CN102690171B - Process for preparing ethanol from synthesis gas via methyl alcohol - Google Patents
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Abstract
The invention relates to a process for preparing ethanol from synthesis gas via methyl alcohol. The synthesis gas is divided into two parts, one part of the synthesis gas is used for methanol synthesis, and the other part is separated as CO (carbon monoxide) and H2 (hydrogen); the synthesis gas and methanol synthesis circulating tail gas are mixed into methanol synthesis material gas; the methanol synthesis material gas is subjected to methanol synthesis reaction under the action of a methanol synthesis catalyst to obtain the methyl alcohol and methanol synthesis circulating tail gas; the CO separated from the synthesis gas and acetic acid synthesis circulating tail gas are mixed and then subjected to carbonylation together with methyl alcohol; acetic acid synthesis reaction is carried out to obtain acetic acid and acetic acid synthesis circulating tail gas; the H2 separated from the synthesis gas is mixed with ethanol synthesis circulating tail gas to enter a reactor; the mixed gas and acetic acid contact the catalyst to carry out the ethanol synthesis reaction by hydrogenation so as to obtain ethanol and by-product and ethanol synthesis circulating tail gas, and a crude product at the outlet of the reactor is separated to obtain ethanol. The process disclosed by the invention has the advantages of high ethanol yield, high energy utilization rate of overall process, low cost and feasibility in mass production.
Description
Technical field
The present invention relates to a kind of technique of preparing ethanol, relate in particular to the technique of a kind of synthesis gas through methanol ethanol processed.
Background technology
Make China face many energy environment pressure such as energy security, environment protection and Sustainable development take coal as main energy consumption structure; the coal resources that utilize China relatively to enrich; develop derived energy chemical technology and the industry of non-oil dependent form; making up the deficiency that oil is supplied with, is the important means that ensures Chinese Energy Safety.
Ethanol is large Chemicals, what is more important, and ethanol has become whole world common recognition as the advantage of fuel dope.Many countries or have promoted the use of alcohol fuel in the world.China encourages to support the development of ethanol petrol always, the production and application of ethanol petrol has been put into effect to some supports and subsidy policy, and put into effect the authorized documentss such as national technical standard, some areas of 10 provinces such as Heilungkiang, Jilin are as the model regions of ethanol petrol.China's alcohol fuel production capacity breach is huge, needs novel mass-producing alcohol production technology badly.
At present, the alcohol production of the overwhelming majority all adopts the fermentation method take grain and cash crop as raw material, and this causes two bottlenecks of fuel ethanol industrial development, expensive problem and threaten national food and arable land safety.Non-grain route alcohol production technology comprises following several: Mierocrystalline cellulose (being mainly biomass straw) fermentation method, synthetic gas synthesizing alcohol method etc.Cellulose fermentation (patent CN101235392) ethanol technology processed is not directly used grain and cash crop, can effectively alleviate the problem that grain fermentation method consumes grain, occupies cultivated land, but this technological deficiency is: (1) is because agricultural crop straw energy density is little, transportation cost is high, is difficult to realize the scale operation of ethanol; (2) cellulase cost is high, and current cellulosic ethanol cost is still higher than grain alcohol.Ethanol synthetic technology take synthetic gas as raw material is an important development direction of alcohol fuel manufacturing technology.
Summary of the invention
The object of the invention is to propose a kind of cost low, the technique of the synthesis gas through methanol ethanol processed can be mass-produced.
Specific embodiment of the present invention comprises as follows:
(1) synthetic gas (CO+H
2) being divided into two portions, a part of synthetic gas is synthetic for methyl alcohol, and rest part is separated into CO and H
2;
(2) synthetic gas and methyl alcohol synthesis cycle tail gas are mixed into methyl alcohol synthetic raw gas, and methyl alcohol synthetic raw gas carries out methyl alcohol building-up reactions under methanol synthesis catalyst effect, obtain methyl alcohol and methyl alcohol synthesis cycle tail gas;
(3) after synthetic gas being separated to the CO obtaining and mixing with acetic acid synthesis cycle tail gas, then carry out carbonylation reaction with methyl alcohol, carry out acetic acid building-up reactions, obtain acetic acid and acetic acid synthesis cycle tail gas;
(4) synthetic gas separates the H obtaining
2be mixed into reactor with ethanol synthesis cycle tail gas, gas mixture contacts with catalyzer with acetic acid hydrogenation reaction generation ethanol and by product (acetaldehyde and ethyl acetate) and ethanol synthesis cycle tail gas occurs, and reactor outlet crude product is through separating to obtain ethanol.
It is to adopt disclosed CO, the H such as patent CN102191086A and CN102133498A that synthetic gas as above separates
2separating technology.The technique of CN102133498A is adsorbed for unstripped gas is sent into the first adsorption tower from bottom, obtains CO gas product in the enrichment of the bottom of the first adsorption tower, and the mixed gas that the first adsorption tower top obtains is sent to the second adsorption tower; Mixed gas is after the second adsorption tower absorption, and the outlet of the second adsorption tower obtains highly purified hydrogen product gas.CN102191086A is the integrating device of a kind of producing synthesis gas from coal coproduction carbon monoxide, methyl alcohol, hydrogen, refining synthetic gas, and CO low temperature separation process unit wherein and pressure swing adsorption hydrogen production unit can be used to hydrogen manufacturing and CO processed.
Methyl alcohol as above is synthetic is to adopt ICI multistage cold shock tower low pressure methanol synthesis technique, Lurgi tubular type isothermal synthetic tower low pressure methanol synthesis technique or Linde spiral coiled pipe isothermal synthetic tower methanol synthesizing process etc.The synthetic gas of Lurgi low pressure methanol synthesis is prepared by Sweet natural gas, steam reforming, synthetic gas through purify, cooling after, send into centrifugal turbo-compressor, be depressed into after 4-5 MPa, send into synthetic tower.Synthetic gas reacts methanol under copper catalyst exists.The reaction heat that synthesizing methanol produces is in order to produce high pressure steam, and as the power of turbocompressor.Synthetic tower outlet is cooling containing gas and the gas mixture heat exchange of methyl alcohol, then through air or water cooling, makes thick methanol condensed, in separator, separates.The thick methyl alcohol of condensation, to flash tank flash distillation, is delivered to rectifier unit exquisiteness.ICI low pressure methanol synthesis method is first by H
2, CO, CO
2and a small amount of CH
4the synthetic gas process transformationreation of composition is to regulate CO/CO
2ratio, then boosts to 5 MPa with centrifugal compressor, and sending into temperature is 270 ℃ of quench type reactors, and reacted gas is through cooling and isolating methyl alcohol, and compressed the boosting of unreacted gas mixed and again entered reactor with fresh feed gas.Linde isothermal synthetic tower is the novel energy-conservation isothermal tower of single hop.In tower, spiral coiled pipe is placed in beds, passes into the feedwater of 4.5 MPa from coiled pipe bottom, discharges middle pressure steam and recirculated water from above.Synthetic gas enters from top of tower, through beds, discharges from tower bottom.
Methanol synthesis catalyst can adopt C302, C302-1, C302-2, the CNJ206 etc. of the C79-5GL type catalyzer Southwest Chemical Research and Design Institute of ICI51-1, ICI51-2, ICI51-7 type catalyzer, the Lurgi company of ICI company exploitation.
Acetic acid as above is synthetic is to adopt Celanese AO Plus technique, BP Cativa technique or thousand generation field Acetica techniques.Celanese AO Plus technique is by adding the inorganic iodine (being mainly lithium iodide) of high density to change the composition of catalyzer, make reactor in 4%～5% time operation of low water content, the productive rate and the refining ability that have improved carbonylation reaction, total iodine content of product residue is lower than 5 × 10
-12.BP Cativa technique, in its conventional process techniques, changes rhodium series catalysts into iridium series catalysts.The multiple rare metals such as this process using rhenium, ruthenium, osmium are promotor, the catalytic activity of iridium series catalysts apparently higher than rhodium is, when water-content is lower, iridium series catalysts stability is high, the by products such as energy consumption is low, propylene are few, and can be in water-content≤5% time operation, traditional methanol carbohylation process be can greatly improve, productive expense and investment reduced.In addition, because of reduced water content, the utilising efficiency of CO improves, and steam consumption reduces.The catalyst system of the thousand heterogeneous rhodium catalysts of generation field Acetica process using and polyvinylpyridine resin combination, this catalyst system can improve the catalytic activity of rhodium, makes the productive rate of acetic acid exceed 99%.Do promotor with methyl iodide, adopt the solid rhodium based composite catalyst suspending, under 175 ℃, the condition of 2.8MPa, in the closed circuit reactor of bubble tower type, react, reaction product obtains finished product, transformation efficiency >=99% of methyl alcohol through flash distillation, dehydration, after refining.
Ethanol as above is synthetic is that the employing patent No. is 201210057568.8 or 201210057475.5 catalyzer and technique.The patent No. is 201210057568.8 method for preparing catalyst for by transition metal Ni, Co, Fe, W, V, Mo, Nb, the compound of Cr, Ta etc. one or more and Secondary ammonium phosphate join in deionized water by the stoichiometric ratio of catalyzer composition, and add citric acid, and wherein the mol ratio of citric acid and transition metal is 0.5-3:1.The solution obtaining is stirred at 50-90 ℃ to 8-24 h, dry 18-24 h at 100-110 ℃, afterwards by sample foamed solidification 10-20 h at 120-150 ℃, by the sample roasting 3-6 h in 400 ~ 650 ℃ of air after solidifying.By the sample after roasting at H
2under atmosphere, rise to 400-800 ℃ with the temperature rise rate of 0.5-3 ℃/min, constant temperature 3-8 h, H
2gas space velocity is 3000-9000 h
-1, sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2/ N
2passivation 2-5 h obtains catalyzer.The patent No. is 201210057475.5 method for preparing catalyst for first by transition metal Ni, Co, Fe, W, V, Mo, Nb, Cr, one or more compounds of Ta etc. and Secondary ammonium phosphate join in deionized water by the stoichiometric ratio of catalyzer composition, for the solution that has precipitation to generate, in solution, add nitric acid with dissolution precipitation, by the solution incipient impregnation configuring in aluminium sesquioxide, molecular sieve, silicon-dioxide, titanium dioxide, on the carrier such as zirconium white or diatomite, wherein transistion metal compound: deionized water: carrier=0.15-8.2 g:10-30 ml:10-20 g.Carrier after carrying transition metal compound is at room temperature placed 2-5 h, dry 2-5 h at 30-60 ℃, dry 6-12 h at 100-120 ℃, then in 400-650 ℃ of air roasting 3-6 h.By the sample after roasting at H
2under atmosphere, be warming up to 400-800 ℃ with the speed of 0.5-3 ℃/min, at this temperature, reduce 3-8 h, H
2air speed is 3000-9000 h
-1.Sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2 /n
2passivation 2-5 h, obtains catalyzer.
Synthesizing alcohol temperature of reaction is within the scope of 200-300 ℃, and reaction pressure is at 1.0-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: acetic acid mol ratio is 5-50.Acetic acid transformation efficiency is 100%, and ethanol selectivity is greater than 90%.
First product separation as above adopts the acetaldehyde in simple distillation separated product, adopts afterwards the disclosed extraction rectifying method separating alcohol of patent CN1706799A, ethyl acetate and water.The step of patent CN1706799A salting, compounding, extracting, rectifying separating ethyl acetate-ethanol-water mixed liquid is: (1) ethyl acetate, ethanol, water mixed liquid add 10～20 %NaAc; (2) the thick product of composite extractant extracting and separating, tower top obtains ethyl acetate, and tower top temperature is controlled at 77～78 ℃; Tower reactor flows out saliferous mixed extractant, and extraction agent is through regenerator column processing, the processing of regenerator column top of tower fractionation lease making ethanol recovery tower, and all the other cuts are returned and are used, and saliferous extraction agent recycles.Thick product, after separating, can obtain 40% acetaldehyde, more than 99.5% ethyl acetate, more than 95% ethanol.
The present invention compared with prior art tool has the following advantages:
1, operational path provided by the invention is made up of synthesize-ethanol synthesis technique unit of synthesize-acetic acid of synthetic gas separation-methyl alcohol, methyl alcohol synthesizes and acetic acid synthetic technology maturation, target product selectivity is high, and acetic acid hydrogenation synthesizing alcohol technique ethanol yield is high, and integrated artistic capacity usage ratio is high.
2, cost is low, can be mass-produced.
Accompanying drawing explanation
The process flow diagram of Fig. 1 synthesis gas through methanol of the present invention ethanol processed.
Embodiment
In order to understand better the present invention, provide several illustrative rather than restrictive embodiment below.
Embodiment 1:
480000 tons/year of ethanol synthetic (to move every year 300 days)
By H
2: CO=2:1, output are 2,460,000 m
3the synthetic gas in/sky is divided into two portions, 1,230,000 m of first part
3/ it is synthetic for methyl alcohol, second section 1,230,000 m
3/ sky is for CO and H
2separate the synthetic and synthetic raw material of ethanol as acetic acid.Adopt CO and H in the disclosed method low temperature separation process of patent CN102133498A synthetic gas
2, after separating, the output of CO is 1,070,000 m
3/ day, H
2output be 160,000 m
3/ day.
The synthetic Lurgi tubular type isothermal synthetic tower low pressure synthesis technique that adopts of methyl alcohol.Material synthesis gas amount is 1,230,000 m
3/ day, the inlet tower gas after heat exchange, temperature is 225 ℃, directly enters in the reaction tubes of synthetic tower from top, methanol reacts under catalyst action.Methanol synthesis catalyst adopts the C79-5GL type copper catalyst of Lurgi company, and bed internal pressure is that 5 MPa, temperature are 250 ℃.The water vapor generation middle pressure steam that the reaction heat of emitting in reaction process is synthesized in tower shell side is taken away, reacted gas enters after interchanger heating inlet tower gas, after methanol condenser, separator separation of methanol, recycle, circulation gas is 5:1 with the ratio of virgin gas.Methanol output is 1160 tons/day.
The synthetic AO Plus acetic acid synthesis technique that adopts Celanese Corp. of acetic acid, raw material inlet amount methyl alcohol is 1160 tons/day, CO is 1,070,000 m
3/ day.190 ℃ of temperature of reaction, pressure 3 MPa, reaction adopts rhodium catalyst, and adds lithium iodide to improve the stability of catalyzer, and in reactor, water-content remains on 5%.Acetic acid acetic acid productive rate is 99%, and output is 2151 tons/day.
The CoNbP catalyzer that the synthetic employing of the ethanol patent No. is 201210057568.8, by acetic acid synthetic carbonylation workshop section and H
2as raw material, carry out ethanol and synthesize.Temperature of reactor is 200 ℃, and reaction pressure is 1.5 MPa, H
2with acetic acid mol ratio be 50:1, acetic acid transformation efficiency is 100%.Adopt the disclosed method of patent CN1706799 to carry out extractive distillation thick acetic acid hydrogenation product.Thick product adds 15% NaAc, in compound extracting tower extracting and separating, obtains more than 99.5% ethyl acetate and 95% ethanol.Ethanol production is 1584 tons/day.
Embodiment 2:
280000 tons/year of ethanol synthetic (to move every year 300 days)
By H
2: CO=2:1, output are 1,480,000 m
3the synthetic gas in/sky is divided into two portions, 740,000 m of first part
3/ it is synthetic for methyl alcohol, second section 740,000 m
3/ sky is for CO and H
2separate the synthetic and synthetic raw material of ethanol as acetic acid.Adopt CO and H in the disclosed method separating synthetic gas of patent CN102191086A
2, after separating, the output of CO is 640,000 m
3/ day, H
2output be 100,000 m
3/ day.
The synthetic ICI multistage cold shock tower low pressure synthesis technique that adopts of methyl alcohol, reaction tower is divided into 4 beds, and catalyzer adopts ICI51-7 type catalyzer.Material synthesis gas amount is 980,000 m
3/ day, after the inlet tower gas after heat exchange mixes with part quench gas, temperature is 220 ℃, enters first paragraph bed reaction methanol by tower top, emits heat simultaneously and makes reaction gas be warming up to 260 ℃.Leave the reaction gas of first paragraph catalytic bed and the cold shock charging of second segment mixes, temperature is down to 220 ℃ and is then entered second segment catalytic bed and continue reaction, so circulation.In tower, working pressure is 6 Mpa, and circulation gas and virgin gas ratio are 10:1, and methanol output is 696 tons/day.
The synthetic Acetica technique that adopts thousand Dai Tian companies of acetic acid, raw material inlet amount methyl alcohol is 696 tons/day, CO is 640,000 m
3/ day.180 ℃ of temperature of reaction, pressure 3.5 MPa, reaction adopts rhodium catalyst, and in reactor, water-content is 8%.Liquid-phase product separates iodide, and acetic acid productive rate is 99%, and output is 1291 tons/day.
By acetic acid synthetic carbonylation workshop section with separated the H obtaining by synthetic gas
2as raw material, adopt the FeNb/ZrO that the patent No. is 201210057475.5
2it is synthetic that catalyzer carries out ethanol.Temperature of reactor is 240 ℃, and reaction pressure is 3.5 MPa, and circulation gas is 30:1 with the ratio of virgin gas, and acetic acid transformation efficiency is 100%.Adopt the disclosed method of patent CN1706799 to carry out extractive distillation thick acetic acid hydrogenation product.Thick product adds 20% NaAc, in compound extracting tower extracting and separating, obtains more than 99.5% ethyl acetate and 95% ethanol.Alcohol yied 92%, output is 920 tons/day.
Embodiment 3:
360000 tons/year of ethanol synthetic (to move every year 300 days)
By H
2: CO=2:1, output are 1,850,000 m
3the synthetic gas in/sky is divided into two portions, 92.5 ten thousand m of first part
3/ it is synthetic for methyl alcohol, second section 92.5 ten thousand m
3/ sky is for CO and H
2separate the synthetic and synthetic raw material of ethanol as acetic acid.Adopt CO and H in the disclosed method low temperature separation process of patent CN102133498A synthetic gas
2, after separating, the output of CO is 80.5 ten thousand m
3/ day, H
2output be 120,000 m
3/ day.
The synthetic Linde spiral coiled pipe isothermal synthetic tower methanol synthesizing process that adopts of methyl alcohol.Material synthesis gas amount is 92.5 ten thousand m
3/ day, the inlet tower gas after heat exchange, temperature is 225 ℃, directly enters in the reaction tubes of synthetic tower from top, methanol reacts under catalyst action.Methanol synthesis catalyst adopts the CNJ206 catalyzer of Southwest Chemical Research and Design Institute, and in reaction tower, spiral coiled pipe is placed in beds, passes into the feedwater of 4.5 MPa from coiled pipe bottom, discharges middle pressure steam and recirculated water from above.Synthetic gas enters from top of tower, through beds, discharges from tower bottom., methanol output is 870 tons/day.
The synthetic Cativa acetic acid synthesis technique that adopts BP company of acetic acid, raw material inlet amount methyl alcohol is 870 tons/day, CO is 80.5 ten thousand m
3/ day.Reaction adopts iridium catalyst, water-content <5% in reactor, and acetic acid productive rate is 99%, output is 1613 tons/day.
The FeMoTaP catalyzer that the synthetic employing of the ethanol patent No. is 201210057568.8, by acetic acid synthetic carbonylation workshop section and H
2as raw material, carry out ethanol and synthesize.Temperature of reactor is 230 ℃, and reaction pressure is 3.5 MPa, H
2with acetic acid mol ratio be 50:1, acetic acid transformation efficiency is 100%.Adopt the disclosed method of patent CN1706799 to carry out extractive distillation thick acetic acid hydrogenation product.Thick product adds 15% NaAc, in compound extracting tower extracting and separating, obtains more than 99.5% ethyl acetate and 95% ethanol.Ethanol production is 1188 tons/day.
Claims (2)
1. a technique for synthesis gas through methanol ethanol processed, is characterized in that comprising the steps:
(1) synthetic gas is divided into two portions, and a part of synthetic gas is synthetic for methyl alcohol, and rest part is separated into CO and H
2;
(2) synthetic gas and methyl alcohol synthesis cycle tail gas are mixed into methyl alcohol synthetic raw gas, and methyl alcohol synthetic raw gas carries out methyl alcohol building-up reactions under methanol synthesis catalyst effect, obtain methyl alcohol and methyl alcohol synthesis cycle tail gas;
(3) after synthetic gas being separated to the CO obtaining and mixing with acetic acid synthesis cycle tail gas, then carry out carbonylation reaction with methyl alcohol, carry out acetic acid building-up reactions, obtain acetic acid and acetic acid synthesis cycle tail gas;
(4) synthetic gas separates the H obtaining
2be mixed into reactor with ethanol synthesis cycle tail gas, gas mixture contacts generation hydrogenation and carries out ethanol building-up reactions with catalyzer with acetic acid, obtain ethanol and by product and ethanol synthesis cycle tail gas, and reactor outlet crude product is through separating to obtain ethanol;
It is to adopt ICI multistage cold shock tower low pressure methanol synthesis technique, Lurgi tubular type isothermal synthetic tower low pressure methanol synthesis technique or Linde spiral coiled pipe isothermal synthetic tower methanol synthesizing process that the methyl alcohol of described step (2) synthesizes;
It is employing method 1 that the synthetic gas of described step (3) separates: unstripped gas is sent into the first adsorption tower from bottom and adsorbed, obtain CO gas product in the enrichment of the bottom of the first adsorption tower, the mixed gas that the first adsorption tower top obtains is sent to the second adsorption tower; Mixed gas is after the second adsorption tower absorption, and the outlet of the second adsorption tower obtains highly purified hydrogen product gas; Or method 2: the integrating device of a kind of producing synthesis gas from coal coproduction carbon monoxide, methyl alcohol, hydrogen, refining synthetic gas, CO low temperature separation process unit wherein and pressure swing adsorption hydrogen production unit can be used to hydrogen manufacturing and CO processed;
It is to adopt Celanese AO Plus technique, BP Cativa technique or thousand generation field Acetica techniques that the acetic acid of described step (3) synthesizes;
It is employing method 1 that the ethanol of described step (4) synthesizes: method for preparing catalyst is by transition metal Ni, Co, Fe, W, V, Mo, Nb, Cr, one or more join the compound of Ta in deionized water by the stoichiometric ratio of catalyzer composition with Secondary ammonium phosphate, and add citric acid, wherein the mol ratio of citric acid and transition metal is 0.5-3:1, the solution obtaining is stirred at 50-90 ℃ to 8-24 h, dry 18-24 h at 100-110 ℃, afterwards by sample foamed solidification 10-20 h at 120-150 ℃, by the sample roasting 3-6 h in 400-650 ℃ of air after solidifying,
By the sample after roasting at H
2under atmosphere, rise to 400-800 ℃ with the temperature rise rate of 0.5-3 ℃/min, constant temperature 3-8 h, H
2gas space velocity is 3000-9000 h
-1, sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2/ N
2passivation 2-5 h obtains catalyzer; Synthesizing alcohol temperature of reaction is within the scope of 200-300 ℃, and reaction pressure is at 1.0-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: acetic acid mol ratio is 5-50;
Or method 2: method for preparing catalyst is for first by transition metal Ni, Co, Fe, W, V, Mo, Nb, Cr, one or more compounds of Ta and Secondary ammonium phosphate join in deionized water by the stoichiometric ratio of catalyzer composition, for the solution that has precipitation to generate, in solution, add nitric acid with dissolution precipitation, by the solution incipient impregnation configuring in aluminium sesquioxide, molecular sieve, silicon-dioxide, titanium dioxide, on zirconium white or diatomite support, wherein transistion metal compound: deionized water: carrier=0.15-8.2 g:10-30 ml:10-20 g, carrier after carrying transition metal compound is at room temperature placed 2-5 h, dry 2-5 h at 30-60 ℃, dry 6-12 h at 100-120 ℃, roasting 3-6 h in 400-650 ℃ of air again, by the sample after roasting at H
2under atmosphere, be warming up to 400-800 ℃ with the speed of 0.5-3 ℃/min, at this temperature, reduce 3-8 h, H
2air speed is 3000-9000 h
-1,
Sample is at H
2atmosphere drops to after room temperature, uses O
2content is the O of 0.5-2%
2/ N
2passivation 2-5 h, obtains catalyzer; Synthesizing alcohol temperature of reaction is within the scope of 200-300 ℃, and reaction pressure is at 1.0-3.5 MPa, acetic acid liquid air speed 0.5-3 h
-1, H
2: acetic acid mol ratio is 5-50;
It is the acetaldehyde first adopting in simple distillation separated product that the crude product of described step (4) separates, and adopts afterwards extraction rectifying method separating alcohol, ethyl acetate and water;
Described extraction rectifying method separating alcohol, ethyl acetate and water are that (1) ethyl acetate, ethanol, water mixed liquid add 10～20% NaAc; (2) the thick product of composite extractant extracting and separating, tower top obtains ethyl acetate, and tower top temperature is controlled at 77～78 ℃; Tower reactor flows out saliferous mixed extractant, and extraction agent is through regenerator column processing, the processing of regenerator column top of tower fractionation lease making ethanol recovery tower, and all the other cuts are returned and are used, and saliferous extraction agent recycles.
2. the technique of a kind of synthesis gas through methanol as claimed in claim 1 ethanol processed, is characterized in that described step (2) methanol synthesis catalyst adopts ICI51-1, ICI51-2, the ICI51-7 type catalyzer of ICI company exploitation, the C79-5GL type catalyzer of Lurgi company, C302, C302-1, C302-2 or the CNJ206 of Southwest Chemical Research and Design Institute.
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| US9382177B2 (en) | 2014-04-28 | 2016-07-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising a promoter metal |
| US9024088B1 (en) | 2014-04-28 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide comprising nickel |
| US9073815B1 (en) | 2014-04-28 | 2015-07-07 | Celanese International Corporation | Hydrogenation catalysts comprising a mixed oxide and processes for producing ethanol |
| CN104263411A (en) * | 2014-10-13 | 2015-01-07 | 安徽淮化股份有限公司 | Co-production system for methanol and deeply processed ethanol gasoline and use method of co-production system |
| CN109928864B (en) * | 2019-03-14 | 2021-03-09 | 厦门大学 | Multifunctional composite catalyst and application thereof in direct preparation of ethanol from synthesis gas |
| CN111039753B (en) * | 2019-12-13 | 2021-08-13 | 中国科学院山西煤炭化学研究所 | Process for producing ethylene glycol from synthesis gas |
| CN111714913B (en) * | 2020-07-31 | 2021-12-17 | 中国科学院上海应用物理研究所 | Rotary belt distillation device and method for separating ethanol in wine products |
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