CN101941887A - Method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen - Google Patents
Method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen Download PDFInfo
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Abstract
The invention discloses a method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen, which comprises the following steps of: first synthesizing an acetic acid by using the CO and methanol by a carbonylation method, then esterifying the acetic acid and different low-carbon alcohols to produce corresponding acetic esters, and finally catalytically hydrogenating the acetic esters to indirectly produce the ethanol and alcohols corresponding to the esters of the ethanol. By a process flow of catalytically hydrogenating the acetic esters to indirectly synthesize the ethanol in a way of taking the CO and H2 as basic raw materials, the method has the advantages of developing a new approach for the preparation of the ethanol and finding new raw material sources for the production of the ethanol, and is applied to the condition of abundant coal resources in China. Compared with fermentation methods and chemical synthesis methods in the prior art, the method is popularized and applied to relieve the contradiction of increasingly tense food supply in China, reduce dependence on oil resources and produce important and positive effects on food and energy security in China. The method for synthesizing the ethanol by taking the CO and H2 as the raw materials has significance in the rational utilization of coal resources, the development of clean energy and reduction in environmental pollutions.
Description
Technical field
The invention belongs to the alcoholic acid preparing technical field, be specifically related to the method for a kind of carbon monoxide and the indirect synthesizing alcohol of hydrogen.
Background technology
Ethanol is the fermentation industry product that production history is the longest in the world, output is maximum at present.Alcohol production realizes that industrialization started from for 19 end of the centurys, and over one hundred year history has been arranged so far.It is widely used in industries such as food, chemical industry, medicine, dyestuff, national defence, it is again crucial clean energy, ethanol is made the detonation suppressor of gasoline as the not only alternative tetraethyllead of clean energy, also can make ethanol petrol and make automobile fuel, when significantly reducing gasoline combustion to the pollution of environment.
The alcoholic acid production method is divided into department of botany's material and is the fermentation method of raw material and is that material is the chemical synthesis of raw material with oil.The fermentation method alcohol production is the maximum industry in basis in the current biological industry, mainly utilize cellulose raw materials such as saccharine materials such as starchy material, molasses such as corn, paddy, Chinese sorghum, wheat, potato class and corn cob, under action of microorganisms through fermentation, distillation and ethanol production.The chemical synthesis alcohol production is that the ethene with the petroleum cracking gained is raw material, generates ethanol through chemosynthesis reaction.Production method can be divided into two kinds of indirect hydration method and direct hydration methods, and hydration method (claiming sulfuric acid hydration process again) is that sulfuric acid and ethene generate vinic acid through addition indirectly, and vinic acid is hydrolyzed again, generation ethanol and sulfuric acid; Direct hydration method be ethene and water vapour in the presence of catalyzer, through high temperature, high pressure effect, addition reaction directly takes place generates ethanol.The present industrial ethene direct hydration method that generally adopts.
Because chemical synthesis is produced the used production unit of ethanol and is required to have higher acidproof, withstand voltage properties, working condition and cost are all higher, and the Energy Situation of China is rich coal, deficency, few oil, the crude resources relative shortage, and the raw materials used ethene of chemical synthesis derives from non-reproducible petroleum resources, objectively also limited of popularization and the development of chemical method synthesizing alcohol, so China generally produces ethanol without this method in China.On industrial production, China mainly adopts fermentation method producing and ethanol in next life at present, promptly all is basically to adopt starchy material, saccharine material or cellulose raw material through zymotechnique producing and ethanol in next life.According to statistics, China has the factory more than 95% to adopt fermentative Production ethanol approximately.Along with edible and industrial alcohol, the particularly rising of the development of fuel ethanol industrial and demand, there is lack of raw materials, and problem also becomes increasingly conspicuous, and causes domestic staple food supply day by day to be becoming tight, cause the food shortage price suddenly to rise, influenced national economic stability and social stability harmony.
Technology by carbon monoxide and the direct synthesizing alcohol of hydrogen is disclosed in the prior art, but this reaction catalyst system therefor is generally and supports rhodium catalyst, lot of domestic and foreign scholar and scientific research institution study for a long period of time to this, also obtained certain progress, but finally do not realize industrialization, reason is that rhodium catalyst specific activity in the technology of synthesizing alcohol is lower, and catalyst levels is many and price is high, and products therefrom is C such as ethanol, acetate and acetaldehyde
2Oxygen-containing mixture, the alcoholic acid selectivity is low etc.
China has the abundant in coal resource, is that the technology of raw material preparing synthetic gas is ripe with the coal, can guarantee the synthetic gas CO and the H that enrich
2Adopt with CO and H in the source
2For the technology of raw material synthesizing alcohol to rationally utilizing coal resources, exploitation clear energy sources and reduce environmental pollution and all have crucial meaning.
Summary of the invention
Technical problem
The objective of the invention is to overcome defective of the prior art, the method of a kind of carbon monoxide and the indirect synthesizing alcohol of hydrogen is provided, this method has outstanding technological innovation, flow process is simple, raw material sources are extensive and cheap, the reaction conditions gentleness, can significantly reduce the cost of investment of fixture, be very beneficial for suitability for industrialized production, alcoholic acid quality that makes simultaneously and yield are all very high.
Technical scheme
The present invention is achieved by the following technical programs.
The method of a kind of carbon monoxide and the indirect synthesizing alcohol of hydrogen, preparation process is as follows: the synthetic gas that (1) coal gasifier comes out is isolated carbon monoxide and hydrogen through dedusting, wet desulphurization, smart desulfurization, transformation absorption and catalytic dehydrogenation series operation, at first acetic acid synthesized through carbonylation method in autoclave by carbon monoxide and methyl alcohol, temperature of reaction is 175 ~ 200 ℃, reaction pressure is 1.5 ~ 3.5 MPa, uses the iodate rhodium as catalyzer in the carbonylation process; (2) gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, and acetic acid and low-carbon alcohol esterification generate corresponding acetic ester in reaction fractionating tower, and temperature of reaction is 60 ~ 110 ℃, and reaction pressure is under the normal pressure, uses esterifying catalyst in the esterification process; (3) acetic ester that makes is delivered to fixed-bed reactor through dewatering after refining, and then generate the alcohol of ethanol and ester correspondence through shortening, the weight space velocity of acetic ester is 0.25 ~ 3 h
-1, temperature of reaction is that 150 ~ 300 ℃, reaction pressure are that 0.5 ~ 2 MPa, hydrogen/ester mol ratio are 20 ~ 150 conditions, uses Cu-series catalyst in the shortening process.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, the purity of the purity of described carbon monoxide 〉=98.5%, described hydrogen 〉=99%.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, described esterifying catalyst is a kind of in sulfuric acid or the Witco 1298 Soft Acid liquid acid catalyst, or a kind of in the molecular sieve, silicotungstic acid, phospho-molybdic acid solid acid catalyst, or a kind of in the sulfuric acid modified zirconium dioxide, sulfuric acid modified titania modified oxide catalyst.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, described acetic ester is an acetic acid alkyl ester, its alkyl carbon number is 1-20.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, described Cu-series catalyst is made up of active ingredient, auxiliary agent and carrier, described active ingredient is the oxide compound of copper or copper or both mixtures, described auxiliary agent is one or more in the oxide compound of zinc, manganese, chromium, calcium, barium, iron, nickel, these several metals of magnesium, and carrier is silicon sol or aluminum oxide.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, the composition of described Cu-series catalyst is a benchmark with the quality of catalyzer, and the quality percentage composition of active ingredient is 30% ~ 70%, the quality percentage composition of auxiliary agent is 10% ~ 30%, the quality percentage composition 5% ~ 60% of carrier.
The above-mentioned a kind of carbon monoxide and the method for the indirect synthesizing alcohol of hydrogen, wherein, the transformation efficiency of acetic ester 〉=90% in the described catalytic hydrogenation reaction, alcoholic acid selectivity 〉=98%;
The preparation method of above-mentioned Cu-series catalyst is as follows: (a) salts solution of the salts solution of active ingredient copper, auxiliary agent and carrier or carrier forerunner are made into mixing solutions 1; (b) precipitation agent is configured to solution 2, be heated to 60～100 ℃ stand-by, described precipitation agent is yellow soda ash, sodium bicarbonate, saleratus, salt of wormwood, ammoniacal liquor or urea; (c) stirred solution 2 limits in limit add solution 1 in the solution 2, and controlled temperature is at 55～100 ℃, and reaction end pH value is 7～8, and the slip that obtains is reactive precursor; (d) reactive precursor was through bubbling, washing, filtration and 60～120 ℃ dry 2～24 hours down; (e) dried reactive precursor is ground, 350～500 ℃ of following roastings 2～5 hours, moulding, finally make the target catalyzer.
The reaction equation of carbon monoxide and the indirect synthesizing alcohol of hydrogen is: (square formula 1,2,3)
Reaction also generates several by products such as ethyl acetate except that the low-carbon alcohol that generates ethanol and ester correspondence, the low-carbon alcohol that generates in the reaction can be returned the acetic ester synthesizing section and recycle, and ethyl acetate can be returned hydrogenation system and continue reaction generation ethanol.
Beneficial effect
Adopt CO and methyl alcohol earlier acetic acid synthesized through carbonylation method, acetic acid generates corresponding acetic ester with different low-carbon alcohol esterifications again, and the technology that last acetic ester shortening generates ethanol and ester alcohol corresponding thereof is not indirectly seen document and patent report.The present invention is based on coal resources in China reserves abundant advantage and characteristics, has explored one with CO and H
2Be basic raw material,, compare that the present invention has following characteristics with other technologies that China present alcohol production is adopted through the brand-new route and the technical process of the indirect synthesizing alcohol of acetic ester:
(1) the present invention is with CO and H
2Be the technical process of basic raw material, opened up the new way of ethanol preparation, started the new raw material sources of alcohol production through the indirect synthesizing alcohol of acetic ester shortening.Because China has the abundant in coal resource, be that the technology of raw material preparing synthetic gas is ripe with the coal, can guarantee the synthetic gas CO and the H that enrich
2Adopt with CO and H in the source
2For the technology of raw material synthesizing alcohol to rationally utilizing coal resources, exploitation clear energy sources and reduce environmental pollution and all have crucial meaning.With respect to fermentation method of the prior art and chemical synthesis, the promotion and application of this technology can be alleviated the contradiction that China's staple food supply is becoming tight day by day, also can reduce dependency, will produce important and active influence China's grain and energy security to petroleum resources; Simultaneously also find a brand-new outlet that has development prospect, thereby have important scientific meaning, outstanding technological innovation and significant social economic benefit for being at present production capacity serious methyl alcohol and acetic acid industry superfluous, market continued downturn predicament.
(2) raw material sources required for the present invention are extensive, and are technical grade product, and are cheap, can reduce production costs greatly;
(3) technical process of the present invention is simple, and reaction conditions gentleness, temperature of reaction are that 150 ~ 300 ℃, reaction pressure are 0.5 ~ 2MPa, can significantly reduce the cost of investment of fixture, highly beneficial to suitability for industrialized production, the transformation efficiency of acetic ester 〉=90%, alcoholic acid selectivity 〉=98%;
(4) heavy constituent content is few in the final gained reaction product of the present invention, and target product is easy to separate, and product purity reaches 99%.
Description of drawings
Fig. 1 is the process flow diagram of carbon monoxide of the present invention and the indirect synthesizing alcohol of hydrogen.
Embodiment
As Fig. 1.
Embodiment 1
The synthetic gas that coal gasifier comes out obtains the CO (carbon monoxide converter) gas of purity 〉=98.5%, the hydrogen of purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 195 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 3.0MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and methyl alcohol under the sulfuric acid catalysis effect under 60 ℃ of condition of normal pressure esterification generate ritalin, through dewater refining after ritalin purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
Preparation Cu-series catalyst: with 220gCu (NO
3)
23H
2O, 36.6g Zn (NO
3)
26H
2O and 36.8g Al (NO
3)
39H
2O places beaker, adds 1500g distilled water it is dissolved fully; 86g urea is poured in the there-necked flask, is added 2000g distilled water, stir and to make it to dissolve fully, and be heated to 75 ℃ stand-by; The limit is stirred the urea soln limit mixed salt solution of preparing is added wherein, and stirring is warming up to 90 ℃, back flow reaction control endpoint pH is 8.0, bubbling 2 hours again after reaction finishes, catalyzer through washing, filter after 100 ℃ of dryings 14 hours, grind then,, form the particle of 3 * 5mm again through compressing tablet 500 ℃ of following roastings 3 hours.The specific surface area of catalyst 152m of above-mentioned preparation
2/ g, pore volume are 0.6cm
3/ g, average pore radius is 15nm.
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 220 ℃ with 10 ℃/h, and at 220 ℃ of reduction 4h, hydrogen gas space velocity 3000h
-1About, with ritalin solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the ritalin air speed is 1.1 h
-1, hydrogen/ester mol ratio is 50, reaction process condition and the results are shown in Table 1;
Embodiment 2
The synthetic gas that coal gasifier comes out obtains the hydrogen of purity 〉=98.5% CO (carbon monoxide converter) gas, purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 185 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 2.0MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and ethanol under the Witco 1298 Soft Acid katalysis under 70 ℃ of condition of normal pressure esterification generate vinyl acetic monomer, through dewater refining after vinyl acetic monomer purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
Preparation Cu-series catalyst: with 220gCu (NO
3)
23H
2O, 36.6gZn (NO
3)
26H
2O, 31.8gMg (NO
3)
26H
2O and 36.8g Al (NO
3)
39H
2O places beaker, adds 1500g distilled water it is dissolved fully; With 143.3gKHCO
3Pour in the there-necked flask, add 2000g distilled water, stir and to make it to dissolve fully, and be heated to 80 ℃ stand-by; KHCO is stirred on the limit
3The solution limit adds the mixed salt solution of preparation wherein, and stirring is warming up to 90 ℃, back flow reaction control endpoint pH is 8.0, reaction finished bubbling 2 hours again, catalyzer through washing, filter after 90 ℃ of dryings 11 hours, grind then,, form the particle of 3 * 5mm again through compressing tablet 500 ℃ of following roastings 2 hours.The specific surface area of catalyst of above-mentioned preparation is 160 m
2/ g, pore volume are 0.6 cm
3/ g, average pore radius is 12nm.
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 200 ℃ with 10 ℃/h, and at 200 ℃ of reduction 4h, hydrogen gas space velocity 4000h
-1About, with vinyl acetic monomer solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the vinyl acetic monomer air speed is 0.8 h
-1, hydrogen/ester mol ratio is 80, reaction process condition and the results are shown in Table 1;
Embodiment 3
The synthetic gas that coal gasifier comes out obtains the CO (carbon monoxide converter) gas of purity 〉=98.5%, the hydrogen of purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 200 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 3.3MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and n-propyl alcohol under the molecular sieve catalytic effect under 85 ℃ of condition of normal pressure esterification generate n-propyl acetate, through dewater refining after n-propyl acetate purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
Preparation Cu-series catalyst: with 190.2gCu (NO
3)
23H
20,94.7gCr (NO
3)
39H
20,8.6gCa (NO
3)
24H
20 and the 35.3g solid content be that 25% silicon sol places beaker, add 2000g distilled water it dissolved fully; With 299gK
2CO
3Pour in the there-necked flask, add 2000g distilled water, stir and to make it to dissolve fully, and be heated to 70 ℃ stand-by; K is stirred on the limit
2CO
3The solution limit adds the mixed salt solution of preparation wherein, and stirring is warming up to 93 ℃, back flow reaction control endpoint pH is 7.6, bubbling 2 hours again after reaction finishes, catalyzer through washing, filter after 95 ℃ of dryings 10 hours, grind then,, form the particle of 3 * 5mm again through compressing tablet 450 ℃ of following roastings 3 hours.The specific surface area of catalyst of above-mentioned preparation is 213m
2/ g, pore volume are 1.3cm
3/ g, average pore radius is 16nm.
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 240 ℃ with 10 ℃/h, and at 240 ℃ of reduction 4h, hydrogen gas space velocity 5000h
-1About, with n-propyl acetate solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the n-propyl acetate air speed is 0.7 h
-1, hydrogen/ester mol ratio is 100, reaction process condition and the results are shown in Table 1;
Embodiment 4
The synthetic gas that coal gasifier comes out obtains the CO (carbon monoxide converter) gas of purity 〉=98.5%, the hydrogen of purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 195 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 3.0MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and Virahol under the phospho-molybdic acid katalysis under 75 ℃ of condition of normal pressure esterification generate Iso Butyl Acetate, through dewater refining after Iso Butyl Acetate purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
The preparation method of Cu-series catalyst is with embodiment 1;
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 240 ℃ with 10 ℃/h, and at 240 ℃ of reduction 4h, hydrogen gas space velocity 5000h
-1About, with Iso Butyl Acetate solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the Iso Butyl Acetate air speed is 0.7 h
-1, hydrogen/ester mol ratio is 110, reaction process condition and the results are shown in Table 1;
Embodiment 5
The synthetic gas that coal gasifier comes out obtains the CO (carbon monoxide converter) gas of purity 〉=98.5%, the hydrogen of purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 180 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 2.0MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and propyl carbinol under the silicotungstic acid katalysis under 110 ℃ of condition of normal pressure esterification generate n-butyl acetate, through dewater refining after n-butyl acetate purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
The preparation method of Cu-series catalyst is with embodiment 2;
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 230 ℃ with 10 ℃/h, and at 230 ℃ of reduction 4h, hydrogen gas space velocity 3000h
-1About, with n-butyl acetate solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the n-butyl acetate air speed is 0.5h
-1, hydrogen/ester mol ratio is 130, reaction process condition and the results are shown in Table 1;
Embodiment 6
The synthetic gas that coal gasifier comes out obtains the CO (carbon monoxide converter) gas of purity 〉=98.5%, the hydrogen of purity 〉=99% through dedusting, wet desulphurization, smart desulfurization, transformation absorption, catalytic dehydrogenation series operation, purity is volume percent and calculates, gained CO (carbon monoxide converter) gas and methyl alcohol are catalyzer with the iodate rhodium in autoclave, are that 200 ℃, pressure are the synthetic acetic acid of low pressure carbonylation under the 3.0MPa condition in temperature; Gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, in reaction fractionating tower acetic acid and Pentyl alcohol under the sulfuric acid modified zirconium dioxide katalysis under 60 ℃ of condition of normal pressure esterification generate n-Amyl acetate, through dewater refining after n-Amyl acetate purity calculate by percentage to the quality greater than 99%(), as follow-up shortening raw material;
The preparation method of Cu-series catalyst is with embodiment 3;
Take by weighing the 100g Cu-series catalyst, Cu-series catalyst is placed position, fixed-bed reactor flat-temperature zone, under pure hydrogen atmosphere, progressively be warming up to 250 ℃ with 10 ℃/h, and at 250 ℃ of reduction 4h, hydrogen gas space velocity 3000h
-1About, with n-Amyl acetate solution by volume pump with enter fixed-bed reactor after hydrogen mixes, wherein the n-Amyl acetate air speed is 0.4 h
-1, hydrogen/ester mol ratio is 150, reaction process condition and the results are shown in Table 1;
Claims (7)
1. the method for carbon monoxide and the indirect synthesizing alcohol of hydrogen, it is characterized in that, preparation process is as follows: the synthetic gas that (1) coal gasifier comes out is isolated carbon monoxide and hydrogen through dedusting, wet desulphurization, smart desulfurization, transformation absorption and catalytic dehydrogenation series operation, at first acetic acid synthesized through carbonylation method in autoclave by carbon monoxide and methyl alcohol, temperature of reaction is 175 ~ 200 ℃, reaction pressure is 1.5 ~ 3.5 MPa, uses the iodate rhodium as catalyzer in the carbonylation process; (2) gained acetic acid is delivered to reaction fractionating tower after making with extra care through dewatering, and acetic acid and low-carbon alcohol esterification generate corresponding acetic ester in reaction fractionating tower, and temperature of reaction is 60 ~ 110 ℃, and reaction pressure is under the normal pressure, uses esterifying catalyst in the esterification process; (3) acetic ester that makes is delivered to fixed-bed reactor through dewatering after refining, and then generate the alcohol of ethanol and ester correspondence through shortening, the weight space velocity of acetic ester is 0.25 ~ 3 h
-1, temperature of reaction is that 150 ~ 300 ℃, reaction pressure are that 0.5 ~ 2 MPa, hydrogen/ester mol ratio are 20 ~ 150, uses Cu-series catalyst in the shortening process.
2. the method for a kind of carbon monoxide as claimed in claim 1 and the indirect synthesizing alcohol of hydrogen is characterized in that, the purity of the purity of described carbon monoxide 〉=98.5%, described hydrogen 〉=99%.
3. the method for a kind of carbon monoxide as claimed in claim 1 and the indirect synthesizing alcohol of hydrogen, it is characterized in that, described esterifying catalyst is a kind of in sulfuric acid or the Witco 1298 Soft Acid liquid acid catalyst, or a kind of in the molecular sieve, silicotungstic acid, phospho-molybdic acid solid acid catalyst, or a kind of in the sulfuric acid modified zirconium dioxide, sulfuric acid modified titania modified oxide catalyst.
4. the method for a kind of carbon monoxide as claimed in claim 1 and the indirect synthesizing alcohol of hydrogen is characterized in that, described acetic ester is an acetic acid alkyl ester, and its alkyl carbon number is 1-20.
5. the method for a kind of carbon monoxide as claimed in claim 1 and the indirect synthesizing alcohol of hydrogen, it is characterized in that, described Cu-series catalyst is made up of active ingredient, auxiliary agent and carrier, described active ingredient is the oxide compound of copper or copper or both mixtures, described auxiliary agent is one or more in the oxide compound of zinc, manganese, chromium, calcium, barium, iron, nickel, these several metals of magnesium, and carrier is silicon sol or aluminum oxide.
6. the method for a kind of carbon monoxide as claimed in claim 5 and the indirect synthesizing alcohol of hydrogen, it is characterized in that, the composition of described Cu-series catalyst is a benchmark with the quality of catalyzer, the quality percentage composition of active ingredient is 30% ~ 70%, the quality percentage composition of auxiliary agent is 10% ~ 30%, the quality percentage composition 5% ~ 60% of carrier.
7. the method for a kind of carbon monoxide as claimed in claim 1 and the indirect synthesizing alcohol of hydrogen is characterized in that, the transformation efficiency of acetic ester 〉=90% in the described catalytic hydrogenation reaction, alcoholic acid selectivity 〉=98%.
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| CN103012062A (en) * | 2012-12-20 | 2013-04-03 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN103288594A (en) * | 2013-06-04 | 2013-09-11 | 临海市联盛化学有限公司 | Method for preparing methanol and ethanol by methyl acetate by way of hydrogenation |
| CN103586025A (en) * | 2012-08-17 | 2014-02-19 | 亚申科技研发中心（上海）有限公司 | Catalyst for preparing ethanol by hydrogenation of acetic ester, and preparation method and application thereof |
| CN103787832A (en) * | 2014-01-22 | 2014-05-14 | 天津普莱化工技术有限公司 | Process method for preparing ethanol by hydrogenating methyl acetate |
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| CN106995363A (en) * | 2016-01-25 | 2017-08-01 | 河南顺达化工科技有限公司 | A kind of hydrogenation coupled technique for preparing ethanol of acetic acid |
| CN107899583A (en) * | 2017-11-22 | 2018-04-13 | 山东玉皇化工有限公司 | It is a kind of to prepare catalyst of ethanol and preparation method thereof for methyl methanol syngas |
| CN108299157A (en) * | 2018-01-29 | 2018-07-20 | 安徽皖维高新材料股份有限公司 | A method of preparing ethyl alcohol using calcium carbide stove exhaust |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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