CN105503526A - Method for producing sec-butyl alcohol and co-producing ethanol through sec-butyl acetate hydrogenation - Google Patents
Method for producing sec-butyl alcohol and co-producing ethanol through sec-butyl acetate hydrogenation Download PDFInfo
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Abstract
The invention relates to a method for producing sec-butyl alcohol and co-producing ethanol through sec-butyl acetate hydrogenation, and is mainly used for solving the problem of relatively high energy consumption and hydrogen consumption in the prior art. The method for producing sec-butyl alcohol and co-producing ethanol through sec-butyl acetate hydrogenation comprises the following steps: (1) making hydrogen and vaporized sec-butyl acetate contact with a copper-containing catalyst in a reactor for a hydrogenation reaction to obtain a material flow containing sec-butyl alcohol and ethanol; and performing two levels of gas-liquid separation to obtain a mixture of crude sec-butyl alcohol and ethanol; (2) treating the mixture of crude sec-butyl alcohol and ethanol by a sec-butyl alcohol-ethanol separation tower to obtain crude sec-butyl alcohol and crude ethanol respectively; and (3) separating the crude ethanol to obtain a product of industrial ethanol or absolute ethanol; and separating the crude sec-butyl alcohol to obtain a product of industrial sec-butyl alcohol. By adopting the technical scheme, the problem is solved relatively well, and the method can be used for producing sec-butyl alcohol and co-producing ethanol through sec-butyl acetate hydrogenation.
Description
Technical field
The present invention relates to a kind of method that 2-butyl acetate hydrogenation produces sec-butyl alcohol co-producing ethanol.
Background technology
One of 2-butyl acetate four isomer belonging to N-BUTYL ACETATE, for colourless, inflammable, are with fruity liquid, and can dissolve various kinds of resin and organism.Usually, 2-butyl acetate is all similar in most instances to the performance of other isomerss, and just it has lower boiling point and evaporation rate faster.At present, 2-butyl acetate is mainly used in the industries such as medicine, coating, ink, tackiness agent, solidifying agent, clean-out system, thinner, production of resins and acetic acid dehydration.
Sec-butyl alcohol (SBA), also known as 2-butanols, is important industrial chemicals and intermediate.Because sec-butyl alcohol can increase processing characteristics and the ductility of coating, therefore can be used as that nitro sprays paint, the solubility promoter of thinner for nitrocellulose finishes.Can be used as again the raw material producing spices, dyestuff, wetting agent, flotation agent etc., also can be used as the intermediate producing methylethylketone.In current industrial production, sec-butyl alcohol is mainly for the preparation of methylethylketone (MEK), and small portion is used as solvent, dressing agent, softening agent, weedicide etc., and methylethylketone is mainly used to produce coating, lube oil finishing solvent and binding agent etc.The production of current sec-butyl alcohol mainly with the n-butene in naphtha cracking ethene and refinery catalytic cracking by-product C 4 fraction for raw material, adopt direct hydration method explained hereafter.
At present, the production of sec-butyl alcohol mainly adopts n-butylene hydration method, comprises indirect hydration and direct hydration two kinds of techniques.Indirect hydration method refers to n-butene sulphating, then obtains sec-butyl alcohol with this sulfuric ester of steam hydrolysis.CN10481296A discloses and utilizes improving one's methods of reactive distillation.This technique, owing to using sulfuric acid, not only there is corrosion of equipment, Waste Sulfuric Acid process, side reaction is many, technical process is complicated shortcoming, and energy consumption is large.Direct hydration method refers to n-butene and water to be reacted under an acidic catalyst effect prepares sec-butyl alcohol.CN101289368 discloses butylene direct hydration method on strong acidic ion resin catalyzer and prepares the technology of isopropylcarbinol.This technique take strong-acid ion exchange resin as catalyzer, 150 ~ 170 DEG C, 5 ~ 7MPa, water/n-butene mol ratio react under being the processing condition of 15:1 ~ 20:1, the per pass conversion of n-butene general only about 6%, a large amount of n-butene circulation, energy consumption is high.CN101395111A discloses one and utilizes heteropoly acid catalysis direct hydration technique, and major ingredient is molybdophosphate, and adds organometallic compound additive.Reactor efficiency is higher; Shortcoming is that reaction pressure is high.
Ethanol is one of basic industry raw material, is widely used in food, chemical industry, military project, medicine and other fields: (1) sterilizing agent; (2) beverage and food; (3) basic chemical raw materials, can produce acetaldehyde, ether, ethyl acetate, the industrial chemicals such as ethamine, are also produce dyestuff, coating, the raw material of the products such as washing composition; (4) thinner, organic solvent, paint solvent etc.; (5) ethanol or a kind of free of contamination high-octane gasoline dope, as automobile fuel, ethanol can call in gasoline.
Because domestic 2-butyl acetate production capacity expansion was rapid in recent years, greatly exceed domestic needs amount, by 2-butyl acetate Hydrogenation sec-butyl alcohol co-producing ethanol route, can the 2-butyl acetate of consume capacity surplus, 2-butyl acetate is converted into the more wide sec-butyl alcohol of market outlook and ethanol, significant.
At present, patent is not had to relate to the concrete technology of 2-butyl acetate Hydrogenation sec-butyl alcohol co-producing ethanol, this patent describes the technique of 2-butyl acetate Hydrogenation sec-butyl alcohol co-producing ethanol in detail, can produce sec-butyl alcohol and ethanol two kinds of products, and fully utilize energy.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art, energy consumption is higher, hydrogen consumption is larger, provides a kind of new 2-butyl acetate hydrogenation to produce the method for sec-butyl alcohol co-producing ethanol.The method has the advantage that energy consumption is lower, hydrogen consumption is less.
For solving the problem, the technical solution used in the present invention is as follows: a kind of 2-butyl acetate hydrogenation produces the method for sec-butyl alcohol co-producing ethanol, comprises following step:
(1) raw hydrogen contacts with copper containing catalyst in hydrogenator with the 2-butyl acetate of vaporization, is obtained by reacting the logistics containing sec-butyl alcohol, ethanol, obtains crude secbutyl alcohol and alcohol mixture after two-stage gas-liquid separation;
(2) described crude secbutyl alcohol obtains crude secbutyl alcohol and coarse ethanol with alcohol mixture after sec-butyl alcohol separation of ethanol tower is separated;
(3) coarse ethanol is separated through alcohol product tower and obtains industrial alcohol or dehydrated alcohol product, and crude secbutyl alcohol is separated through sec-butyl alcohol product tower and obtains industrial sec-butyl alcohol product;
Wherein, described hydrogenator is isothermal fixed-bed reactor or insulation fix bed, and service temperature is 170 ~ 270 DEG C, and the mol ratio of hydrogen and 2-butyl acetate is 2 ~ 60, pressure counts 1 ~ 8MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.3 ~ 3g/ (g catalyzer h).
In technique scheme, preferably, in the gas phase that second stage gas-liquid separation obtains, 90-99.99% feeding circulating hydrogen suction port of compressor storage tank carries out circulation and stress by weight, and all the other gas phases speed to put.
In technique scheme, preferably, the 2-butyl acetate of raw hydrogen and vaporization first and after the heat exchange of hydrogenator outlet streams, is all vaporizated into gas, then enters hydrogenator.
In technique scheme, preferably, service temperature in isothermal fixed-bed reactor described in step (1) or insulation fix bed reactor is 180 ~ 230 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 10 ~ 50, pressure counts 2 ~ 6MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.5 ~ 2g/ (g catalyzer h).
In technique scheme, more preferably, the mol ratio of hydrogen and 2-butyl acetate is 20 ~ 40, and pressure counts 4 ~ 6MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.8 ~ 1.5g/ (g catalyzer h).
In technique scheme, preferably, alcohol product column overhead obtains the azeotrope of EtOH-EtOAc-butanone, and 90-99% is circulated to further hydrogenation ethanol production in step (1) by weight, and all the other carry out liquid waste disposal.
In technique scheme, preferably, sec-butyl alcohol product column overhead obtains sec-butyl alcohol product, and tower reactor obtains the heavy constituent logistics containing 2-butyl acetate, 40-55% is circulated to further hydrogenation ethanol production in step (1) by weight, and all the other carry out liquid waste disposal.
In technique scheme, preferably, alcohol product tower operational condition is: tower top pressure counts 0.08-0.12MPa with gauge pressure, tower top temperature 60-65 DEG C, bottom temperature 75-80 DEG C, reflux ratio 8-12, stage number 35-45.
In technique scheme, preferably, sec-butyl alcohol product tower operational condition is: tower top pressure counts 0.08-0.12MPa with gauge pressure, tower top temperature 95-105 DEG C, bottom temperature 120-125 DEG C, reflux ratio 7-8, stage number 18-22.
The present invention adopts 2-butyl acetate hydrogenation to produce the technical process of sec-butyl alcohol co-producing ethanol and produces sec-butyl alcohol and alcohol product, the parallel feeding of hydrogenation workshop section simultaneously utilizes the heat of thermal response gas to be heated to certain temperature, feeding temperature is heated to again through feed heater, take full advantage of the heat of the thermal response gas produced in reactor, reduce energy consumption.In addition, owing to adopting isothermal fixed-bed reactor or insulation fix bed reactor to carry out hydrogenation reaction in the present invention, hydrogenation reaction can be carried out than under condition at lower hydrogen ester, decrease hydrogen consumption, achieve better technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1,2-butyl acetate; 2, sec-butyl alcohol; 3, ethanol; 4, periodic off-gases; 5, hydrogen make-up; 6, gas is discharged; 7, the azeotrope waste liquid of EtOH-EtOAc-butanone; 8, containing the heavy constituent waste liquid of 2-butyl acetate.
Circulating hydrogen enters circulating hydrogen compressor CP301 through circulating hydrogen suction port of compressor storage tank D305, is then mixed to get reaction hydrogen with the hydrogen make-up 5 from hydrogen make-up compressor CP302 at compressor outlet surge tank D306.2-butyl acetate 1, as raw material, with the recycle stream containing 2-butyl acetate and ethanol etc. after head tank D101 mixes, mixes with reaction hydrogen through 2-butyl acetate fresh feed pump P301, obtains parallel feeding.Parallel feeding, after reaction product/feed exchanger E302, enters hydrogenator R301 after feed heater E301 heating.Parallel feeding, under catalyst action, except generating principal product sec-butyl alcohol and ethanol, also generates by product butanone, ethyl acetate, acetaldehyde etc.
Hydrogenator R301 reaction product gas out, after reaction product/feed exchanger E302 and parallel feeding heat exchange, then cools through reaction product water cooler E303, liquid separation circuit of supplying gas.In gas-liquid separation operation, first after one-level gas-liquid separator D303 is separated, gas phase cools through water cooler E304 again, send secondary gas-liquid separator D304, and liquid phase send gas product liquid/gas separator D307.Secondary gas-liquid separator D304 gas phase major part is sent into circulating hydrogen suction port of compressor storage tank D305 and is carried out circulation and stress, and small part speeds to put as periodic off-gases 4, and liquid phase then sends into gas product liquid/gas separator D307.The gas phase that D307 is separated is carried out gas as discharge gas 6 and is speeded to put, and liquid phase is then the thick product of liquid phase containing sec-butyl alcohol and ethanol, sends into product separation operation and is separated.
From the thick product of liquid phase containing sec-butyl alcohol and ethanol of hydrogenation workshop section gas-liquid separation operation, first enter sec-butyl alcohol separation of ethanol tower T301.Thick product is after rectifying tower is separated, and tower top distillates the logistics containing light constituents such as lighter hydrocarbons, acetaldehyde, methyl alcohol, ethyl ester, ethanol, butanone, after sec-butyl alcohol separation of ethanol column overhead water cooler E306 condensing cooling, send alcohol product tower T303.The tower reactor component of sec-butyl alcohol separation of ethanol tower T301 is mainly sec-butyl alcohol, secondary butyl ester, propyl carbinol, C6 alcohol etc., and sec-butyl alcohol product tower T302 is sent in tower reactor logistics.Alcohol product tower T303 tower reactor obtains ethanol 3 product, and tower top obtains the azeotrope of EtOH-EtOAc-butanone, and major part is circulated to D101 and continues to participate in reaction, and small part discharge is carried out waste liquid 7 and processed.Sec-butyl alcohol product tower T302 tower top obtains sec-butyl alcohol 2 product, and tower reactor obtains the logistics containing heavy constituents such as 2-butyl acetates, and major part is circulated to D101 and continues to participate in reaction, and liquid waste disposal is carried out in small part discharge.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Technical process is as follows:
Circulating hydrogen enters circulating hydrogen compressor CP301 through circulating hydrogen suction port of compressor storage tank D305, is then mixed to get reaction hydrogen with the hydrogen make-up from hydrogen make-up compressor CP302 at compressor outlet surge tank D306.2-butyl acetate, as raw material, with the recycle stream containing 2-butyl acetate and ethanol etc. after head tank D101 mixes, boosts to 4MPa through 2-butyl acetate fresh feed pump P301, mixes, obtain parallel feeding with reaction hydrogen.Parallel feeding, after reaction product/feed exchanger E302, is all vaporizated into gas, and the temperature out of parallel feeding about 170 DEG C.The parallel feeding being vaporizated into gas is heated to temperature about 190 DEG C through feed heater E301, enters hydrogenator R301.
Copper-based catalysts is adopted in R301, R301 is insulation fix bed reactor, and service temperature is 210 DEG C, and the mol ratio (being called for short hydrogen ester ratio) of hydrogen and 2-butyl acetate is 30, pressure counts 4MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 1.0g/ (g catalyzer h).Parallel feeding, under catalyst action, except generating principal product sec-butyl alcohol and ethanol, also generates by product butanone, ethyl acetate, acetaldehyde etc.2-butyl acetate transformation efficiency is 98.8%, and ethanol selectivity is 97.6%, and sec-butyl alcohol selectivity is 95.8%.
Hydrogenator R301 reaction product gas out, after reaction product/feed exchanger E302 and parallel feeding heat exchange, then cools through reaction product water cooler E303, liquid separation circuit of supplying gas.In gas-liquid separation operation, first after one-level gas-liquid separator D303 is separated, gas phase cools through water cooler E304 again, send secondary gas-liquid separator D304, and liquid phase send gas product liquid/gas separator D307.In the gas phase that secondary gas-liquid separator D304 obtains, 99.8% feeding circulating hydrogen suction port of compressor storage tank D305 carries out circulation and stress by weight, and all the other speed to put, and liquid phase then sends into gas product liquid/gas separator D307.The gas phase that D307 is separated is carried out gas and is speeded to put, and liquid phase is then the thick product of liquid phase containing sec-butyl alcohol and ethanol, sends into product separation operation and is separated.
From the thick product of liquid phase containing sec-butyl alcohol and ethanol of hydrogenation workshop section gas-liquid separation operation, first enter sec-butyl alcohol separation of ethanol tower T301 (working pressure counts 0.1MPa with gauge pressure).Thick product is after rectifying tower is separated, tower top distillates the logistics containing light constituents such as lighter hydrocarbons, acetaldehyde, methyl alcohol, ethyl ester, ethanol, butanone, after sec-butyl alcohol separation of ethanol column overhead water cooler E306 condensing cooling, send alcohol product tower T303 (working pressure counts 0.1MPa with gauge pressure, tower top temperature 62.5 DEG C, bottom temperature 78.3 DEG C, reflux ratio 10.1, stage number 40).The tower reactor component of sec-butyl alcohol separation of ethanol tower T301 is mainly sec-butyl alcohol, secondary butyl ester, propyl carbinol, C6 alcohol etc., sec-butyl alcohol product tower T302 is sent in tower reactor logistics, and (working pressure counts 0.1MPa with gauge pressure, tower top temperature 99.6 DEG C, bottom temperature 123 DEG C, reflux ratio 7.8, stage number 20).Alcohol product tower T303 tower reactor obtains alcohol product, and tower top obtains the azeotrope of EtOH-EtOAc-butanone, and 98.1% be circulated to D101 continuation participation reaction by weight, liquid waste disposal is carried out in all the other discharges.Sec-butyl alcohol product tower T302 tower top obtains sec-butyl alcohol product, and tower reactor obtains the logistics containing heavy constituents such as 2-butyl acetates, and 54.3% be circulated to D101 continuation participation reaction by weight, all the other carry out liquid waste disposal.
[embodiment 2]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 180 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 30, pressure counts 2MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 1.0g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 98.36%, ethanol selectivity is 99.25%, and sec-butyl alcohol selectivity is 95.91%.
[embodiment 3]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 220 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 30, pressure counts 5MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 0.8g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 99.2%, ethanol selectivity is 97.88%, and sec-butyl alcohol selectivity is 95.32%.
[embodiment 4]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 170 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 2, pressure counts 6MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 3g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 91.5%, ethanol selectivity is 99.51%, and sec-butyl alcohol selectivity is 96.12%.
[embodiment 5]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 170 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 2, pressure counts 6MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 0.3g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 95.6%, ethanol selectivity is 99.23%, and sec-butyl alcohol selectivity is 96.05%.
[embodiment 6]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 270 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 60, pressure counts 6MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 0.3g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 99.7%, ethanol selectivity is 95.12%, and sec-butyl alcohol selectivity is 93.25%.
[embodiment 7]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 230 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 40, pressure counts 5MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 2g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 98.8%, ethanol selectivity is 96.85%, and sec-butyl alcohol selectivity is 96.18%.
[embodiment 8]
According to the condition described in embodiment 1 and step, just R201 is insulation fix bed reactor, service temperature is 180 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 10, pressure counts 8MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 0.5g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 96.3%, ethanol selectivity is 99.25%, and sec-butyl alcohol selectivity is 96.08%.
[embodiment 9]
According to the condition described in embodiment 1 and step, just R201 is isothermal fixed-bed reactor, service temperature is 230 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 20, pressure counts 1MPa with gauge pressure, and 2-butyl acetate liquid hourly space velocity is 0.5g/ (g catalyzer h), and 2-butyl acetate transformation efficiency is 95.3%, ethanol selectivity is 98.06%, and sec-butyl alcohol selectivity is 95.08%.
[embodiment 10]
According to the condition described in embodiment 1 and step, just 97.5% send into circulating hydrogen suction port of compressor storage tank D305 and carry out circulation and stress by weight in the gas phase that obtains of secondary gas-liquid separator D304, all the other speed to put.Alcohol product tower T303 tower reactor obtains alcohol product, and tower top obtains the azeotrope of EtOH-EtOAc-butanone, and 96.3% be circulated to D101 continuation participation reaction by weight, liquid waste disposal is carried out in all the other discharges.Sec-butyl alcohol product tower T302 tower top obtains sec-butyl alcohol product, and tower reactor obtains the logistics containing heavy constituents such as 2-butyl acetates, and 49.5% be circulated to D101 continuation participation reaction by weight, all the other carry out liquid waste disposal.
Alcohol product tower T303 (working pressure counts 0.1MPa with gauge pressure, tower top temperature 63.5 DEG C, bottom temperature 78.6 DEG C, reflux ratio 9.8, stage number 40).Sec-butyl alcohol product tower T302 (working pressure counts 0.1MPa with gauge pressure, tower top temperature 99.5 DEG C, bottom temperature 122.9 DEG C, reflux ratio 7.9, stage number 20).
[embodiment 11]
According to the condition described in embodiment 1 and step, just 95.5% send into circulating hydrogen suction port of compressor storage tank D305 and carry out circulation and stress by weight in the gas phase that obtains of secondary gas-liquid separator D304, all the other speed to put.Alcohol product tower T303 tower reactor obtains alcohol product, and tower top obtains the azeotrope of EtOH-EtOAc-butanone, and 92.5% be circulated to D101 continuation participation reaction by weight, liquid waste disposal is carried out in all the other discharges.Sec-butyl alcohol product tower T302 tower top obtains sec-butyl alcohol product, and tower reactor obtains the logistics containing heavy constituents such as 2-butyl acetates, and 45.5% be circulated to D101 continuation participation reaction by weight, all the other carry out liquid waste disposal.
Alcohol product tower T303 (working pressure counts 0.08MPa with gauge pressure, tower top temperature 63.8 DEG C, bottom temperature 78.8 DEG C, reflux ratio 9.2, stage number 40).Sec-butyl alcohol product tower T302 (working pressure counts 0.08MPa with gauge pressure, tower top temperature 99.4 DEG C, bottom temperature 122.8 DEG C, reflux ratio 7.5, stage number 20).
[embodiment 12]
According to the condition described in embodiment 1 and step, just 90% send into circulating hydrogen suction port of compressor storage tank D305 and carry out circulation and stress by weight in the gas phase that obtains of secondary gas-liquid separator D304, all the other speed to put.Alcohol product tower T303 tower reactor obtains alcohol product, and tower top obtains the azeotrope of EtOH-EtOAc-butanone, and 90% be circulated to D101 continuation participation reaction by weight, liquid waste disposal is carried out in all the other discharges.Sec-butyl alcohol product tower T302 tower top obtains sec-butyl alcohol product, and tower reactor obtains the logistics containing heavy constituents such as 2-butyl acetates, and 40% be circulated to D101 continuation participation reaction by weight, all the other carry out liquid waste disposal.
Alcohol product tower T303 (working pressure counts 0.12MPa with gauge pressure, tower top temperature 64.5 DEG C, bottom temperature 78.9 DEG C, reflux ratio 8.5, stage number 40).Sec-butyl alcohol product tower T302 (working pressure counts 0.12MPa with gauge pressure, tower top temperature 99.2 DEG C, bottom temperature 122.7 DEG C, reflux ratio 6.8, stage number 20).
[comparative example]
According to the condition described in embodiment 1 and step, just the mol ratio of hydrogen and 2-butyl acetate is under the condition of 60, and not only hydrogen consumption is large, and the energy consumption of ton product increases by 13%.
Obviously, adopt method of the present invention, adopt 2-butyl acetate hydrogenation to produce the technical process of sec-butyl alcohol co-producing ethanol and produce sec-butyl alcohol and alcohol product, the parallel feeding of hydrogenation workshop section simultaneously utilizes the heat of thermal response gas to be heated to certain temperature, feeding temperature is heated to again through feed heater, take full advantage of the heat of the thermal response gas produced in reactor, reduce energy consumption.In addition, owing to adopting isothermal fixed-bed reactor or insulation fix bed reactor to carry out hydrogenation reaction in the present invention, hydrogenation reaction can be carried out than under condition at lower hydrogen ester, decrease hydrogen consumption, achieve better technique effect, can be used in industrial production.
Claims (9)
1. 2-butyl acetate hydrogenation produces a method for sec-butyl alcohol co-producing ethanol, comprises following step:
(1) raw hydrogen contacts with copper containing catalyst in hydrogenator with the 2-butyl acetate of vaporization, is obtained by reacting the logistics containing sec-butyl alcohol, ethanol, obtains crude secbutyl alcohol and alcohol mixture after two-stage gas-liquid separation;
(2) described crude secbutyl alcohol obtains crude secbutyl alcohol and coarse ethanol with alcohol mixture after sec-butyl alcohol separation of ethanol tower is separated;
(3) coarse ethanol is separated through alcohol product tower and obtains industrial alcohol or dehydrated alcohol product, and crude secbutyl alcohol is separated through sec-butyl alcohol product tower and obtains industrial sec-butyl alcohol product;
Wherein, described hydrogenator is isothermal fixed-bed reactor or insulation fix bed, and service temperature is 170 ~ 270 DEG C, and the mol ratio of hydrogen and 2-butyl acetate is 2 ~ 60, pressure counts 1 ~ 8MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.3 ~ 3g/ (g catalyzer h).
2. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that in the gas phase that second stage gas-liquid separation obtains, 90-99.99% feeding circulating hydrogen suction port of compressor storage tank carries out circulation and stress by weight, all the other gas phases speed to put.
3. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, and the 2-butyl acetate that it is characterized in that raw hydrogen and vaporization first and after the heat exchange of hydrogenator outlet streams, is all vaporizated into gas, then enters hydrogenator.
4. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that the service temperature in the isothermal fixed-bed reactor described in step (1) or insulation fix bed reactor is 180 ~ 230 DEG C, the mol ratio of hydrogen and 2-butyl acetate is 10 ~ 50, pressure counts 2 ~ 6MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.5 ~ 2g/ (g catalyzer h).
5. 2-butyl acetate hydrogenation according to claim 4 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that the mol ratio of hydrogen and 2-butyl acetate is 20 ~ 40, pressure counts 4 ~ 6MPa with gauge pressure, 2-butyl acetate liquid hourly space velocity 0.8 ~ 1.5g/ (g catalyzer h).
6. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that alcohol product column overhead obtains the azeotrope of EtOH-EtOAc-butanone, 90-99% is circulated to further hydrogenation ethanol production in step (1) by weight, and all the other carry out liquid waste disposal.
7. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that sec-butyl alcohol product column overhead obtains sec-butyl alcohol product, tower reactor obtains the heavy constituent logistics containing 2-butyl acetate, 40-55% is circulated to further hydrogenation ethanol production in step (1) by weight, and all the other carry out liquid waste disposal.
8. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that alcohol product tower operational condition is: tower top pressure counts 0.08-0.12MPa with gauge pressure, tower top temperature 60-65 DEG C, bottom temperature 75-80 DEG C, reflux ratio 8-12, stage number 35-45.
9. 2-butyl acetate hydrogenation according to claim 1 produces the method for sec-butyl alcohol co-producing ethanol, it is characterized in that sec-butyl alcohol product tower operational condition is: tower top pressure counts 0.08-0.12MPa with gauge pressure, tower top temperature 95-105 DEG C, bottom temperature 120-125 DEG C, reflux ratio 7-8, stage number 18-22.
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| CN110639623A (en) * | 2019-11-12 | 2020-01-03 | 淄博齐翔腾达化工股份有限公司 | Activation method and reaction device for preparing methyl ethyl ketone catalyst by sec-butyl alcohol dehydrogenation |
| CN114436850A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for co-producing monoethylamine and sec-butylamine by supergravity method |
| CN115894171A (en) * | 2022-11-17 | 2023-04-04 | 凯瑞环保科技股份有限公司 | Method for preparing sec-butyl alcohol by sec-butyl acetate hydrogenation |
| CN115974660A (en) * | 2022-12-15 | 2023-04-18 | 湖南中创化工股份有限公司 | Method for preparing methyl ethyl ketone by taking sec-butyl acetate as raw material |
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