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 PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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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
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.
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| CN201610053243.0A CN106995363B (en) | 2016-01-25 | 2016-01-25 | A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid |
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| CN201610053243.0A CN106995363B (en) | 2016-01-25 | 2016-01-25 | A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid |
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| CN106995363B true CN106995363B (en) | 2018-07-10 |
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| CN201610053243.0A Active CN106995363B (en) | 2016-01-25 | 2016-01-25 | A kind of hydrogenation coupled technique for preparing ethyl alcohol of acetic acid |
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Address after: 463800 south side of Xingye Road East, Shangcai, Zhumadian, Henan Applicant after: Henan Shunda Amperex Technology Limited Address before: 463000 439 Zhonghua Road, Yicheng District, Zhumadian, Henan Applicant before: Henan Shunda Chemical Industry Science Co., Ltd |
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Denomination of invention: Technology for preparing ethyl alcohol through acetic acid hydrogenation coupling Effective date of registration: 20191012 Granted publication date: 20180710 Pledgee: Zhumadian Rural Commercial Bank Co., Ltd. Pledgor: Henan Shunda Amperex Technology Limited Registration number: Y2019980000246 |
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