CN102718627B - Preparation method of ethanol by adding hydrogen to ethyl acetate - Google Patents
Preparation method of ethanol by adding hydrogen to ethyl acetate Download PDFInfo
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- CN102718627B CN102718627B CN201210210658.6A CN201210210658A CN102718627B CN 102718627 B CN102718627 B CN 102718627B CN 201210210658 A CN201210210658 A CN 201210210658A CN 102718627 B CN102718627 B CN 102718627B
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Abstract
The invention provides a preparation method of ethanol by adding hydrogen to ethyl acetate. A tubular hydrogenation reactor is used for reaction. The reaction is performed in a tubular side with loaded catalyst. The ethyl acetate solution which is used as refrigerant is disposed in a shell side of the tubular hydrogenation reactor. During the reaction process, heat generated by the reaction is transmitted to the ethyl acetate solution in the shell side. Self-balancing of heat in the tubular hydrogenation reactor is guaranteed by controlling adding amount of the ethyl acetate solution and discharging pressure at constant pressure, so that temperature in the reaction tube is basically constant, and the whole reaction tube is in the refrigerant with constant temperature. By the preparation method, reaction heat is fully utilized, temperature fluctuation of the reaction is low, and selectivity and conversion rate of the reaction are increased. Compared with conventional devices using cooling water as refrigerant, repeated heat transfer among multiple heat exchangers is reduced, production process is simplified, productivity is improved, energy consumption is saved, and investment cost is lowered.
Description
Technical field
The present invention relates to ethanol chemical production field, be specifically related to a kind of processing method of ethyl acetate preparation of ethanol by hydrogenating
Background technology
Ethanol is important industrial chemicals and fuel, and it is of many uses.Its as solvent be mainly used in the crystallization, washing composition, extraction agent of organic synthesis, various compounds, as tackiness agent, nitro spray paint, the solvent of varnish, makeup, ink, paint remover etc., edible ethanol can concocted white spirits; As industrial chemicals be mainly used in agricultural chemicals, medicine, rubber, plastics, regenerated fiber, washing composition etc. manufacture raw material, can also do frostproofer, fuel, sterilizing agent etc.In addition, 75% ethanolic soln is often used to medical treatment sterilization; As fuel, ethanol can part petroleum replacing fuel, is a kind of clean energy, is again a kind of good Gasoline oxygenate and octane value blend component, can effectively reduce the CO content in tail gas, reduces environmental pollution.
About the technology of preparing of ethanol, at present main employing method is divided into chemosynthesis and two kinds of routes of biological fermentation.Chemical synthesis route mainly contains that synthetic gas catalyzes and synthesizes, acetic acid hydrogenation synthesis technique.Biological fermentation route mainly contains grain fermentation, non-grain raw material fermentation and synthetic gas fermentation ethanol processed.Wherein, grain fermentative routes, because meeting produces the problem that endangers grain security.Particularly for such populous nation of China, if further develop grain fermentation, can cause the problem of striving grain, striving ground with grain with people.
In chemical synthesis route, the techniques such as traditional ethylene hydration method, due to the few oily many coals of China, its development is also limited by very large.Therefore develop take acetic acid as raw material, for ethanol, can give full play to the advantage of rich coal resources in China through intermediate product ethyl acetate Hydrogenation, can possess and the advantage of traditional grain fermentation with petroleum path competition.Meanwhile, can alleviate on the one hand the predicament of current domestic acetic acid industry in the serious surplus of production capacity, market continued downturn, develop its downstream industry chain; On the other hand, due to the unstable of the non-renewable and oildom of oil, alcohol fuel can be extenuated the fuel energy security problems producing therefrom to a certain extent.
From the achievement in research of having reported, ethyl acetate preparation of ethanol by hydrogenating technique, has adopted CuO-Al at present mostly
2o
3catalyzer, to replace early stage Cu-Cr catalyzer, to overcome the very big harm of Cr to human body and environment.In reaction, the transformation efficiency of ethyl acetate can reach more than 97%, and selectivity can reach more than 98%.In order to suppress the generation of side reaction, hydrogen in reaction is excessive, and the volume ratio of hydrogen and ethyl acetate is 10～60.Meanwhile, be also mixed with a certain amount of ethanol in ethyl acetate charging, the volume ratio of ethanol and ethyl acetate is 0.05～0.6.In conventional production technique, fixed bed or water-cooled shell-and-tube reactor are mostly adopted, technique ubiquity device structure is not compact, control isothermal difficulty, auxiliary facility is many, and investment is large, reference mark is many and loaded down with trivial details, heat utilization efficiency is low, and energy consumption is high, react the problems such as concurrent heating and heat-obtaining difficulty.
Summary of the invention
The object of the present invention is to provide a kind of processing method of efficient, energy-conservation ethyl acetate preparation of ethanol by hydrogenating, this processing method has reduced reaction process, the temperature controls such as reaction are realized, improve the selectivity of reaction, and water coolant and heating steam consumption are saved, realize conserve energy, the effect reducing production costs.
For achieving the above object, the present invention has adopted following technical scheme:
1) ethyl acetate pumps into the first feed preheater by ethyl acetate tundish by the first raw material force (forcing) pump and the second feed preheater carries out preheating successively, and the ethyl acetate after preheating enters into material separator and carries out vapour, liquid phase separation;
2) separate through material separator the liquid phase feed obtaining and pump into drum as refrigerant by the second raw material force (forcing) pump, then entered the shell side of hydrogenation shell and tube reactor by drum, liquid phase feed absorbs hydrogenation reaction institute's liberated heat and evaporates formation steam in shell side, steam enters drum, is then exported by drum;
3) hydrogen enters into the 3rd feed preheater after the phase feed obtaining is converged and carries out preheating with separating through material separator, after preheating with incoming stock well heater together with steam through drum output, in feed heater is heated to enter after 185～256 ℃ the tubulation of hydrogenation shell and tube reactor, carry out shortening send out should, generate gas-phase reaction product;
4) gas-phase reaction product enters respectively the 3rd feed preheater and the second feed preheater carries out heat exchange, and gas-phase reaction product is isolated liquid product after heat exchange cooling, and liquid product flows into finished product holding tank;
5) liquid product in finished product holding tank carries out rectifying by sending into product separation tower after product fresh feed pump pressurization, obtains the ethanol of purifying, and the ethanol of purifying enters the first feed preheater and carries out heat exchange.
In described step 1), ethyl acetate temperature after the two-stage preheating of the first feed preheater and the second feed preheater reaches 184～244 ℃, and pressure is 1.4～2.9Mpa(gauge pressure).
Described step 2) in the level pressure blowdown presssure of steam while being exported by drum be 1.3～2.8Mpa(gauge pressure), temperature is 189～261 ℃.
Described gas-phase reaction product separation goes out after liquid product, after remaining gas-phase reaction product converges, entering recycle hydrogen water cooler further lowers the temperature, the liquid product further forming after cooling flow into finished product holding tank, the small portion of residual gas phase reaction product is discharged as the venting of speeding, most of the 3rd feed preheater that enters after circulating hydrogen compressor supercharging.
Ethyl acetate in described step 5) in liquid product and ethanol form azeotrope and are steamed by product separation column overhead, steam rear inflow ethyl acetate tundish.
In technical process of the present invention, adopt raw acetic acid ethyl ester as refrigerant, hydrogenator is shell and tube reactor, when normal reaction, raw acetic acid ethyl ester reclaims and comes from after the heat that reacts gas-phase product, partial gasification, wherein liquid phase part, via being pumped in the drum on shell and tube reactor top, refrigerant as shell and tube reactor uses, be heated to the unstripped gas of temperature of reaction, enter into shell and tube reactor, reaction is carried out in the tubulation tube side that is mounted with catalyzer, reaction institute liberated heat is passed to rapidly the ethyl acetate of shell side, make it to produce steam, after separating via drum, finally import in phase feed, be to discharge to guarantee that in the level pressure of shell and tube reactor shell side the reaction heat by producing in hydrogenation shell and tube reactor tube side removes in time adding with ethyl acetate of ethyl acetate by controlling refrigerant, can guarantee that in shell and tube reactor, heat is realized self-equilibrating, make temperature substantially constant in reaction tube, make whole reaction tube within isothermal refrigerant.
Unstripped gas of the present invention is ethyl acetate and hydrogen, and product comprises excessive hydrogen and a small amount of unconverted ethyl ester of raw acetic acid completely, and the ethanol generating.Excessive hydrogen pushes back shell and tube reactor by recycle compressor to be continued to use, unreacted completely raw acetic acid ethyl ester after product separation tower rectification and purification, the ethyl acetate that tower top obtains and ethyl alcohol azeotropy article are directly inputted to ethyl acetate tundish, mix as raw material and use with fresh ethyl.Product separation tower is the rectifying tower of atmospheric operation, and overhead extraction temperature is the ethyl acetate of 78 ℃ and the azeotrope of ethanol (mass ratio of ethyl acetate and ethanol is 3:1), and at the bottom of tower, extraction is the product ethanol of mole purity more than 99.9%.
Compared with prior art, when the processing method of ethyl acetate preparation of ethanol by hydrogenating of the present invention can make normal running, temperature of reaction fluctuation is controlled in operating point temperature deviation 5 spends, reduced the transmission of heat repeatedly between many heat-exchange equipments simultaneously, simplify production technique, improve production efficiency, saved energy expenditure and reduced cost.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the processing method of ethyl acetate preparation of ethanol by hydrogenating of the present invention;
In figure: ethyl acetate tundish 1, the first feed preheater 2, the second feed preheaters 3, material separator 4, the three feed preheaters 5, feed heater 6, hydrogenation shell and tube reactor 7, drum 8, finished product holding tank 9, recycle hydrogen water cooler 10, circulating hydrogen compressor 11, product separation tower 12, the first raw material force (forcing) pumps 13, the second raw material force (forcing) pump 14, product fresh feed pump 15.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Referring to Fig. 1, step of the present invention is as follows:
1) ethyl acetate pumps into the first feed preheater 2 by ethyl acetate tundish 1 by the first raw material force (forcing) pump 13 and the second feed preheater 3 carries out preheating successively, and the ethyl acetate after preheating enters into material separator 4 and carries out vapour, liquid phase separation; In described step 1), ethyl acetate temperature after the two-stage preheating of the first feed preheater 2 and the second feed preheater 3 reaches 184～244 ℃, and pressure is 1.4～2.9Mpa(gauge pressure); 2) separate through material separator 4 liquid phase feed obtaining and pump into drum 8 as refrigerant by the second raw material force (forcing) pump 14, then entered the shell side of hydrogenation shell and tube reactor 7 by drum 8, liquid phase feed absorbs hydrogenation reaction institute's liberated heat and evaporates formation steam in shell side, steam enters drum 8, is then exported by drum 8; Described step 2) in the level pressure blowdown presssure of steam while being exported by drum 3 be 1.3～2.8Mpa(gauge pressure), temperature is 189～261 ℃; 3) hydrogen enters into the 3rd feed preheater 5 after the phase feed obtaining is converged and carries out preheating with separating through material separator 4, after preheating together with the steam of exporting through drum 8 incoming stock well heater 6, in feed heater 6 is heated to enter after 185～256 ℃ the tubulation of hydrogenation shell and tube reactor 7, carry out shortening send out should, generate gas-phase reaction product; 4) gas-phase reaction product enters respectively the 3rd feed preheater 5 and the second feed preheater 3 carries out heat exchange, and gas-phase reaction product is isolated liquid product after heat exchange cooling, and liquid product flows into finished product holding tank 9; Described gas-phase reaction product separation goes out after liquid product, after remaining gas-phase reaction product converges, entering recycle hydrogen water cooler 10 further lowers the temperature, the liquid product further forming after cooling flow into finished product holding tank 9, the small portion of residual gas phase reaction product is discharged as the venting of speeding, most of the 3rd feed preheater 5 that enters after circulating hydrogen compressor 11 superchargings; 5) liquid product in finished product holding tank 9 is sent into product separation tower 12 after being pressurizeed by product fresh feed pump 15 and is carried out rectifying, obtains the ethanol of purifying, and the ethanol of purifying enters the first feed preheater 2 and carries out heat exchange; Ethyl acetate in described step 5) in liquid product and ethanol form azeotrope and are steamed by product separation tower 12 tower tops, steam rear inflow ethyl acetate tundish 1.
Embodiment
An energy-efficient technique for ethyl acetate preparation of ethanol by hydrogenating packs CuO-Al in the tubulation tube side of hydrogenation shell and tube reactor
2o
3catalyzer, two sections of tubulation are equipped with and the equigranular porcelain ring of catalyzer, take ethyl acetate as raw material, the reaction pressure of hydrogenation reaction is 2.2Mpa(gauge pressure).
The ethyl acetate-ethanol azeotrope being reclaimed by product separation tower mixes in ethyl acetate tundish with fresh ethyl charging (inlet amount of fresh ethyl is 11968kg/h), after mixing, pump into the first feed preheater by ethyl acetate tundish through the first raw material force (forcing) pump, the first feed preheater with from the product ethanol generation heat exchange preheating of product separation tower, in the first feed preheater, raw material has been preheating to 60 ℃, raw material after preheating enters into the second feed preheater by pipeline, carry out heat exchange at the second feed preheater and the gas-phase reaction product that comes from hydrogenation shell and tube reactor, in the second feed preheater, raw material has further been preheating to 186 ℃, the raw material that leaves the second feed preheater enters into material separator, carry out vapour, liquid phase separation,
After in reaction, required supplementary fresh hydrogen is mixed with circulating hydrogen, (in gas mixture, the volume ratio of hydrogen and nitrogen is 0.2, nitrogen is carrier gas), converge by pipeline and the phase feed that comes from material separator top, then together enter into the 3rd feed preheater via pipeline, in the 3rd feed preheater Yu from the gas-phase reaction product of hydrogenation shell and tube reactor, carry out thermal exchange, in the 3rd feed preheater, raw material has further been preheating to 195 ℃, and the flow of gas mixture is 5321.6m
3/ h;
Liquid in material separator pumps into drum by the second raw material force (forcing) pump, entered the shell side of hydrogenation shell and tube reactor by pipeline as refrigerant, absorption comes from ethyl acetate hydrogenation reaction institute's liberated heat and evaporates, ethyl acetate after evaporation enters drum by pipeline, after being exported by drum, converge via pipeline and the raw material that comes from the 3rd feed preheater, the flow of gas mixture is 5781.6m again
3/ h, enters into feed heater via pipeline after converging again, and in feed heater, raw material is further superheated to 230 ℃ by water vapor, then enters into hydrogenation shell and tube reactor via pipeline, carries out catalytic hydrogenation reaction in the tube side of its tubulation;
The flow that comes from the gas-phase reaction product of hydrogenation shell and tube reactor is 5881.6m
3/ h, temperature is 230 ℃, volume consists of: hydrogen 74.39%, nitrogen 16.41%, ethanol 8.74%, other 0.46%.Gas-phase reaction product is divided into two strands, enter respectively the 3rd feed preheater and the second feed preheater and carry out heat exchange, part gas-phase reaction product is lowered the temperature and is formed product liquid in heat exchange, product liquid flow into finished product holding tank by pipeline respectively, after remaining gas-phase reaction product converges, enter recycle hydrogen water cooler via pipeline, in recycle hydrogen water cooler, be recycled water coolant and further cool to 45 ℃, the product liquid obtaining after cooling enters into finished product holding tank via pipeline, residual gas phase reaction product is recycle hydrogen, the recycle hydrogen of small portion is by discharging as the venting of speeding, all the other most of recycle hydrogens after circulating hydrogen compressor supercharging the fresh hydrogen supplementary with needs mix, enter the 3rd feed preheater via pipeline.
The liquid-phase product that comes from finished product holding tank enters product separation tower after via the pressurization of product fresh feed pump.Product separation tower is the rectifying tower of atmospheric operation, and whole ethyl acetate and ethanol form azeotrope (mass ratio of ethyl acetate and ethanol is 3:1), steamed, and send back to ethyl acetate tundish via pipeline by tower top.Meanwhile, at the bottom of tower, can obtain flow is 12003.9kg/h, the product ethanol of mole purity more than 99.9%.
This process using raw acetic acid ethyl ester solution uses as the refrigerant of hydrogenation shell and tube reactor, take full advantage of the reaction heat of hydrogenation reaction, make to be mounted with temperature of reaction fluctuation in the tubulation tube side of catalyzer very little, selectivity and the transformation efficiency of reaction are effectively increased, compared with the technique that is simultaneously refrigerant with conventional employing water coolant, this technique has reduced the transmission of heat repeatedly between many heat-exchange equipments, simplify production technique, improve production efficiency, saved energy expenditure and reduced cost of investment.
Claims (5)
1. a processing method for ethyl acetate preparation of ethanol by hydrogenating, is characterized in that: comprise the following steps:
1) ethyl acetate pumps into the first feed preheater (2) by ethyl acetate tundish (1) by the first raw material force (forcing) pump (13) and the second feed preheater (3) carries out preheating successively, and the ethyl acetate after preheating enters into material separator (4) and carries out vapour, liquid phase separation;
2) separate through material separator (4) liquid phase feed obtaining and pump into drum (8) as refrigerant by the second raw material force (forcing) pump (14), then entered the shell side of hydrogenation shell and tube reactor (7) by drum (8), liquid phase feed absorbs hydrogenation reaction institute's liberated heat and evaporates formation steam in shell side, steam enters drum (8), is then exported by drum (8);
3) hydrogen enters into the 3rd feed preheater (5) after the phase feed obtaining is converged and carries out preheating with separating through material separator (4), after preheating with incoming stock well heater (6) together with steam through drum (8) output, in feed heater (6) is heated to enter after 185～256 ℃ the tubulation of hydrogenation shell and tube reactor (7), carry out shortening send out should, generate gas-phase reaction product;
4) gas-phase reaction product enters respectively the 3rd feed preheater (5) and the second feed preheater (3) carries out heat exchange, and gas-phase reaction product is isolated liquid product after heat exchange cooling, and liquid product flows into finished product holding tank (9);
5) liquid product in finished product holding tank (9) is sent into product separation tower (12) after by product fresh feed pump (15) pressurization and is carried out rectifying, obtains the ethanol of purifying, and the ethanol of purifying enters the first feed preheater (2) and carries out heat exchange.
2. a kind of processing method of ethyl acetate preparation of ethanol by hydrogenating according to claim 1, it is characterized in that: in described step 1), ethyl acetate temperature after the two-stage preheating of the first feed preheater (2) and the second feed preheater (3) reaches 184～244 ℃, and pressure is 1.4～2.9Mpa.
3. a kind of processing method of ethyl acetate preparation of ethanol by hydrogenating according to claim 1, is characterized in that: described step 2) in the level pressure blowdown presssure of steam while being exported by drum (8) be 1.3～2.8Mpa, temperature is 189～261 ℃.
4. a kind of processing method of ethyl acetate preparation of ethanol by hydrogenating according to claim 1, it is characterized in that: described gas-phase reaction product separation goes out after liquid product, after remaining gas-phase reaction product converges, entering recycle hydrogen water cooler (10) further lowers the temperature, the liquid product further forming after cooling flow into finished product holding tank (9), the small portion of residual gas phase reaction product is discharged as the venting of speeding, most of the 3rd feed preheater (5) that enters after circulating hydrogen compressor (11) supercharging.
5. a kind of processing method of ethyl acetate preparation of ethanol by hydrogenating according to claim 1, it is characterized in that: the ethyl acetate in described step 5) in liquid product and ethanol form azeotrope and steamed by product separation tower (12) tower top, steam rear inflow ethyl acetate tundish (1).
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| CN102942446B (en) * | 2012-12-03 | 2015-09-23 | 大唐国际化工技术研究院有限公司 | A kind of method reclaiming the acetic ester preparation of ethanol by hydrogenating of hydrogen recirculation |
| CN103055766B (en) * | 2012-12-12 | 2014-12-31 | 万华化学集团股份有限公司 | Two-section type switchable tubular reactor and method for preparing alcohol through aldehyde gas phase hydrogenation by using same |
| CN105439816B (en) * | 2014-08-27 | 2017-10-27 | 中国石油化工股份有限公司 | Acetic acid ester through hydrogenation produces the process of ethanol |
| CN104857894B (en) * | 2015-05-04 | 2017-08-29 | 河南顺达化工科技有限公司 | A kind of ethanol synthesis reactor with heat-exchange unit |
| CN104860796B (en) * | 2015-05-04 | 2018-03-02 | 河南顺达化工科技有限公司 | A kind of technique with heat-exchange unit synthesizing alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102399130A (en) * | 2011-12-13 | 2012-04-04 | 西南化工研究设计院 | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid |
| CN102421730A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Process for producing an ester feed stream for esters production and co-production of ethanol |
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| US8575403B2 (en) * | 2010-05-07 | 2013-11-05 | Celanese International Corporation | Hydrolysis of ethyl acetate in ethanol separation process |
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| CN102421730A (en) * | 2010-02-02 | 2012-04-18 | 国际人造丝公司 | Process for producing an ester feed stream for esters production and co-production of ethanol |
| CN102399130A (en) * | 2011-12-13 | 2012-04-04 | 西南化工研究设计院 | Method for simplifying rectification process for preparing ethanol through hydrogenation of acetic acid |
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