CN106995363B - A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid - Google Patents

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid Download PDF

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CN106995363B
CN106995363B CN201610053243.0A CN201610053243A CN106995363B CN 106995363 B CN106995363 B CN 106995363B CN 201610053243 A CN201610053243 A CN 201610053243A CN 106995363 B CN106995363 B CN 106995363B
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acetic acid
reactor
ethyl alcohol
hydrogen
reaction
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CN201610053243.0A
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CN106995363A (en
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汤广斌
潘科
甘道才
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河南顺达化工科技有限公司
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a kind of hydrogenation coupled techniques for preparing ethyl alcohol of acetic acid, add hydrogen, secondary plus three steps of hydrogen including acetic synthesis, acetic acid.For acetic synthesis step using methanol and CO as raw material, cycle prepares acetic acid;Acetic acid hydrogenation step carries out catalytic hydrogenation using acetic acid and hydrogen as raw material, and ethyl alcohol is made;Secondary hydrogenation step carries out secondary plus hydrogen using the hydrogen rich off gas of acetic acid hydrogenation step, acetic acid/acetate as raw material, and the secondary tail gas of generation sends acetic acid hydrogenation step back to after recycle compressor pressurizes, mixes with fresh hydrogen and is used as raw material.Present invention process can make hydrogen obtain deep reaction, and gas circulation amount is reduced, and low energy consumption, and hydracid ratio can be controlled within 60, and raw material has higher conversion ratio and yield, and the conversion per pass of acetic acid is up to more than 99%, and ethanol selectivity is up to more than 95%;The continuity of operation and stability of technique are all very high, and the investment of same size production capacity is greatly lowered, and energy consumption reduces by more than 15% compared with common process energy consumption.

Description

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid

Technical field

The present invention relates to a kind of hydrogenation coupled techniques for preparing ethyl alcohol of acetic acid, belong to ethyl alcohol preparation process.

Background technology

Ethyl alcohol is the main component for finding a kind of fatty alcohol earliest, that purposes is most wide and wine.Ethyl alcohol is nothing at room temperature Color, volatile, inflammable liquid.Ethyl alcohol it is widely used, such as can be used for produce acetaldehyde, ether, ethyl acetate, ethamine, A variety of industrial chemicals such as ethylene oxide, in disinfectant, beverage, diluent, environmental protection coating material, pesticide, medicine, rubber, plastics, artificial The multiple fields such as fiber, detergent are all widely used.

At present, the industrial process of ethyl alcohol mainly has fermentation method and ethylene hydration method.The primary raw material of fermentation method is beautiful The crops such as rice, sugarcane, sorghum, cassava, paddy obtain ethyl alcohol by using the amylofermentation in crops;But fermentation method meeting A large amount of grain is consumed, cost is too high.Ethylene hydration method is developed along with the rise of petrochemical industry, including indirect hydration Method and direct hydration method;But due to the continuous improvement of production cost of ethylene, in China, ethylene legal system ethyl alcohol is substantially at End-of-life state.

In recent years, with the fast development of methanol carbonyl technology, acetate yield significantly improves, and the price of acetic acid drops significantly It is low.Acetic acid is as a kind of important industrial chemicals, although having in the industries such as industrial chemicals preparation, pesticide, medicine intermediate wide General application, but acetic acid production capacity still has very big surplus, has the exploitation of purposes extremely urgent under Dichlorodiphenyl Acetate.

There are two types of the approach that ethyl alcohol is produced using acetic acid as raw material, first, acetic acid direct hydrogenation generates ethyl alcohol;It is another It is that acetic acid first generates acetate, then be hydrogenated to ethyl alcohol by acetate after esterification.In first method, the corrosivity of acetic acid makes Higher corrosion resistance must be had, and catalysts are expensive by obtaining catalytic hydrogenation reaction device so that production cost is high.With A kind of method is compared, and the more step esterification process of second method although reducing corrosivity of the acetic acid to reactor, need Product ethanol cycle is esterified as esterification feed, accordingly increases the size of reactor, and catalytic hydrogenation high energy consumption.

Therefore, how to reduce alcohol production energy consumption, the utilization rate for improving raw material, it made to be more suitable for industrialized production, It is current urgent problem to be solved.

Invention content

To solve the above problem of the existing technology, the purpose of the present invention is to provide a kind of energy consumption is low, raw material The hydrogenation coupled technique for preparing ethyl alcohol of acetic acid that utilization rate is high, reaction yield is high.

To achieve the above object, the technical solution adopted in the present invention is:

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid prepares ethyl alcohol using methanol and CO as starting reaction raw materials, including Acetic synthesis, acetic acid add hydrogen, secondary plus three steps of hydrogen.

The detailed process of the technique includes:

A, acetic synthesis

Methanol is sent into the top of reactor I, high-purity CO is sent into the bottom of reactor I, main reminder is carbonylated in reactor I Carbonylation is carried out under the catalysis of agent and co-catalyst, generates acetic acid crude product;Gained acetic acid crude product is arranged by I top of reactor Go out, detach co-catalyst, acquired acetic acid is sent directly into reactor II, and the co-catalyst isolated comes back to I bottom of reactor Portion carries out cycle catalysis;

B, acetic acid adds hydrogen

Acetic acid and fresh H obtained by step A2Be admitted to the bottom of reactor II together, under the action of hydrogenation catalyst into Row catalytic hydrogenation reaction, generation ethyl alcohol;The liquid ethanol crude product isolated is produced from II lower part of reactor, is then sent directly into second Alcohol rectification step is purified;Hydrogen rich off gas carries out secondary plus hydrogen by overhead extraction, the feeding reactor III of reactor II;

C, secondary plus hydrogen

The hydrogen rich off gas and raw material acetic acid/acetate that are produced by II top of reactor are admitted to the bottom of reactor III together Portion carries out catalytic hydrogenation reaction, generation ethyl alcohol under the action of hydrogenation catalyst;The coarse ethanol isolated is from III lower part of reactor Ethyl alcohol rectification step is sent directly into after extraction to be purified;Tail gas from the overhead extraction of reactor III, by recycle compressor plus The bottom of towe of reactor II is sent after pressure back to again, with fresh H2Mixing is as the unstripped gas of step B, progress acetic acid adds hydrogen anti-again Should, realize process cycles;

Reaction pressure, the reaction temperature of the reactor III are below the reaction pressure of reactor II, reaction temperature.

In the step A, the raw materials components mole ratio of CO and methanol is 0.5:1~3:1, carbonylation major catalyst is catalyzed for rhodium system Agent, co-catalyst are iodide;The pressure of carbonylation is 2.0~5.0MPa, temperature is 170~250 DEG C.

In the step B, the reaction pressure of catalytic hydrogenation is 2.0~5.0MPa, reaction temperature is 250~400 DEG C.

In the step C, the raw material of secondary hydrogenation reaction may be selected from:1. vinegar made from the hydrogen rich off gas of step B and step A The hydrogen rich off gas and acetate of acid product, 2. step B.The hydrogen rich off gas temperature control is sent into reactor after 120~300 DEG C Ⅲ;Secondary plus hydrogen reaction temperature is 200~300 DEG C, and reaction pressure is 1.5~4.5MPa;After secondary hydrogenation reaction, not The secondary tail gas of reaction sends the bottom of towe of reactor II back to again after recycle compressor is pressurized to 2.0~5.0MPa.

For recycling the cooling coil of reaction heat, deoxygenated water is absorbed by cooling coil tube wall for setting in the reactor III Reaction heat, the steam that by-product pressure is 2.1~13.1MPa.

The beneficial effects of the invention are as follows:

The present invention provides a kind of hydrogenation coupled techniques for preparing ethyl alcohol of acetic acid, using methanol and CO as raw material, pass through acetic acid Synthesis, acetic acid add hydrogen, secondary plus three steps of hydrogen, are prepared into the alcohol product of high-purity.The technique can make hydrogen obtain depth Degree reaction, gas circulation amount are reduced, and low energy consumption, and hydracid ratio can be controlled within 60, and raw material has higher conversion ratio and receipts Rate, continuity of operation and stability are all very high, and the investment of same size production capacity is greatly lowered;And to reaction end gas and reaction heat Rational recycling is all carried out, unreacted tail gas re-starts cycle plus hydrogen, improves feed stock conversion, reduces waste Discharge capacity, and by-product high-quality steam simultaneously increase factory's added value.The present invention couples two steps, ensure that anti- The depth answered, the conversion per pass of acetic acid are up to more than 99%, and ethanol selectivity is up to more than 95%, and energy consumption is compared with common process energy Consumption reduces by more than 15%.

In the acetic synthesis step of the present invention, reaction product only needs to detach iodide, can be used as the anti-of catalytic hydrogenation Raw material is answered, does not need to carry out the depth purification of acetic acid, significantly reduces production difficulty, reduce equipment investment;Reaction product detaches The iodide gone out are sent reactor I back to and are catalyzed again, ensure catalytic effect, the service efficiency for improving catalyst;The iodine of separation The complete raw material of the unreacted of entrained with also circular response, avoids wastage of material in compound.The preparation process need not add in water and do Solvent, energy consumption are low.

Rich in hydrogen and the complete acetic acid of unreacted in the tail gas that the acetic acid hydrogenation step of the present invention is isolated, carried out Secondary hydrogenation reaction improves the utilization rate of hydrogen, reduces gas circulation amount, reduces energy consumption.

The secondary hydrogenation step of the present invention is using the hydrogen rich off gas that acetic acid hydrogenation step generates as one of raw material, another raw material Can acetic acid or acetate be selected according to the practical condition of factory, flexibly and easily.Generated secondary tail gas is compressed through cycle Acetic acid hydrogenation step circular response is sent back to after machine pressurization, further improves the utilization rate of hydrogen and acetic acid.Reactor III is set Be useful for recycling reaction heat coil pipe, be on the one hand conducive to keep reactor III in reaction bed temperature it is constant, convenient for technique Control ensures the stabilization of reaction process and product quality, on the other hand can simultaneously a large amount of pressure of by-product up to 2.1~13.1MPa High-grade steam, provide heat source for other workshop sections of factory.

The present invention pressurizes to secondary tail gas, its pressure is made to be sent back to again instead after reaching the reaction pressure of acetic acid hydrogenation reaction Device II is answered, the pressure and heat to secondary tail gas have carried out rational recycling, and gas circulation amount is few, the work(of compressor Consumption is very low.The pressure of the acetic acid hydrogenation reaction is higher than the pressure of secondary hydrogenation reaction, rational technology coupling, therefore saves and follow The investment of ring compressor and circulation power, further reduced energy consumption.

The obtained ethyl alcohol crude product purity of the present invention is high, and rectifying difficulty is low, and with higher temperature, into rectification section Afterwards without being preheated again, rectification section energy consumption is reduced.

Description of the drawings

Fig. 1 is present invention process flow diagram;

Wherein, 1, reactor I, 2, reactor II, 3, reactor III, 4, recycle compressor, 5, drum, 6, Iodide separation Device.

Specific embodiment

The present invention is described in further detail below by specific embodiment, but embodiment is not the scope of the present invention Limitation.

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid, using methanol and CO as starting material prepare acetic acid, again with acetic acid/ Acetate prepares ethyl alcohol for raw material, which includes acetic synthesis, acetic acid adds hydrogen, secondary plus three steps of hydrogen.The technique Detailed process includes:

A, acetic synthesis

The reaction raw materials of step A are methanol and CO, and carbonylating catalyst is rhodium series catalysts, and co-catalyst is iodide.

Methanol is sent into the top of reactor I, high-purity CO is sent into the bottom of reactor I, the major catalyst rhodium in reactor I Carbonylation, generation acetic acid are carried out under the catalysis of based compound and co-catalyst iodide;Carbonylation pressure 2.0~ 5.0MPa, reaction temperature are 170~250 DEG C.Gained acetic acid crude product is discharged by I top of reactor, after separation iodide, is sent Enter step B and carry out hydrogenation reaction, without being further carried out refined purification;It is not anti-that part is still entrained in the iodide isolated The raw material answered sends back to I bottom of reactor again, and iodide continue to react as co-catalyst catalyzed carbonylation, unreacted Feedstock circulation reaction, the utilization rate for improving raw material.

The rhodium series catalysts are preferably rhodium chloride, and iodide are preferably an iodomethane;The pressure of carbonylation is excellent 3.5~4.5MPa is selected as, reaction temperature is preferably 180~220 DEG C.

B, acetic acid adds hydrogen

The reaction raw materials of step B are the acetic acid from step A and fresh H2, reactor used II is Chinese patent The synthesis reactor that charging medium is heated using autoreactivity heat disclosed in CN104826557A.

Acetic acid and fresh H2 are admitted to the bottom of reactor II together, and catalytic hydrogenation is carried out under the action of hydrogenation catalyst Reaction, generation ethyl alcohol;Acetic acid hydrogenation reaction pressure is 2.0~5.0MPa, reaction temperature is 250~400 DEG C.The liquid isolated Ethyl alcohol crude product produces from II lower part of reactor and then is sent directly into ethyl alcohol rectification section and purified, and alcohol product to be achieved refers to Up to ethyl alcohol finished product after mark;Hydrogen rich off gas includes the complete acetic acid of unreacted and hydrogen, by the overhead extraction of reactor II, send The reactor III for entering step C carries out secondary plus hydrogen;

The fresh hydrogen is high pressure hydrogen, and high pressure hydrogen pressure is 2.0~3.5MPa, temperature is 20~35 DEG C;Reaction Catalyst is noble metal catalyst;It is preferably 300~350 DEG C that reaction pressure, which is preferably 2.5~4.5MPa, reaction temperature,.

C, secondary plus hydrogen

The reaction raw materials of secondary hydrogenation reaction may be selected two kinds, 1. the hydrogen rich off gas of step B, acetic acid production made from step A Product, the 2. hydrogen rich off gas of step B, the acetate from other workshop sections or outsourcing.Reactor III is Chinese patent Ethyl alcohol disclosed in CN204638162U is around pipe synthesis reactor.

When 1. carrying out secondary hydrogenation reaction using raw material, reaction process is:

The product rich in hydrogen produced by II top of reactor is controlled in acetic acid made from 120~300 DEG C and step A Product is admitted to the bottom of reactor III together, carries out catalytic hydrogenation reaction, generation ethyl alcohol under the effect of the catalyst, and catalysis adds Hydrogen reaction temperature is 200~300 DEG C, and pressure is 1.5~4.5MPa;Coarse ethanol is sent directly into second after being produced from III lower part of reactor Alcohol rectification section is purified, and up to ethyl alcohol finished product after alcohol product index to be achieved, is sold;Unreacted tail gas is from anti- After the overhead extraction for answering device III, sent back to again after recycle compressor is forced into 2.0~5.0MPa reactor II bottom of towe, with Fresh H2Acetic acid hydrogenation reaction is carried out after mixing again, realizes process cycles.

When 2. carrying out secondary hydrogenation reaction with raw material, reaction process is:

The product rich in hydrogen produced by II top of reactor controls the bottom that reactor III is admitted at 120~300 DEG C Portion, acetate sterling are admitted to the top of reactor III, and catalytic hydrogenation reaction, generation second are carried out under the action of hydrogenation catalyst Alcohol, catalytic hydrogenation reaction temperature are 200~300 DEG C, and pressure is 1.5~4.5MPa;Coarse ethanol is produced from from III lower part of reactor After be sent directly into ethyl alcohol rectification section, up to ethyl alcohol finished product after alcohol product index to be achieved, sold;Unreacted tail gas After the overhead extraction of reactor III, the tower of reactor II is sent back to again after recycle compressor is forced into 2.0~5.0MPa Bottom and fresh H2Acetic acid hydrogenation reaction is carried out after mixing again, realizes process cycles.

Acetic acid catalyst for hydrogenation is noble metal catalyst;Reaction pressure is preferably that 2.0~3.5MPa, reaction temperature are excellent It is selected as 220~260 DEG C.

The catalytic hydrogenation reaction is exothermic reaction, and reaction heat is about 43.9kJ/mol;It is effective in order to be carried out to reaction heat On the one hand recycling, the interior setting cooling tube of reactor III, deoxygenated water are conducive to keep anti-by the tube wall absorbing reaction heat of cooling tube The constant of reaction bed temperature in device III is answered, convenient for technology controlling and process, ensures reaction process and product quality, on the other hand, deoxidation Steam is vaporizated into after water heat absorption, steam pressure serves many purposes in the factory up to 2.1~13.1MPa.

In the present invention, acetic acid hydrogenation reaction unit can independently be used as ethyl alcohol synthetic reaction device and ethyl alcohol rectifier unit Collectively constitute the ethanol production process system of complete set;Secondary hydrogenation reaction unit also can be filled independently as ethyl alcohol synthetic reaction Put and ethyl alcohol rectifier unit composition complete set ethanol production process system;When acetic acid hydrogenation reaction unit and secondary plus hydrogen When reaction member coupling shares, a set of ethyl alcohol rectifier unit can be shared and carry out ethyl alcohol purification.It is all provided between reaction unit of the present invention Valve is put, flexible combination can be carried out according to factory's practical condition, it is applied widely.

Embodiment 1

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid prepares acetic acid, again with acetic acid using methanol and CO as starting material Ethyl alcohol is prepared for raw material.Specific embodiment is as follows:

A, acetic synthesis

Methanol is sent into the top of reactor I, high-purity CO is sent into the bottom of reactor I, the catalyst trichlorine in reactor I Change and carbonylation, generation acetic acid are carried out under the catalysis of one iodomethane of rhodium and co-catalyst;Carbonylation pressure 3.5~ 4.5MPa, reaction temperature are 180~200 DEG C.Gained acetic acid crude product is discharged by I top of reactor, after separation iodide, is sent into step Rapid B carries out hydrogenation reaction;The iodide isolated send back to the reaction of I bottom cycle of reactor again.

B, acetic acid adds hydrogen

Step A is produced into acetic acid and fresh H2It is sent into the bottom of reactor II together, under the action of noble metal catalyst Carry out catalytic hydrogenation reaction, generation ethyl alcohol;Acetic acid hydrogenation reaction pressure is 3.0~4.0MPa, reaction temperature is 300~350 DEG C. The liquid ethanol crude product isolated produces from II lower part of reactor and then is sent directly into ethyl alcohol rectification section and purified, and waits to reach Up to ethyl alcohol finished product after to alcohol product index;Hydrogen rich off gas includes the complete acetic acid of unreacted and hydrogen, by reactor II Overhead extraction, the reactor III for being sent into step C carries out secondary plus hydrogen;

C, secondary plus hydrogen

Acetate products made from step A and 120~300 DEG C of hydrogen rich off gas are admitted to the bottom of reactor III together, Catalytic hydrogenation reaction, generation ethyl alcohol are carried out under the action of noble metal catalyst, catalytic hydrogenation reaction temperature is 220~250 DEG C, pressure Power is 2.0~2.5MPa;Coarse ethanol is sent directly into ethyl alcohol rectification section after being produced from III lower part of reactor and is purified, to be achieved Up to ethyl alcohol finished product after alcohol product index, sold;Unreacted tail gas is after the overhead extraction of reactor III, by following Ring compressor is forced into the bottom of towe for sending reactor II after 2.5~3.5MPa back to again and fresh H2Acetic acid is carried out after mixing again Hydrogenation reaction realizes process cycles.

Embodiment 2

The present embodiment to the comparative example of embodiment 1, raw materials used, catalyst, reaction unit, reaction condition with reality It is identical to apply example 1, difference lies in:Be not provided with recycle compressor between reactor II and reactor III, reactor III generate two Secondary tail gas is directly entered emission-control equipment, not circular response.

Embodiment 3

A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid, ethyl alcohol is prepared using methanol and CO as starting material, the technique packet Include acetic synthesis, acetic acid adds hydrogen, secondary plus three steps of hydrogen.The detailed process of the technique includes:

A, acetic synthesis

Methanol is sent into the top of reactor I, high-purity CO is sent into the bottom of reactor I, the major catalyst three in reactor I Carbonylation, generation acetic acid are carried out under the catalysis of one iodomethane of radium chloride and co-catalyst;Carbonylation pressure 3.5~ 4.5MPa, reaction temperature are 180~220 DEG C.Gained acetic acid crude product is discharged by I top of reactor, after separation iodide, is sent into step Rapid B carries out hydrogenation reaction;The iodide isolated send back to the reaction of I bottom cycle of reactor again.

B, acetic acid adds hydrogen

Step A is produced into acetic acid and fresh H2It is admitted to the bottom of reactor II together, in the effect of noble metal catalyst Lower progress catalytic hydrogenation reaction, generation ethyl alcohol;Acetic acid hydrogenation reaction pressure is 3.0~4.0MPa, reaction temperature is 300~350 ℃.The liquid ethanol crude product isolated produces from II lower part of reactor and then is sent directly into ethyl alcohol rectification section and purified, and treats Reach after alcohol product index up to ethyl alcohol finished product, sold;Hydrogen rich off gas includes the complete acetic acid of unreacted and hydrogen, By the overhead extraction of reactor II, the reactor III for being sent into step C carries out secondary plus hydrogen.

C, secondary plus hydrogen

120~300 DEG C of hydrogen rich off gas is admitted to the bottom of reactor III, and ethyl acetate sterling is admitted to reactor III Top, carries out catalytic hydrogenation reaction, generation ethyl alcohol under the action of noble metal catalyst, catalytic hydrogenation reaction temperature for 220~ 250 DEG C, pressure is 2.0~2.5MPa;Coarse ethanol is sent directly into ethyl alcohol rectification section after being produced from III lower part of reactor and is carried It is pure, up to ethyl alcohol finished product after alcohol product index to be achieved, sold;Unreacted tail gas is from the overhead extraction of reactor III Afterwards, the bottom of towe of reactor II and fresh H are sent back to again after recycle compressor is forced into 2.5~3.5MPa2After mixing again Acetic acid hydrogenation reaction is carried out, realizes process cycles.

Embodiment 4

The present embodiment to the comparative example of embodiment 3, raw materials used, catalyst, reaction unit, reaction condition with reality It is identical to apply example 3, difference lies in:Be not provided with recycle compressor between reactor II and reactor III, reactor III generate two Secondary tail gas is directly entered emission-control equipment, not circular response.

Acetic acid conversion per pass, the ethanol selectivity of 1~embodiment of embodiment 4 are calculated, and calculates and often produces one Electricity and 1.6MPa quantity of steam spent by ton ethyl alcohol.Result of calculation see the table below.

Present invention process significantly reduces energy consumption of reaction, acetic acid conversion per pass, ethyl alcohol it can be seen from data in table Selectivity all compared with common process height, is very suitable for industrialization promotion.Above-described embodiment is used for illustrating the present invention rather than right The present invention is limited, within the scope of the invention as claimed, to the present invention make any modification, equivalent replacement, It improves, both falls within protection scope of the present invention.

Claims (7)

1. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid, it is characterised in that:It is prepared using methanol and CO as starting reaction raw materials Ethyl alcohol adds hydrogen, secondary plus three steps of hydrogen including acetic synthesis, acetic acid;
The detailed process of the technique includes:
A, acetic synthesis
Methanol is sent into the top of reactor I, high-purity CO is sent into the bottom of reactor I, major catalyst is carbonylated in reactor I With carry out carbonylation under the catalysis of co-catalyst, generate acetic acid crude product;Gained acetic acid crude product by discharge at the top of reactor I, Detach co-catalyst, the acetic acid of gained is sent directly into reactor II, the co-catalyst isolated come back to reactor I bottoms, Carry out cycle catalysis;
B, acetic acid adds hydrogen
Acetic acid and fresh H obtained by step A2It is admitted to the bottom of reactor II together, is catalyzed under the action of hydrogenation catalyst Hydrogenation reaction, generation ethyl alcohol;The liquid ethanol crude product isolated is produced from reactor II lower parts, is then sent directly into ethyl alcohol rectifying Step is purified;Hydrogen rich off gas carries out secondary plus hydrogen by overhead extraction, the feeding reactor III of reactor II;
C, secondary plus hydrogen
Reactor III is admitted to by the hydrogen rich off gas and raw material acetic acid/acetate that are produced at the top of reactor II together, is urged adding hydrogen Catalytic hydrogenation reaction, generation ethyl alcohol are carried out under the action of agent;The coarse ethanol isolated is direct after being produced from reactor III lower parts Ethyl alcohol rectification step is sent into be purified;Tail gas is sent again from the overhead extraction of reactor III after recycle compressor pressurizes The bottom of towe of reactor II is returned, with fresh H2It mixes the unstripped gas as step B, carry out acetic acid hydrogenation reaction again, realize technique Cycle;
Reaction pressure, the reaction temperature of the reactor III is below the reaction pressure of reactor II, reaction temperature.
2. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as described in claim 1, it is characterised in that:In the step A, The raw materials components mole ratio of CO and methanol is 0.5:1~3:1;Major catalyst is rhodium series catalysts, and co-catalyst is iodide;Carbonylation The pressure of reaction is 2.0~5.0MPa, temperature is 170~250 DEG C.
3. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as described in claim 1, it is characterised in that:In the step B The reaction pressure of catalytic hydrogenation is 2.0~5.0MPa, temperature is 250~400 DEG C.
4. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as described in claim 1, it is characterised in that:In the step C, The raw material of secondary hydrogenation reaction may be selected from:1. the hydrogen-rich of acetate products, 2. step B made from the hydrogen rich off gas of step B and step A Tail gas and acetate.
5. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as described in claim 1, it is characterised in that:In the step C, It is controlled by the hydrogen rich off gas temperature produced at the top of reactor II and reactor III is sent into after 120~300 DEG C;It is secondary plus hydrogen anti- It is 200~300 DEG C to answer temperature, and reaction pressure is 1.5~4.5MPa;After secondary hydrogenation reaction, unreacted secondary tail gas Send the bottom of towe of reactor II back to again after recycle compressor is pressurized to 2.0~5.0MPa.
6. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as described in claim 1, it is characterised in that:The reactor For recycling the cooling coil of reaction heat, deoxygenated water passes through cooling coil tube wall absorbing reaction heat, byproduct steam for setting in III.
7. a kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid as claimed in claim 6, it is characterised in that:The reactor The steam pressure of III by-products is 2.1~13.1MPa.
CN201610053243.0A 2016-01-25 2016-01-25 A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid CN106995363B (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6657078B2 (en) * 2001-02-07 2003-12-02 Celanese International Corporation Low energy carbonylation process
CN101941887A (en) * 2010-09-30 2011-01-12 江苏丹化煤制化学品工程技术有限公司 Method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen
CN101965324A (en) * 2008-02-28 2011-02-02 埃讷肯公司 Production of ethanol from methanol
CN102311311A (en) * 2008-07-31 2012-01-11 国际人造丝公司 Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
CN102421732A (en) * 2010-02-02 2012-04-18 国际人造丝公司 Process for vaporizing acetic acid for hydrogenation processes to produce ethanol
CN102442883A (en) * 2008-07-31 2012-05-09 国际人造丝公司 Ethanol production from acetic acid utilizing a cobalt catalyst
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
CN103119008A (en) * 2011-08-19 2013-05-22 国际人造丝公司 Integrated process for producing ethanol from methanol
CN103159591A (en) * 2011-12-19 2013-06-19 西南化工研究设计院 Technique of synthesizing ethanol with acetic acid

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6657078B2 (en) * 2001-02-07 2003-12-02 Celanese International Corporation Low energy carbonylation process
CN101965324A (en) * 2008-02-28 2011-02-02 埃讷肯公司 Production of ethanol from methanol
CN102311311A (en) * 2008-07-31 2012-01-11 国际人造丝公司 Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
CN102442883A (en) * 2008-07-31 2012-05-09 国际人造丝公司 Ethanol production from acetic acid utilizing a cobalt catalyst
CN102421732A (en) * 2010-02-02 2012-04-18 国际人造丝公司 Process for vaporizing acetic acid for hydrogenation processes to produce ethanol
CN101941887A (en) * 2010-09-30 2011-01-12 江苏丹化煤制化学品工程技术有限公司 Method for indirectly synthesizing ethanol by using carbon monoxide and hydrogen
CN103119008A (en) * 2011-08-19 2013-05-22 国际人造丝公司 Integrated process for producing ethanol from methanol
CN103159591A (en) * 2011-12-19 2013-06-19 西南化工研究设计院 Technique of synthesizing ethanol with acetic acid
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

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