CN103861635A - Catalyst for ethanol preparation through direct hydrogenation of acetic acid, preparation method and application thereof - Google Patents
Catalyst for ethanol preparation through direct hydrogenation of acetic acid, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for ethanol preparation through direct hydrogenation of acetic acid, a preparation method and an application thereof. The catalyst comprises a carrier, an active component, and an auxiliary active component, wherein the active component and the auxiliary active component are loaded on the carrier, the active component is Pt, Pd or a mixture of Pt and Pd, the active component accounts for 0.2 to 10% of the total weight of the catalyst, the auxiliary active component at least comprises one component selected from: Sn, Mo, Re and Ru, and the auxiliary active component accounts for 0.2 to 10% of the total weight of the catalyst. The catalyst can prominently reduce the reaction pressure and energy consumption of the acetic acid and hydrogen gas reaction system, and increases the selectivity of the reaction so as to increase the ethanol yield.
Description
Technical field
The present invention relates to a kind of catalyst for the production of alcohols, particularly relate to a kind of catalyst, its preparation method and application of preparing ethanol for the direct gas phase hydrogenation of acetic acid.
Background technology
Before 2008, owing to being subject to technology limitation, domestic enterprise mostly adopts ethylene process and Ethanol Method to produce acetic acid, and the high acetic acid market price that causes of production cost is high, and adopts the same period acetic acid enterprise profit of oxo synthesis abundant.Along with domestic enterprise progressively grasps correlation technique, acetic acid becomes one of Chinese important Coal Chemical Industry product.Be accompanied by the fast development of industry, production capacity is superfluous rapidly, and price depression is depressed.
Ethanol is important industrial chemicals, is widely used in the manufacturing of paint, coating, ink and medicine etc. at chemical industry and other industrial circle; Ethanol, as a kind of good vehicle fuel, has also worldwide obtained and has promoted and approval simultaneously, wherein particularly successful in the U.S. and Brazil.
The demand of China industrial ethyl alcohol is about annual 3500000 tons, estimates that annual growth is between 8% to 10%.And the demand of vehicle fuel ethanol is also in continuous growth, estimate that China's automobile pollution in 2015 will reach 1.6 hundred million-1.8 hundred million, product oil demand will reach 3.3 hundred million tons, wherein gasoline consumption figure will reach 100,000,000 tons of left and right, according to domestic current normally used E10 (ethanol of blending 10%) criterion calculation, if all adopt ethanol petrol, will reach 1,000 ten thousand tons to the demand of alcohol fuel when the time comes.
Within 2011, China's total ethanol output is about 6,700,000 tons, and wherein non-grain ethanol is only 200,000 tons.Ethanol consumption potentiality is huge, and Chinese Government is but lowering the subsidy of grain alcohol.Since 2009, country reduced year by year to the financial subsidies of fixed point fuel ethanol production enterprise.2012 years the alcohol fuel take grain as raw material, allowance standard is 500 yuan/ton.In November, 2011, country announces, will in 5 years, phase out alcohol fuel industry value-added tax refund policy, progressively recovers to impose 5% the consumption tax simultaneously.
Stop at grain alcohol under the background of development, China is to alcohol fuel and the huge potential consumption demand of industrial alcohol, with the limited deliverability of ethanol, for acetic acid preparation of ethanol by hydrogenating has brought the good market opportunity.
It seems from market, ethanol is one of few in number chemicals that price stiffened even goes up before and after financial crisis, and it is high that situation remains the tight valency of goods.China's oil relative inadequacy of resources, ethene is in short supply, and coal resources are relatively abundant.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 again the coal resources of China's abundant, can also open up new technological approaches for China's alcohol production, solve environmental issue, there is significance extremely.
USP7,863489B2 discloses and has been applicable to the silica of acetic acid gas phase hydrogenation ethanol, the catalyst based patent of activated carbon supported Pt.USP4,398,039 and USP4,443,639 to disclose respectively two kinds of Ru catalyst based, and such catalyst is applicable to the patent of the corresponding carbon number alcohol of hydrogenation of carboxylic acids system.USP4,517,391 have reported Co-Cu-Mn-Mo sedimentation type catalyst, acetic acid gas phase hydrogenation can be converted into ethanol, and alcohol getting rate is greater than 97%.USP4,777,303 and USP4,826,795 to have disclosed Pd-W (Mo) catalyst based, generates the process of the alcohol of corresponding carbon number with sub-C2-C12 carbon number hydrogenation of carboxylic acids.USP4,804,791, USP4,990,655 and USP5,061,671 discloses the catalyst based patent for acetic acid and propionic acid preparation of ethanol by hydrogenating and propyl alcohol of activated carbon supported Pd-Re.USP4,985,572 have reported the patent for the Pd-Re-Ag/HSAG catalyst of acetic acid and the corresponding alcohols of hydrogenation of carboxylic acids system.USP5,149,680 disclose the patent of load P d-Re-W (or Mo) catalyst for hydrogenation of carboxylic acids alcohols processed.
CN 102229520 A disclose a kind of method that acetic acid gas phase hydrogenation is prepared ethanol, and reaction system is made up of acetic acid, hydrogen and catalyst; Reaction temperature is 120～300 ℃, and reaction pressure is 1.0～20.OMPa, and acetic acid liquid air speed is 0.5～10.5h
-1, H
2/ acetic acid=1～250(mol ratio); Catalyst is take active carbon as carrier, main active component be transition metal W and or Mo in a kind of or two kinds.Auxiliary agent is one or more in the noble metals such as Pd, Re, Pt, Rh and Ru; Acetic acid and hydrogen can high activities under the effect of catalyst, highly selective is converted into ethanol.
These current method ubiquity reaction pressures are high, the shortcoming of poor selectivity.
Summary of the invention
The object of the invention is to, a kind of Catalysts and its preparation method of preparing ethanol for the direct gas phase hydrogenation of acetic acid is provided, technical problem to be solved is to reduce the required reaction pressure of this reaction system, improves the selective of ethanol simultaneously.
Another object of the present invention is to, a kind of method that above-mentioned catalyst acetic acid and hydrogen reaction are prepared ethanol of applying is provided.
The object of the invention to solve the technical problems realizes by the following technical solutions.What propose according to the present invention prepares the catalyst of ethanol for the direct gas phase hydrogenation of acetic acid, it is with carrier loaded active component and helps active component, wherein: active component is one or both in Pt, Pd, the load capacity of active component is total catalyst weight 0.2～10%; Helping active component is one or more in Sn, Mo, Re and Ru, and the load capacity that helps active component is total catalyst weight 0.2～10%.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid catalyst, wherein said carrier be in micro porous molecular sieve ZSM-5, mesoporous material, aluminium oxide, silica and amorphous aluminum silicate or sodium metasilicate or sodium aluminate any two or two or more.
Aforesaid catalyst, the micro porous molecular sieve ZMS-5 that wherein said carrier is is 60～1000 by silica alumina ratio and boehmite gained.
Aforesaid catalyst, micro porous molecular sieve ZMS-5, mesoporous material and boehmite gained that wherein said carrier is is 60～1000 by silica alumina ratio.
The object of the invention to solve the technical problems also realizes by the following technical solutions.The preparation method of the catalyst as the aforementioned proposing according to the present invention, it is to support this active component by infusion process to help active component with this.
The object of the invention to solve the technical problems also realizes in addition by the following technical solutions.What propose according to the present invention prepares the method for ethanol by the direct gas phase hydrogenation of acetic acid, and it is the catalyst of application of aforementioned.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
The direct gas phase hydrogenation of aforesaid acetic acid is prepared the method for ethanol, and its reaction condition is: hydrogen and acetic acid mol ratio 1～300,100～300 ℃ of reaction temperatures, reaction pressure 0.3～3.0MPa, acetic acid liquid air speed 0.5～12h
-1.
The direct gas phase hydrogenation of aforesaid acetic acid is prepared the method for ethanol, and wherein catalyst activates with hydrogen local reduction way before use.
The present invention compared with prior art has obvious advantage and beneficial effect.By technique scheme, catalyst, its preparation method and application that the present invention prepares ethanol for the direct gas phase hydrogenation of acetic acid can reach suitable technological progress and practicality, and there is the extensive value in industry, it at least has following advantages: catalyst of the present invention can significantly reduce reaction pressure and the energy consumption of acetic acid and hydrogen reaction system, improves the selective of product ethanol.
Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of description, and for above and other object of the present invention, feature and advantage can be become apparent, especially exemplified by preferred embodiment, be described in detail as follows below.
Accompanying drawing explanation
Nothing
The specific embodiment
Technological means and effect of taking for reaching predetermined goal of the invention for further setting forth the present invention, below in conjunction with preferred embodiment, prepare catalyst, its preparation method of ethanol and apply its specific embodiment, structure, feature and effect thereof for the direct gas phase hydrogenation of acetic acid what propose according to the present invention, being described in detail as follows.
The invention provides a kind of method of directly preparing ethanol take acetic acid and hydrogen as raw material in fixed bed reactors reactor.Reaction system is made up of acetic acid, hydrogen and catalyst.After in above-mentioned system, acetic acid contacts certain hour with catalyst with hydrogen under certain temperature and pressure, high activity, highly selective are converted into ethanol.The present invention can directly be pumped into acetic acid liquid in blender and H
2mix, enter in preheater, after preheating, enter into fixed bed reactors.
The technical scheme that the present invention prepares ethanol by the direct gas phase hydrogenation of acetic acid is: according to hydrogen: acetic acid=1～300(mol ratio) ratio make acetic acid, hydrogen and catalyst under 100～300 ℃, the reaction pressure of 0.3～3.0MPa, acetic acid liquid air speed is 0.5～12h
-1condition under react, the content>=95%wt of ethanol in the product obtaining.
Described raw material adopts conventional industrial acetic acid, also can adopt thick acetic acid, if content of iodine is for being less than lOppb for de-iodinating and refining acetic acid, or common acetic acid content of iodine is for being less than 40ppb.Hydrogen is conventional general hydrogen or pure hydrogen, and total sulfur content is not more than 0.lppm, and oxygen content is not more than lppm.
Described catalyst is that wherein active component is one or both in Pt, Pd with carrier loaded active component and help active component, and the load capacity of active component is total catalyst weight 0.2～10.0%; Helping active component is one or more in Sn, Mo, Re or Ru, and the load capacity that helps active component is total catalyst weight 0.2～10.0%.
Preferably reaction condition is:
Reaction pressure is 0.5～2.5MPa;
Reaction temperature is 120～280 ℃;
Acetate solution liquid air speed is 0.5～10.0h
-1;
Hydrogen: acetic acid=2～250(mol ratio).
ZSM Series Molecules take ZSM-5 as representative sieve is a kind of high silicon, has the novel molecular sieve of three dimensional intersection straight channel, and it has oleophylic, hydrophobic, heat endurance high.Most apertures are 0.6nm left and right, and its catalytic activity depends on surface acidity, and these acid site overwhelming majority are positioned at the vestibule of molecular sieve, due to special pore passage structure and the acting in conjunction in acid site, make it have special Studies On The Shape-selective Catalysis.
Mesoporous material is the new material with huge surface area and three-dimensional open-framework of a kind of aperture between micropore and macropore.It has the excellent specific property that other porous material does not have: the pore passage structure with high-sequential; The single distribution in aperture, and aperture size can change at relative broad range; Mesoporous shape is various, and hole wall composition and character can regulate and control; Can obtain high thermal stability and hydrothermal stability by optimizing synthesis condition.
According to chemical composition classification, mesoporous material generally can be divided into silicon system and non-silicon is two large classes.
Silica-base material can be divided into two classes according to pure silicon and other elements of doping again.And then can carry out classification according to doped chemical kind and different element number differences.Heteroatomic doping can be regarded as the position that hetero atom has replaced original silicon atom, and different heteroatomic introducing meetings bring a lot of new character, variation, the variation of hydrophilic and hydrophobic matter and variation of catalytic activity of for example stability etc. to material.
One of catalyst carrier of the present invention is stripe shape carrier, select two or more in micro porous molecular sieve ZMS-5, mesoporous material, aluminium oxide, silica and amorphous aluminum silicate, through soda acid processing, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 400 ℃ of roastings obtain stripe shape carrier, stripe shape carrier is of a size of diameter 1.5～5.5mm, length 3～30mm.
Another of described catalyst carrier is ball-type carrier, select two or more in micro porous molecular sieve ZMS-5, mesoporous material, aluminium oxide, silica and amorphous aluminum silicate or sodium metasilicate or sodium aluminate, through mixing, rolling moulding is prepared into spherical, again through super-dry, pelletizing, high-temperature roasting obtains ball-type carrier.
Described molecular sieve mainly adopts high silica ZSM-5 molecular sieve, its silica alumina ratio 60-1000.
It is mesoporous material that described mesoporous material mainly adopts the silicon such as MCM-41, MCM-48, KIT-1, FSM-16, SBA-15.
Described aluminium oxide mainly adopts the precursor of boehmite or other aluminium oxide.
Described silica mainly adopts the precursor of Ludox, silica or other silica.
The employing precipitation method such as described amorphous aluminum silicate, sodium metasilicate, sodium aluminate prepare.
Described catalyst is with two or more carrier prepared in micro porous molecular sieve ZMS-5, mesoporous material, aluminium oxide, silica and amorphous aluminum silicate or sodium metasilicate or sodium aluminate, by infusion process or other conventional method load active components with help active component.Active component and help active component to flood respectively separately, also may be mixed together dipping.
Catalyst can adopt conventional hydrogen local reduction way to activate before use, condition routinely: GHSV=lOOOh
-1, normal pressure, 300 ℃, 5 hours recovery times.
Embodiment 1
Micro porous molecular sieve ZMS-5 and commercially available boehmite (nA1 take silica alumina ratio as 60～1000
2o
3h
2o) mix, add rare nitric acid and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 400 ℃ of bars that roasting obtains, prepare stripe shape carrier a series according to the composition of table 1.
Table 1 stripe shape carrier a series composition
| Numbering | ZSM-5 content %(Si/Al) | Alumina content % |
| a1 | 85（60） | 15 |
| a2 | 80（100） | 20 |
| a3 | 75（300） | 25 |
| a4 | 60（500） | 40 |
| a5 | 50（1000） | 50 |
Embodiment 2
Micro porous molecular sieve ZMS-5, mesoporous material and commercially available boehmite (nA1 take silica alumina ratio as 60-1000
2o
3h
2o) mix, add rare nitric acid and water, mediate evenly, extrusion, 110 ℃ of oven dry, pelletizing, 400 ℃ of roastings obtain bar, prepare stripe shape carrier b series according to the composition of table 2.
Table 2 stripe shape carrier b series composition
| Numbering | ZSM-5 content %(Si/Al) | Mesoporous material | Alumina content % |
| b1 | 80（60） | 5（MCM-41） | 15 |
| b2 | 75（100） | 10（MCM-48） | 15 |
| b3 | 70（300） | 5（FSM-16） | 25 |
| b4 | 60（500） | 5（KIT-1） | 35 |
| b5 | 50（1000） | 25（SBA-15） | 25 |
Embodiment 3
The micro porous molecular sieve ZMS-5 that is 60～1000 by silica alumina ratio and commercially available boehmite (nA1
2o
3h
2o) after co-grinding, fully mix, ball milling is to more than 400 orders, add rolling moulding still, the dilution proportion that binding agent and water are pressed to 1:5～1:10, sprays in the mixture of molecular sieve and carrier continuous rolling moulding off and on by atomization plant, be the bead of 1.5～8.0 millimeters until be shaped to diameter, then at 80～120 ℃ dry 2～10 hours, 500～600 ℃ of roasting temperatures 1～6 hour, obtain ball-type carrier of the present invention.Prepare bead carrier c series according to the composition of table 3.
Table 3 bead carrier c series composition
| Numbering | ZSM-5 content, %(Si/Al) | Alumina content, % |
| c1 | 65（60） | 35 |
| c2 | 70（100） | 30 |
| c3 | 75（300） | 25 |
| c4 | 60（500） | 40 |
| c5 | 50（1000） | 50 |
Embodiment 4
The micro porous molecular sieve ZMS-5 that just silica alumina ratio is 60-1000 and mesoporous material and commercially available boehmite (nA1
2o
3h
2o) after co-grinding, fully mix, ball milling is to more than 400 orders, add rolling moulding still, the dilution proportion that binding agent and water are pressed to 1:5～1:10, sprays in the mixture of molecular sieve and carrier continuous rolling moulding off and on by atomization plant, be the bead of 2～8.0 millimeters until be shaped to diameter, then at 80～120 ℃ dry 2～10 hours, 500～600 ℃ of roasting temperatures 1～6 hour, obtain ball-type carrier of the present invention.Prepare bead carrier d series according to the composition of table 4.
Table 4 bead carrier d series composition
| Numbering | ZSM-5 content, %(Si/Al) | Mesoporous material | Alumina content, % |
| d1 | 60（60） | 5（MCM-41） | 35 |
| d2 | 55（100） | 10（MCM-48） | 35 |
| d3 | 65（300） | 5（FSM-16） | 30 |
| d4 | 60（500） | 5（KIT-1） | 35 |
| d5 | 50（1000） | 25（SBA-15） | 25 |
Embodiment 5
The present embodiment is for illustrating the preparation method of catalyst of the present invention.
Take the two mixed liquor of a certain amount of soluble-salt (palladium bichloride) solution that is dissolved in platinum acid chloride solution in quantitative deionized water or palladium or its, pour in the container that contains quantitative carrier (a1), stir, flood 24 hours, slowly dry, 105 ℃ of left and right, dry 4 hours, and then 400 ℃ of left and right, roasting 8 hours.Take a certain amount of quantitative soluble-salt solution containing stannous chloride solution, molybdic acid, rhenium or ruthenium in sour deionized water that is dissolved in, or in its both above mixture solutions, pour in baked carrier, stir, flood 20 hours, slowly dry, 110 ℃ of left and right, dry 4 hours, and then 450 ℃ of left and right, roasting 6 hours.Obtain catalyst A 11.Flood the composition of element according to table 5, the catalyst of preparing take a1 carrier is A1 series.
Catalyst composition prepared by table 5
Embodiment 6
Flood the composition of element according to table 5, the catalyst of preparing take a2 carrier, as A2 series, is numbered A2i.
Embodiment 7
Flood the composition of element according to table 5, the catalyst of preparing take a3 carrier, as A3 series, is numbered A3i.
Embodiment 8
Flood the composition of element according to table 5, the catalyst of preparing take a4 carrier, as A4 series, is numbered A4i.
Embodiment 9
Flood the composition of element according to table 5, the catalyst of preparing take a5 carrier, as A5 series, is numbered A5i.
Embodiment 10
Flood the composition of element according to table 5, the catalyst of preparing take b1 carrier, as B1 series, is numbered B1i.
Embodiment 11
Flood the composition of element according to table 5, the catalyst of preparing take b2 carrier, as B2 series, is numbered B2i.
Embodiment 12
Flood the composition of element according to table 5, the catalyst of preparing take b3 carrier, as B3 series, is numbered B3i.
Embodiment 13
Flood the composition of element according to table 5, the catalyst of preparing take b4 carrier, as B4 series, is numbered B4i.
Embodiment 14
Flood the composition of element according to table 5, the catalyst of preparing take b5 carrier, as B5 series, is numbered B5i.
Embodiment 15
Adopt and use the same method, to being processed by embodiment 3 and 4 gained ball-type carriers, obtain C catalyst series respectively, be numbered Cii (i=1～5), and D catalyst series, be numbered Dii (i=1～5).
In table 6, list by the prepared partially catalyzed agent of above-described embodiment 5-15 and formed.
Partially catalyzed agent numbering and composition prepared by table 6
Embodiment 16
Adopt the prepared partially catalyzed agent of above-described embodiment, refer to table 7, carry out reactivity worth evaluation at lOml fixed bed reactors loading catalyst.Catalyst is through hydrogen activation before reaction, and activation condition is: hydrogen volume air speed is lOOOh
-1, normal pressure, 300 ℃, 5 hours recovery times.Evaluate reaction condition in table 8, sample analysis.Gas phase effluent adopts gas-chromatography to analyze; Product liquid sample adopts gas-chromatography off-line analysis, and butanols is that interior mark carries out quantitative analysis.Evaluation result is in table 7.
The evaluation result that the agent of table 7 partially catalyzed is optimized
The reaction condition of table 8 evaluate catalysts reactivity worth
Experimental result by table 7 can be found out, preparing in the reaction system of ethanol take acetic acid and hydrogen as unstripped gas phase reaction, catalyst of the present invention shows excellent catalytic performance, feed stock conversion and gained ethanol are selectively high, all can reach more than 95%, the high selectivity of product can reduce energy consumption significantly, realizes energy-saving and emission-reduction; On the other hand, use catalyst of the present invention, can reduce the required reaction pressure of reaction system (0.3MPa～3MPa), reduce equipment investment, make operation safer simultaneously.
The above, it is only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction, although the present invention discloses as above with preferred embodiment, but not in order to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations, in every case be the content that does not depart from technical solution of the present invention, any simple modification of above embodiment being done according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (8)
1. prepare a catalyst for ethanol for the direct gas phase hydrogenation of acetic acid, it is with carrier loaded active component and helps active component, it is characterized in that:
Active component is one or both in Pt, Pd, and the load capacity of active component is total catalyst weight 0.2～10%; Help active component be in Sn, Mo, Re and Ru two kinds or more than, the load capacity that helps active component is total catalyst weight 0.2～10%.
2. catalyst according to claim 1, it is characterized in that described carrier be in micro porous molecular sieve ZSM-5, mesoporous material, aluminium oxide, silica and amorphous aluminum silicate or sodium metasilicate or sodium aluminate any two or two or more.
3. catalyst according to claim 2, micro porous molecular sieve ZMS-5 and boehmite gained that the carrier described in it is characterized in that is is 60～1000 by silica alumina ratio.
4. catalyst according to claim 2, micro porous molecular sieve ZMS-5, mesoporous material and boehmite gained that the carrier described in it is characterized in that is is 60～1000 by silica alumina ratio.
5. a preparation method for the catalyst as described in claim as arbitrary in claim 1-4, is characterized in that supporting this active component by infusion process helps active component with this.
6. prepared a method for ethanol by the direct gas phase hydrogenation of acetic acid, it is characterized in that application rights requires the catalyst described in 1-4 arbitrary claim.
7. the direct gas phase hydrogenation of acetic acid according to claim 6 is prepared the method for ethanol, it is characterized in that reaction condition is:
Hydrogen and acetic acid mol ratio 1～300,100～300 ℃ of reaction temperatures, reaction pressure 0.3～3.0MPa, acetic acid liquid air speed 0.5～12h
-1.
8. the direct gas phase hydrogenation of acetic acid according to claim 7 is prepared the method for ethanol, it is characterized in that catalyst activates with hydrogen local reduction way before use.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707058A (en) * | 2018-04-11 | 2018-10-26 | 华东师范大学 | A kind of two-step method inverting biological grease is the method for linear alpha-alkene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102311311A (en) * | 2008-07-31 | 2012-01-11 | 国际人造丝公司 | Use platinum/tin catalyst to prepare ethanol by the direct selectivity of acetate |
| CN102658165A (en) * | 2012-04-06 | 2012-09-12 | 华东理工大学 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
| CN102690170A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
| WO2012148510A1 (en) * | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Process for producing ethanol using multiple beds each having different catalysts |
-
2012
- 2012-12-13 CN CN201210538576.4A patent/CN103861635A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102311311A (en) * | 2008-07-31 | 2012-01-11 | 国际人造丝公司 | Use platinum/tin catalyst to prepare ethanol by the direct selectivity of acetate |
| CN102690170A (en) * | 2011-03-22 | 2012-09-26 | 中国科学院大连化学物理研究所 | Method for preparing ethanol by acetic acid gas phase hydrogenation |
| WO2012148510A1 (en) * | 2011-04-26 | 2012-11-01 | Celanese International Corporation | Process for producing ethanol using multiple beds each having different catalysts |
| CN102658165A (en) * | 2012-04-06 | 2012-09-12 | 华东理工大学 | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707058A (en) * | 2018-04-11 | 2018-10-26 | 华东师范大学 | A kind of two-step method inverting biological grease is the method for linear alpha-alkene |
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Application publication date: 20140618 |