas from coal resources; 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 catalyst 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 catalyst, 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 catalyst 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) catalyst is used for hydrogenation of carboxylic acids system alcohols.USP 7,608, and 744 have reported the catalyst based patent of mineral carbon load Co that is applicable to acetate gas phase hydrogenation ethanol.But above-mentioned technological reaction pressure and energy consumption are high, and the selectivity of ethanol product is low.
Summary of the invention
The objective of the invention is to overcome the catalyst that the problems referred to above of the prior art provide a kind of acetate gas phase hydrogenation ethanol production.Compared with prior art, catalyst of the present invention can significantly cut down the consumption of energy, and improves the selectivity that acetate and hydrogen can be converted into ethanol, simultaneously, can adopt the common acetate that need not to make with extra care as raw material.
For realizing above-mentioned purpose, catalyst provided by the invention is made up of main active component, auxiliary agent and carrier three parts, and the percentage by weight of main active component is 0.1～30.0%, and the weight percent of auxiliary agent is 0.1～20.0%;
Main active component is metal Pd and/or Pt;
Auxiliary agent be among Au, Ag, Fe, Re, Ru and the Cu one or more;
Carrier is active carbon or graphite or multiple-wall carbon nanotube.
When carrier was active carbon, its specific area was 600～1800m
2/ g, average pore size is 2～120nm;
When carrier was graphite, its specific area was 50～400m
2/ g, average pore size is 5～50nm;
When carrier was multiple-wall carbon nanotube, its specific area was 10～300m
2/ g, average pore size is 5～30nm.
Below set forth in detail content of the present invention.
Catalyst of the present invention is to be used for the reaction that acetate and hydrogen can be converted into ethanol.Catalyst is made up of main active component, auxiliary agent and carrier three parts.Main active component be metal Pd with or the Pt neutralization one or more, preferred Pd.Auxiliary agent is one or more in metals such as Au, Ag, Fe, Re, Cu and Ru or the oxide.Carrier is selected active carbon, graphite and multiple-wall carbon nanotube etc. for use.Acetate and hydrogen is under gas phase condition and this catalyst action in fixed bed reactors, is major product but high activity, highly selective are converted into ethanol.This reaction condition and the operating procedure etc. of utilizing catalyst of the present invention to carry out the ethanol hydrogenation reaction can be carried out with reference to prior art, therefore no longer launch narration.
In the reaction system of the present invention, can be directly acetic acid solution be pumped in the preheater and H
2Enter into fixed bed reactors after being preheated to 230 ℃ after the mixing.
Reaction of the present invention can be adopted fixed bed reactors, also can adopt paste state bed reactor.Preferred immobilization bed bioreactor wherein.
Catalyst of the present invention, the preferable weight percentage of metal is 0.1～30%, optimum weight content is 0.5～5.0%; The preferable weight percentage of auxiliary agent is 0.1～20.0%, and best content is 0.5～10.0%; Carrier can be selected active carbon for use, and its specific area is preferably 600～1800m
2/ g, average pore size is 2～120nm; Best specific area is that the specific area of active carbon is 800～1400m
2/ g, average pore size is 4～100nm; Specific area that also can graphite is preferably 50～400m
2/ g, average pore size is preferably 5～50nm, and best specific area is 110～300m
2/ g, the optimum aperture is 6～45nm; Carrier can also adopt multiple-wall carbon nanotube, and the preferable specific area of multiple-wall carbon nanotube is 10～300m
2/ g,, best specific area is 12～250m
2/ g, it is 5～30nm that average pore size is preferably average pore size, the optimum aperture is 8～25nm.
Preparation of catalysts method of the present invention contains the solution of said active component and auxiliary agent by the part by weight preparation of main active component and auxiliary agent in the said catalyst for (1); (2) said solution impregnating carrier is prepared into catalyst.Said solution is the aqueous solution that contains main active component and auxiliary agent solubility nitrate, hydrochloride or metal acid-salt.
Reaction temperature of the present invention is 230 ℃, and hydrogen reaction pressure is 8.0MPa, and the acetic acid liquid volume space velocity is 1.3h
-1And H
2/ acetate=20 (mol ratio).The catalyst loading amount is 10ml.
Catalyst of the present invention can carry out activation through the hydrogen treat under the certain condition before using.Use the condition of hydrogen activating catalyst to be: air speed 500～5000h
-1, preferable condition is: GHSV=1000h
-1, pressure is normal pressure～1.0MPa, temperature is 100～500 ℃, 1～10 hour recovery time.
The specific embodiment
Through specific embodiment the present invention is further specified below.
Embodiment 1
The catalyst of embodiment 1 is a 1.5%Pd-5.0%Re-2.0%Au/ coconut husk charcoal.Take by weighing 9.15 gram coconut husk charcoals (20-40 order), use preceding warp 3% nitric acid dousing to boil 4 hours, about distillation washing system pH=7.0, dried 6 hours for 120 ℃, dispose 15ml and contain 0.2521 gram PdCl
2, 0.7205 gram NH
4ReO
4With 0.7700 gram AuCl
3The aqueous solution dries naturally, 120 ℃ of oven for drying 4 hours.Before using in 300 ℃ of hydrogen (normal pressure, 1000h
-1) reduction activation 5 hours.
Embodiment 2
The catalyst 1.5%Pt-5.0%Re-2.0%Au/ coconut husk charcoal of embodiment 2.Except configuration 15ml contains 0.3983 gram H
2PtCl
66H
2Outside the O aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 3
The catalyst 1.5%Pd-5.0%Re-2.0%Ag/ coconut husk charcoal of embodiment 3.Except configuration 15ml contains 0.3150 gram AgNO
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 4
The catalyst 1.5%Pd-5.0%Re-2.0%Fe/ coconut husk charcoal of embodiment 4.Except configuration 15ml contains 1.4468 gram Fe (NO
3)
39H
2Outside the O aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 5
The catalyst 1.5%Pd-5.0%Re-2.0%Cu/ coconut husk charcoal of embodiment 5.Except configuration 15ml contains 0.7603 gram Cu (NO
3)
23H
2Outside the O aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 6
The catalyst 1.5%Pd-5.0%Re-2.0%Ru/ coconut husk charcoal of embodiment 6.Except configuration 15ml contains 0.4105 gram RuCl
3Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 7
The catalyst 1.5%Pd-5.0%Re2.0%Ag/ graphite charcoal of embodiment 7.Except taking by weighing 9.15 gram graphite charcoals, remaining preparation process is identical with embodiment 1.
Embodiment 8
The catalyst 1.5%Pd-5.0%Re2.0%Ag/ multiple-wall carbon nanotube charcoal of embodiment 8.Except taking by weighing 9.15 gram multiple-wall carbon nanotube charcoals, remaining preparation process is identical with embodiment 1.
Embodiment 9
The catalyst 2.0%Pd-5.0%Re/ coconut husk charcoal of embodiment 9.Contain 0.3361 gram PdCl except taking by weighing 9.3 gram coconut husk charcoals with configuration 15ml
2, 0.7205 gram NH
4ReO
4Outside the aqueous solution, remaining preparation process is identical with embodiment 1.
Embodiment 10
The catalyst 2.0%Pt-5.0%Re/ coconut husk charcoal of embodiment 10 is except configuration 15ml contains 0.5310 gram H
2PtCl
66H
2Outside the O aqueous solution, remaining preparation process is identical with embodiment 2.
The catalyst of method for preparing is selected fixed bed reactors for use, is 240 ℃ in reaction temperature, and Hydrogen Vapor Pressure is 8.0MPa, H
2/ acetate=20 (mol ratio), acetic acid liquid air speed are 0.8h
-1, the reaction time is 50h, sample analysis.The gas phase effluent adopts gas-chromatography to analyze Porapark Q packed column, TCD detector; The gas chromatographic analysis of product liquid samples using, FFAP capillary chromatographic column, fid detector.Amylalcohol is that interior mark carries out quantitative analysis.
Reaction result is summarised in the table 1.
Table 1: the acetate gas phase hydrogenation is converted into the condition optimizing evaluation result of ethanol
Press the catalyst of embodiment 3, reaction condition and raw material are formed, and have carried out more than 1000 hour stability test, and active and selectivity remains unchanged basically.
The coconut husk charcoal that adopts 2-3mm is as carrier, and the activity of such catalysts component is identical with embodiment 3 with auxiliary agent content, has carried out the catalyst feather weight and has amplified preparation; And at liter level single tube fixed bed reactors (internal diameter is 25mm; Height is 3000mm, and material is 316L, and the catalyst loading amount is 1 liter; Fill magnet ring for two sections) carried out reaction condition and embodiment 3 identical scale-ups, the result shows: activity of such catalysts and selectivity are basic identical.
Claims (9)
1. the catalyst of an acetate gas phase hydrogenation ethanol production, wherein:
This catalyst is made up of main active component, auxiliary agent and carrier three parts, and the weight of main active component is 0.1～30.0% of catalyst weight, and the weight of auxiliary agent is 0.1～20.0% of catalyst weight;
Main active component is metal Pd and/or Pt;
Auxiliary agent is the metal of Au, Ag, Fe, Cu, Re and Ru or in the metal oxide one or more;
Carrier is active carbon or graphite or multiple-wall carbon nanotube;
When carrier was active carbon, its specific area was 600～1800m
2/ g, average pore size is 2～120nm;
When carrier was graphite, its specific area was 50～400m
2/ g, average pore size is 5～50nm;
When carrier was multiple-wall carbon nanotube, its specific area was 10～300m
2/ g, average pore size is 5～30nm.
2. catalyst according to claim 1, wherein, main active component percentage by weight is 0.5～5.0%.
3. catalyst according to claim 1, wherein, the percentage by weight of auxiliary agent is 0.5～10.0%.
4. catalyst according to claim 1, wherein, the specific area of active carbon is 800～1400m
2/ g, average pore size is 4～100nm.
5. catalyst according to claim 1, wherein, the specific area of graphite was 50～400m during carrier was heavy
2/ g, average pore size is 5～50nm.
6. catalyst according to claim 1, wherein, the specific area of multiple-wall carbon nanotube is 10～300m in the carrier
2/ g, average pore size is 5～30nm.
7. said Preparation of catalysts method of claim 1 is one or more combinations in the precipitation method, infusion process, the hydrothermal synthesis method, and adopts following step:
(1) prepares the solution that contains said active component and auxiliary agent by the part by weight of main active component and auxiliary agent in the said catalyst;
(2) said solution impregnating carrier is prepared into catalyst.
8. preparation method according to claim 7, said solution is the aqueous solution that contains main active component and auxiliary agent solubility nitrate, hydrochloride or metal acid-salt.
9. carry out reduction activation in following condition before the said catalyst of claim 1 reaction that is used for acetate gas phase hydrogenation ethanol production is used: pressure is normal pressure～1.0MPa, and temperature is 100～500 ℃, and air speed is 500～5000h
-1
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100721285A CN102688758A (en) | 2011-03-22 | 2011-03-22 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103331167A (en) * | 2013-07-19 | 2013-10-02 | 新地能源工程技术有限公司 | Catalyst for directly preparing ethanol from acetic acid, preparation method and application |
| CN103894193A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof |
| CN109046342A (en) * | 2018-07-13 | 2018-12-21 | 南京卡邦科技有限公司 | A kind of preparation method of nanocatalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102420A (en) * | 1985-04-13 | 1986-10-08 | Bp化学有限公司 | The method of carboxylic acid alcohols production by hydrogenation |
| CN1030072A (en) * | 1987-03-31 | 1989-01-04 | 英国石油公司 | Carboxylic acid and acid anhydride thereof generate the shortening of alcohol and/or ester |
-
2011
- 2011-03-22 CN CN2011100721285A patent/CN102688758A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102420A (en) * | 1985-04-13 | 1986-10-08 | Bp化学有限公司 | The method of carboxylic acid alcohols production by hydrogenation |
| CN1030072A (en) * | 1987-03-31 | 1989-01-04 | 英国石油公司 | Carboxylic acid and acid anhydride thereof generate the shortening of alcohol and/or ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894193A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof |
| CN103331167A (en) * | 2013-07-19 | 2013-10-02 | 新地能源工程技术有限公司 | Catalyst for directly preparing ethanol from acetic acid, preparation method and application |
| CN109046342A (en) * | 2018-07-13 | 2018-12-21 | 南京卡邦科技有限公司 | A kind of preparation method of nanocatalyst |
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Application publication date: 20120926 |