CN106146298B - The co-production of acetic acid esters and ethylene glycol - Google Patents
The co-production of acetic acid esters and ethylene glycol Download PDFInfo
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- CN106146298B CN106146298B CN201510171318.0A CN201510171318A CN106146298B CN 106146298 B CN106146298 B CN 106146298B CN 201510171318 A CN201510171318 A CN 201510171318A CN 106146298 B CN106146298 B CN 106146298B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
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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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the co-productions of a kind of acetic acid esters and ethylene glycol, mainly solve existing acetic acid esters production technology generation water and form the technical problem that a variety of azeotropic mixtures cause process complexity, separating energy consumption high.Under the conditions of the present invention is by using existing for the catalyst, acetic acid is added in single reactive distillation column middle and upper part, C is added in lower part1~C5The at least one of alcohol, ethylene oxide, acetic acid and alcohol occur esterification and generate acetic acid esters and water, ethylene oxide reacts coproduction ethylene glycol with the water that esterification generates, reaction distillation tower top obtains acetate mixture, the further rectifying separation of acetate mixture, reaction distillation tower reactor obtains ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol, ethylene glycol product is respectively obtained using rectifying, diethylene glycol product, the technical solution of the heavy constituents such as triethylene glycol product and polyethylene glycol, preferably solves the problems, such as this, it can be used for the coproduction industrial production of acetic acid esters and ethylene glycol.
Description
Technical field
The present invention relates to the co-productions of a kind of acetic acid esters and ethylene glycol.
Background technique
Acetic acid esters is important organic solvent, is widely used in the numerous areas such as coating, binder, medicine.With environmental protection
It is required that reinforcement and environmental consciousness raising, acetic acid esters will gradually substitute coating, the methyl ethyl ketone in the products such as adhesive, toluene,
The solvent to environment and human hazard such as benzene.Most of esterification production technology processes, the separation in the presence of acid, alcohol, ester and water are asked
Topic, there are alcohol-water, alcohol -ester, ester-water binary azeotrope, alcohol-water -ester ternary azeotrope to lead to traditional acetic acid for system
The esters technological process of production is to be reacted with acid with alcohol mostly, then undergoes a series of separation process, long flow path, energy consumption height.Such as
N-butyl acetate is a kind of organic solvent of function admirable, is widely used in the industries such as pharmacy, coating.Industrial n-butyl acetate
Synthesis generally make catalyst using the concentrated sulfuric acid, but there is side reactions more, seriously corroded, post-processing be complicated and pollution etc. is asked
Topic.It can be to avoid problem above using solid catalyst using reaction distillation technique.Heat can be broken using reaction distillation technique
Mechanical balance limitation improves reaction speed and conversion ratio, simplifies equipment, saves equipment investment, reduces energy consumption ([moral] Song De
Mach you, gold, which is strangled, to be compiled reaction distillation [M] Zhu Jianhua and translate Beijing: Chemical Industry Press, 2005).But reaction distillation technique and
The same azeotropic problem that can not all eliminate water Yu the reactant not converted completely and reaction product of traditional handicraft, therefore how to eliminate
Azeotropic problem is the simplified technological process of production, reduces the key of production energy consumption.
Ethylene glycol is very important Organic Chemicals, is mainly used to produce polyester fiber (PET), plastics, rubber, gather
Ester paint, adhesive, nonionic surfactant, ethanol amine and explosive are also largely used as solvent, lubricant, plasticizer and prevent
Freeze agent etc., wherein having the call, increasing most fastly to produce polyester.Conventional petroleum route uses direct oxidation of ethylene to EO, EO
Direct hydration EG, water occur that ring-opening reaction is replaced to generate EG with EO, production technology is mainly by SHELL, SD as nucleopilic reagent
It is monopolized with tri- company of DOW.The status of China's glycol unit at present, hydration ethylene glycol technology path fall behind, the choosing of ethylene glycol
Selecting property is low, and device material consumption is high；Water is than high, and production technology is complicated, long flow path, and energy consumption is high；Small scale, the market competitiveness be not strong.Mesh
The preceding advanced ethylene oxide hydration device of foreign countries, ethylene glycol yield can reach 99% or more, and the unit consumption of ethylene glycol is than China
It is low 10% (status of the beautiful ethylene oxide hydration preparing ethylene glycol of Zhao Lan, Li Weizhen, Gu Yan, technical progress and suggest [J] chemical industry into
Exhibition, 2009, (S1)).
Reaction distillation production acetic acid esters technique has the advantages that process flow is simple, equipment investment and operating cost are low etc., grinds
The person of studying carefully just has begun from the 1930s has carried out theoretical and experimental study.But in addition to methyl formate industrialization, remaining
Acetate esters are there is not yet industrialization reported success.Acetic acid esters production technology (Tang YT, Chen YW, Huang HP, et
al.Design of reactive distillations for acetic acid esterification[J].AIChE
Journal, 2005,51 (6): 1683-1699) cause since esterification generation water forms a variety of azeotropic mixtures with acetic acid esters, alcohol
The problems such as separating energy consumption is high, process is complicated, discharge of wastewater is more.
Producing glycol by virtue of hydration of ethylene oxide mainly uses tubular type or shell and tube reactor at present, fast with cooling mediums such as water
Speed withdraws heat, is safely operated reactor.Water is reacted in production ethylene glycol technique as reaction raw materials in ethylene oxide hydration,
Ethylene oxide and water reaction speed are fast, after generating ethylene glycol, remove at once from tower reactor, in reactive distillation column ethylene oxide concentration
Low, the reaction was continued generates diethylene glycol (DEG) and the amount of triethylene glycol is extremely low for ethylene oxide and ethylene glycol, to obtain ethylene glycol high-class product, to anti-
It answers rectifying column kettle liquid to carry out rectifying, respectively obtains ethylene glycol product, diethylene glycol product, triethylene glycol product and polyethylene glycol etc.
Heavy constituent.Reactive distillation production acetic acid esters reboiler needs to provide heat, and ethylene oxide hydration can be made full use of to react anti-
Heat is answered, reduces reboiler, while reducing equipment investment.
Summary of the invention
The technical problem to be solved by the present invention is to present in traditional acetic acid esters production technology due to esterification generate
Water and acetic acid esters, alcohol form a variety of azeotropic mixtures, lead to problems such as separating energy consumption height, process complicated, provide a kind of new acetic acid esters
With the co-production of ethylene glycol.This method has many advantages, such as that separating energy consumption is low, process is simple.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: a kind of coproduction of acetic acid esters and ethylene glycol
Method, under the conditions of existing for the catalyst, acetic acid and alcohol occur esterification and generate acetic acid esters and water, and ethylene oxide and esterification are anti-
The water reaction that should be generated comprising the steps of:
A) acetic acid is added on single reactive distillation column top, the mixture of pure and mild ethylene oxide is added in lower part；Acetic acid feed
Position is rectifying section to tower top, is conversion zone, alcohol between acetic acid feed position and the mixture feed entrance point of pure and mild ethylene oxide
It is stripping section with the mixture feed entrance point of ethylene oxide to tower reactor；
B) rectifying section fills filler, conversion zone catalyst filling and filler, and stripping section fills filler；
C) esterification generation acetic acid esters and water occur for acetic acid and alcohol, while the water that ethylene oxide and esterification generate is sent out
Raw hydration reaction generates ethylene glycol；
D) by the rectifying action of reactive distillation column, reactive distillation tower top obtains acetic acid esters product, tower reactor obtain ethylene glycol,
Diethylene glycol, triethylene glycol and polyethylene glycol；
E) reactive distillation tower bottoms respectively obtains ethylene glycol product, diethylene glycol product, triethylene glycol product by rectifying
And the heavy constituents such as polyethylene glycol.
In above-mentioned technical proposal, alcohol is preferably selected from C1~C5Positive at least one of structure or isomery alcohols, are more preferably selected
From at least one of ethyl alcohol, isopropanol, normal propyl alcohol or n-butanol；The molar ratio of alcohol and acetic acid is preferably 0.8:1~1.30:1；
The molar ratio of alcohol and ethylene oxide is preferably 0.8:1~1.30:1；Amount is few in ethylene oxide and neutralization reaction raw material (acid and alcohol)
Component molar than be preferably 0.95:1~1.05:1；The theoretical cam curve of reactive distillation column is preferably 40~70 pieces, tower top behaviour
It is preferably 60~145 DEG C as temperature, tower top operating pressure is preferably 100~150kPa, and tower reactor operating pressure is preferably 120~
160kPa, tower reactor operation temperature are preferably 180~240 DEG C, and reflux ratio is preferably 0.5~5；The theoretical cam curve of reactive distillation column
More preferably 50~65 pieces, tower top operation temperature is more preferably 75~125 DEG C, and tower top operating pressure is more preferably 100~
120kPa, tower reactor operating pressure are more preferably 130~150kPa, and tower reactor operation temperature is more preferably 190~210 DEG C, reflux ratio
More preferably 2~4；The theoretical cam curve of reactive distillation column conversion zone is preferably 10~20 pieces, and the theoretical cam curve of rectifying section is excellent
10~30 pieces are selected as, the theoretical cam curve of stripping section is preferably 10~20 pieces.Ethylene glycol high-class product is from purifying ethylene glycol tower side line
Extraction, tower top are ethylene glycol Grade A.Acetate mixture obtains acetic acid esters product by rectifying
Esterification:
R-OH+CH3COOH→CH3COOR+H2O
Hydration reaction:
Overall reaction:
Wherein: R-OH C1~C5Alcohol, CH3COOR is C1-C5Acetic acid esters corresponding to alcohol, esterification are micro- endothermic reaction
(ethyl acetate system reaction heat 13.02kJ/mol), ethylene oxide hydration reaction are strong exothermal reaction, reaction heat 80kJ/
mol。
Table 1 is acetic acid esters (C under 1atm4~C6) system azeotropic point temperature and composition.
Table 1
Note: * is dual azeotropic mixture.
As can be seen from Table 1, since esterification generates water, the pure and mild equal shape of acetic acid product ester in the water and system of generation
At azeotropic mixture, aqueous azeotropic mixture causes and the rectifying column of the production technology of acetic acid esters needs 2 or more, since reflux ratio is big,
The latent heat of vaporization of water is big, and separating energy consumption is high, every production 1mol acetic acid esters, discharges 1mol waste water.
Esterification and ethylene oxide hydration reaction are to carry out under conditions, and reaction temperature and reaction pressure can be fine
Matching.Water and 1mol acetic acid esters that esterification generates 1mol, the water that esterification generates occur for the pure and mild 1mol acetic acid of 1mol
It is consumed in time by hydration reaction, it is suppressed that the formation of water-alcohol, water-acetic acid esters -ol, water-acetic acid esters azeotropic mixture, tower top
Distillate is acetic acid esters product, reduces the energy consumption of separation water.
Ethylene oxide hydration is irreversible exothermic reaction, under general industry working condition, the conversion ratio of ethylene oxide
Be close to 100%, hydration reaction generate heat can be distillated process utilization, further decrease process energy consumption.
Ethylene glycol, diethylene glycol, the triethylene glycol of by-product can be isolated by subsequent rectifying.In order to guarantee second two
The product quality of alcohol can reach the requirement of top grade product.The thick ethylene glycol product of ethylene glycol purifying column T-102 overhead extraction, T-102
Side take-off ethylene glycol high-class product.T-103 tower top obtains pure diethylene glycol product, and T-104 tower top obtains pure triethylene glycol
Product.Thick acetic acid esters 3 obtains two acetic acid esters products after T105, T106 separation.Logistics 3 is isolated light into T-105
Acetate product logistics 11, thick weight acetic acid esters product stream 12 enter the acetic acid esters product 13 that weight is isolated at the top of T-106, tower
Kettle is blowdown 14.
Using technical solution of the present invention, the theoretical cam curve of reactive distillation column is 50 pieces (number of plates is counted from top to bottom),
Tower top operating pressure is 100kPa, and tower top operation temperature is 76.8 DEG C, and tower reactor operating pressure is 130kPa, and tower reactor operation temperature is
205 DEG C, reflux ratio 3.5, joint production process reactive distillation column reboiler is to individually produce acetic acid esters technique reboiler
30%.The present invention passes through the matching of reaction feed molar ratio, esterification and ethylene oxide in the same reactive distillation column
Hydration reaction is coupled, coproduction acetic acid esters and ethylene glycol, while reducing equipment investment and process energy consumption, can also reduce useless
The discharge amount of water achieves preferable technical effect.
Detailed description of the invention
Fig. 1 is the process flow diagram that coproduction of the present invention produces acetic acid esters and ethylene glycol.
In Fig. 1, T-101 is reactive distillation column, and 1 is acetic acid feed, and 2 feed for the mixture of pure and mild ethylene oxide, and 3 be second
Acid ester product, 4 be the by-products such as ethylene glycol.T-102 is ethylene glycol purifying column, and 5 be ethylene glycol crude product, and 6 be ethylene glycol product,
7 be diethylene glycol, triethylene glycol mixture.T-103 is diethylene glycol purifying column, and 8 be diethylene glycol product, and 9 be thick three second two
Alcohol.T-104 is that triethylene glycol proposes tower, and 10 be triethylene glycol product, and 11 be high-boiling components.T-105 tower top is that light acetic acid esters produces
Product, logistics 12 are that thick heavy acetic acid esters product enters T-106, and the acetic acid esters product that logistics 13 is attached most importance to, 14 be blowdown logistics.
In Fig. 1, acetic acid feed 1 enters above reactive distillation column T-101 conversion zone, the mixture of pure and mild ethylene oxide into
Material 2 enters below reactive distillation column T-101 conversion zone, and the logistics 3 containing acetic acid esters is distillated from tower top, the object containing ethylene glycol
Stream 4 enters T-102 after distillating from tower reactor, ethylene glycol crude product produces at the top of T-102, and ethylene glycol product is adopted from T-102 side line
Out, thick diethylene glycol product 7 enters T-103, and diethylene glycol product is from T-103 overhead extraction, and thick triethylene glycol is from T-103 tower reactor
Enter T-104 after extraction, logistics 10 is that triethylene glycol product produces at the top of T-104, and high-boiling components are produced from T-104 tower reactor.Object
After stream 3 enters T-105, the light acetic acid esters product stream 11 of overhead extraction, tower reactor produces big and heavy acetic acid esters product 12 and enters T-106
After purification, logistics 13 is attached most importance to acetic acid esters product, and tower reactor 14 is blowdown.
In (Tang YT, Chen YW, Huang HP, et al.Design of reactive distillations
For acetic acid esterification [J] .AIChE Journal, 2005,51 (6): 1683-1699) it arranges in a text
C is lifted1~C5The reaction distillation process and flow chart of esterification production acetic acid esters occur for alcohol and acetic acid.
Specific embodiment
[embodiment 1]
Under the conditions of existing for the catalyst, the mixture and acetic acidreaction of pure and mild ethylene oxide, coproduction acetic acid esters and second two
Alcohol comprising the steps of:
A) acetic acid is added on single reactive distillation column top, the mixture of pure and mild ethylene oxide is added in lower part；Acetic acid feed
Position is rectifying section to tower top, is conversion zone, alcohol between acetic acid feed position and the mixture feed entrance point of pure and mild ethylene oxide
It is stripping section with the mixture feed entrance point of ethylene oxide to tower reactor；
B) rectifying section fills filler, conversion zone catalyst filling and filler, and stripping section fills filler；
C) esterification generation acetic acid esters occurs for acetic acid and alcohol, while water occurs for the water that ethylene oxide and esterification generate
It closes reaction and generates ethylene glycol；
D) by the rectifying action of reactive distillation column, reactive distillation column overhead obtains acetic acid esters product, and tower reactor obtains second two
Alcohol product.
The alcohol used is ethyl alcohol and isopropanol, wherein ethyl alcohol: isopropanol: acetic acid: molar ratio=0.4:0.4:
1:1。
The theoretical cam curve of reactive distillation column T-101 is 40 pieces (number of plates is counted from top to bottom), and tower top operating pressure is
100kPa, 60 DEG C of tower top operation temperature, tower reactor operating pressure is 120kPa, and tower reactor operation temperature is 180 DEG C, reflux ratio 0.5.
The rectifying section theoretical cam curve of reactive distillation column is 10 pieces (the 1st~20 piece).
The conversion zone theoretical cam curve of reactive distillation column is 20 pieces (the 21st~40 piece).
The stripping section theoretical cam curve of reactive distillation column is 10 pieces (the 41st~50 piece).
Ethyl acetate product is distillated from T101 tower top, and ethylene glycol product is distillated from T101 tower reactor.Tower top, tower reactor product quality
Composition is shown in Table 2.The ethyl acetate product that content is 98.6% by T105 overhead extraction, isopropyl acetate that content is 99.9% by
T106 overhead extraction.Content be 99.4% ethylene glycol product, 99.2% diethylene glycol, 99.2% triethylene glycol product difference
By T102, T103, T104 overhead extraction.Joint production process reactive distillation column reboiler is to individually produce ethyl acetate technique again
Boil the 90% of device load.
Table 2
[embodiment 2]
Under the conditions of existing for the catalyst, the mixture and acetic acidreaction of pure and mild ethylene oxide, coproduction acetic acid esters and second two
Alcohol comprising the steps of:
A) acetic acid is added on single reactive distillation column top, the mixture of pure and mild ethylene oxide is added in lower part；Acetic acid feed
Position is rectifying section to tower top, is conversion zone, alcohol between acetic acid feed position and the mixture feed entrance point of pure and mild ethylene oxide
It is stripping section with the mixture feed entrance point of ethylene oxide to tower reactor；
B) rectifying section fills filler, conversion zone catalyst filling and filler, and stripping section fills filler；
C) esterification generation acetic acid esters occurs for acetic acid and alcohol, while water occurs for the water that ethylene oxide and esterification generate
It closes reaction and generates ethylene glycol；
D) by the rectifying action of reactive distillation column, reactive distillation column overhead obtains acetic acid esters product, and tower reactor obtains second two
Alcohol product.
The alcohol used is ethyl alcohol and normal propyl alcohol, wherein ethyl alcohol: normal propyl alcohol: acetic acid: molar ratio=0.65:
0.65:1.06:1。
The theoretical cam curve of reactive distillation column is 70 pieces (number of plates is counted from top to bottom), and tower top operating pressure is 150kPa,
Tower top operation temperature is 145 DEG C, and tower reactor operating pressure is 160kPa, and tower reactor operation temperature is 240 DEG C, reflux ratio 0.5.
The rectifying section theoretical cam curve of reactive distillation column is 20 pieces (the 1st~25 piece).
The conversion zone theoretical cam curve of reactive distillation column is 30 pieces (the 26th~40 piece).
The stripping section theoretical cam curve of reactive distillation column is 20 pieces (the 41st~55 piece).
Ethyl acetate product is distillated from T101 tower top, and ethylene glycol product is distillated from tower reactor T101.Tower top, tower reactor product quality
Composition is shown in Table 3.The ethyl acetate product that content is 90% by T105 overhead extraction, n-propyl acetate that content is 99.1% by
T106 overhead extraction.Content be 99.2% ethylene glycol product, 99.4% diethylene glycol, 99.3% triethylene glycol product difference
By T102, T103, T104 overhead extraction.Joint production process reactive distillation column reboiler is to individually produce ethyl acetate technique again
Boil the 85% of device load.
Table 3
[embodiment 3]
Under the conditions of existing for the catalyst, the mixture and acetic acidreaction of pure and mild ethylene oxide, coproduction acetic acid esters and second two
Alcohol comprising the steps of:
A) acetic acid is added on single reactive distillation column top, the mixture of pure and mild ethylene oxide is added in lower part；Acetic acid feed
Position is rectifying section to tower top, is conversion zone, alcohol between acetic acid feed position and the mixture feed entrance point of pure and mild ethylene oxide
It is stripping section with the mixture feed entrance point of ethylene oxide to tower reactor；
B) rectifying section fills filler, conversion zone catalyst filling and filler, and stripping section fills filler；
C) esterification generation acetic acid esters occurs for acetic acid and alcohol, while water occurs for the water that ethylene oxide and esterification generate
It closes reaction and generates ethylene glycol；
D) by the rectifying action of reactive distillation column, reactive distillation column overhead obtains acetic acid esters product, and tower reactor obtains second two
Alcohol product.
The alcohol used is ethyl alcohol, normal propyl alcohol, n-butanol, wherein ethyl alcohol: normal propyl alcohol: n-butanol: acetic acid: molar
Than=0.32:0.34:0.34:0.99:1.
The theoretical cam curve of reactive distillation column is 50 pieces (number of plates is counted from top to bottom), and tower top operating pressure is 120kPa,
Tower top operation temperature is 75 DEG C, and tower reactor operating pressure is 150kPa, and tower reactor operation temperature is 196 DEG C, reflux ratio 4.
The rectifying section theoretical cam curve of reactive distillation column is 25 pieces (the 1st~25 piece).
The conversion zone theoretical cam curve of reactive distillation column is 15 pieces (the 26th~40 piece).
The stripping section theoretical cam curve of reactive distillation column is 10 pieces (the 41st~55 piece).
Ethyl acetate product is distillated from T101 tower top, and ethylene glycol product is distillated from T101 tower reactor.Tower top, tower reactor product quality
Composition is shown in Table 4.The ethyl acetate product that content is 98.8% by T105 overhead extraction, n-propyl acetate that content is 99.1% by
T106 overhead extraction.T106 tower bottoms carries out rectifying again and obtains the n-butyl acetate product that content is 98.7%.Due to three second two
Alcohol content is less, thus content be 99.3% ethylene glycol product, 99.4% diethylene glycol product respectively by T102, T103 tower
Top extraction.Joint production process reactive distillation column reboiler is individually produce n-propyl acetate technique reboiler 93%.
Table 4
Claims (6)
1. the co-production of a kind of acetic acid esters and ethylene glycol, under the conditions of existing for the catalyst, esterification occurs for acetic acid and alcohol
It generates acetic acid esters and water, ethylene oxide reacts coproduction acetic acid esters and ethylene glycol with the water that esterification generates comprising the steps of:
A) acetic acid is added on single reactive distillation column top, the mixture of pure and mild ethylene oxide is added in lower part；Acetic acid feed position
It is rectifying section to tower top, is conversion zone, pure and mild ring between acetic acid feed position and the mixture feed entrance point of pure and mild ethylene oxide
The mixture feed entrance point of oxidative ethane to tower reactor be stripping section；
B) rectifying section fills filler, conversion zone catalyst filling and filler, and stripping section fills filler；
C) esterification generation acetic acid esters and water occur for acetic acid and alcohol, while water occurs for the water that ethylene oxide and esterification generate
It closes reaction and generates ethylene glycol；
D) by the rectifying action of reactive distillation column, reactive distillation tower top obtains acetic acid esters product, and tower reactor obtains ethylene glycol, diethyl
Glycol, triethylene glycol and polyethylene glycol；
E) reactive distillation tower bottoms respectively obtains ethylene glycol product, diethylene glycol product, triethylene glycol product by rectifying and gathers
Ethylene glycol heavy constituent；
Wherein, the alcohol is selected from C1~C5Positive at least one of structure or isomery alcohols；
Wherein, the theoretical cam curve of the reactive distillation column is 40~70 pieces, and tower top operating pressure is 100~150kPa, tower top
Operation temperature is 60~145 DEG C, and tower reactor operating pressure is 120~160kPa, and tower reactor operation temperature is 180~240 DEG C, reflux ratio
It is 0.5~5；
Wherein, the theoretical cam curve of the reactive distillation column conversion zone is 10~20 pieces；The reason of the reactive distillation column rectifying section
It is 10~30 pieces by the number of plates；The theoretical cam curve of the reactive distillation column stripping section is 10~20 pieces.
2. the co-production of acetic acid esters according to claim 1 and ethylene glycol, it is characterised in that the alcohol is selected from ethyl alcohol, different
At least one of propyl alcohol, normal propyl alcohol or n-butanol.
3. the co-production of acetic acid esters according to claim 1 and ethylene glycol, it is characterised in that the molar ratio of alcohol and acetic acid
For 0.8:1~1.30:1.
4. the co-production of acetic acid esters according to claim 1 and ethylene glycol, it is characterised in that alcohol and ethylene oxide rub
You are than being 0.8:1~1.30:1.
5. the co-production of acetic acid esters according to claim 1 and ethylene glycol, it is characterised in that the reactive distillation column
Theoretical cam curve is 50~65 pieces, and tower top operating pressure is 100~120kPa, and tower top operation temperature is 75~125 DEG C, tower reactor behaviour
Making pressure is 130~150kPa, and tower reactor operation temperature is 190~210 DEG C, and reflux ratio is 2~4.
6. the co-production of acetic acid esters according to claim 1 and ethylene glycol, it is characterised in that ethylene glycol high-class product is from second
Glycol treating column side take-off, tower top are ethylene glycol Grade A.
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| DE2555901A1 (en) * | 1974-12-19 | 1976-06-24 | Mitsubishi Chem Ind | PROCESS FOR THE PRODUCTION OF METHACRYLIC ACID ESTERS |
| CN1268594C (en) * | 2004-02-18 | 2006-08-09 | 中国石油化工股份有限公司 | Method of preparing ethylene glycol |
| CN102875327B (en) * | 2012-10-30 | 2014-05-21 | 中国海洋大学 | Technique for preparing absolute ethanol from near-azeotropic-concentration ethanol-water mixture |
| CN104418701B (en) * | 2013-09-11 | 2016-09-28 | 中国科学院过程工程研究所 | A kind of method utilizing carbon dioxide synthesizing diethyl carbonate coproduction dihydroxylic alcohols |
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