CN109081779A - A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester - Google Patents
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester Download PDFInfo
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- CN109081779A CN109081779A CN201810715366.5A CN201810715366A CN109081779A CN 109081779 A CN109081779 A CN 109081779A CN 201810715366 A CN201810715366 A CN 201810715366A CN 109081779 A CN109081779 A CN 109081779A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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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
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Abstract
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, is related to a kind of technique of synthesis of oxalic acid symmetrical ester, and the present invention starts a process route with dimethyl oxalate and various alcohol (higher alcohols such as ethyl alcohol, propyl alcohol, butanol) transesterification synthesis of oxalate.It realizes and dimethyl oxalate and a variety of alcohol is directly catalyzed respectively in fixed-bed catalytic rectifying column and reaction kettle rectifying simple separation technology with multi-functional compound basic matterial.For preparing high-purity oxalic acid diethylester, product diethy-aceto oxalate and methanol or ethyl alcohol not azeotropic, pass through simple rectifying, isolate methanol, continue driving a reaction to carry out to positive direction, high-purity diethy-aceto oxalate ethanol solution is obtained in final tower bottoms, after decompression essence isolates ethyl alcohol, crystallizes out high-purity oxalic acid diethylester.
Description
Technical field
The present invention relates to a kind of techniques of synthesis of oxalic acid symmetrical ester, more particularly to one kind by transesterification path synthesis of oxalic acid
The technique of symmetrical ester.
Background technique
Oxalate is widely used in field of fine chemical such as important Organic Chemicals: preparing various dyestuffs, doctor
Medicine, solvent, extractant and various intermediates.It is wherein especially the most extensive with the purposes of diethy-aceto oxalate, diethy-aceto oxalate
(Diethyl oxalate can be abbreviated as DEO) also known as diethyl oxalate are a kind of colourless oil liquids under room temperature, there is virtue
Fragrance taste, can be miscible with the common solvents such as ethyl alcohol, ether, meets water facile hydrolysis.
Diethy-aceto oxalate is important Organic Chemicals, can produce the objects such as ethylene glycol as important chemical intermediate
Matter, and can be reacted with many heterocyclic compounds such as aliphatic ester；It can be used to synthesize the chest as intermediate in terms of medicine
Gland alkali, thymine can further manufacture into the drugs such as bright karr, phenobarbital and penicillin；It can be used for making in terms of organic synthesis
Make the organic substances such as plastics promotor, dyestuff, cellulose esters；Solvent be can be used as in the industrial production for television picture tube yin
The production of pole spray solution, and auxiliary agent and the lubricant of low temperature resistant high pressure etc. that can be used as textile industry.
There are mainly two types of the synthetic methods of oxalate: alcoholic acid esterification method and CO catalytic coupling method, the specific mistake of two methods
Journey is as follows.
(1) alcoholic acid esterification method
Traditional oxalate synthetic method is to hand over using oxalic acid and alcohol as raw material in inorganic acid (such as concentrated sulfuric acid) or strong acidic ion
Changing resin is that the water that the crystallization water and reaction in oxalic acid generate is sloughed using low boiling point solvent under catalyst.This method it is anti-
Answer equation as follows:
HOOCCOOH + 2 ROH →ROOCCOOR + 2 H2O (1)
Due to generating a large amount of water in reaction process, and the water generated is unfavorable for the positive of esterification and carries out, therefore needs
The water that reaction is generated in time removes system.Usually subtract in the reaction system when industrial production into a certain amount of water entrainer,
To remove a large amount of water produced in reaction process.Oxalate production is introduced by taking the generation technique of traditional diethy-aceto oxalate as an example
Method: carrying out first time esterification to the mixed liquor of oxalic acid, ethyl alcohol and water entrainer first, and heating divides after water reflux a period of time to production
Product are distilled；And then secondary esterification and distillation are carried out with the mixed liquor of water entrainer and ethyl alcohol, obtain crude product oxalic acid diethyl
Ester can obtain finished product diethy-aceto oxalate after vacuum distillation.
(2) CO is coupled synthesis of oxalate
Under the conditions of existing for the anhydrous, high pressure and oxygen, the catalyst PdCl into reaction system2–CuCl2, CO and methanol
It generates dimethyl oxalate (vapor phase method), this reaction process also may extend to CO and react generation diethy-aceto oxalate with ethyl alcohol or n-butanol
Or dibutyl oxalate (liquid phase method), reaction equation is as follows:
2CO+2 ROH+ 1/2 O2→ ROOCCOOR+H2O(2)
The reaction process of gas phase coupling method are as follows: normal pressure coupling reaction generates oxalic acid diformazan under the action of catalyst for CO and nitrous acid ester
Ester and nitric oxide, nitric oxide, which separates to react with methanol and oxygen under rear room temperature with product, generates methyl nitrite, and returns
Coupling process recycles.This gas phase coupling method can overcome high production cost, equipment corrosion and the problems such as catalyst loss, and gas
It is at low cost that phase coupling method produces dimethyl oxalate, therefore prepares other oxalates with substantial worth by dimethyl oxalate.
Traditional esterification would generally use inorganic acid (such as concentrated sulfuric acid) for catalyst, but since inorganic acid is easily rotten
Equipment is lost, and the processing of waste water is relatively complicated；CO liquid phase coupling synthesis of oxalate is there are high production cost, equipment corrosion and urges
The problems such as agent is lost.With science and technology fast development, people's environmental consciousness generally improve and environmental regulation increasingly
Perfect, the advantage of solid catalyst is also increasingly valued by people, and selection is prepared using other Novel solid-catalysts
Oxalate has become to be selected imperatively.
In recent years, domestic and foreign scholars made the catalyst with oxalic acid and various alcohol esterification methods and CO coupling synthesis of oxalate
A large amount of research work, but the report of real investment industrialized production is seldom, it is inefficient to be primarily present catalyst,
The problems such as preparation process is complicated, stability difference and reuse number are few.
Zhang Shuxin etc. is prepared for four kinds of acidic ion liquids to catalyze and synthesize oxalate, has investigated reaction time, reaction
Influence of the factors such as temperature, raw materials components mole ratio to diethy-aceto oxalate yield, and optimal process conditions have been determined, at n (ethyl alcohol):
N (oxalic acid)=4:1,0.1 mol of oxalic acid, 20 mL of toluene, 0.1 mol of acidic ion liquid, 100 DEG C of reaction temperature, reflux are anti-
Under the reaction condition for answering 90 min, the ultimate yield of diethy-aceto oxalate is 84.8%, but the reaction process belongs to homogeneous catalysis body
The process intensification of system, it is energy-saving, but ionic liquid reuses number and economy waits to discuss.
He Liming etc. is with Pd/Al2O3For catalyst, has studied CO in fixed bed reactors and be coupled synthesis of oxalic acid dibutyl ester
Reaction, the selectivity and CO conversion ratio of comparison differential responses temperature, raw materials components mole ratio and different air speeds to dibutyl oxalate
It influences；The result shows that the optimum condition of reaction are as follows: 135 ~ 145 DEG C of reaction temperature, CO and dibutyl oxalate initial molar ratio are 1.2
~ 1.6, air speed is 2800 ~ 3600h-1, with this condition, the selectivity of dibutyl oxalate is reached up to 94% or so, CO conversion ratio
46%.But the reaction, under conditions of reaction temperature is high, air speed is big, catalyst effect is poor, is not used to industrial metaplasia
It produces.
Compared with liquid phase coupling method, CO gas phase coupling is with reaction condition is mild, reaction pressure is low, product is easily separated, urges
Agent is lost the advantages such as reduction, and production dimethyl oxalate (gas phase coupling method) is at low cost, therefore prepares it by dimethyl oxalate
He has substantial worth by oxalate.
There is the report of numerous studies ester exchange reaction in the country, as propene carbonate and methanol transesterification prepare carbonic acid diformazan
Ester, dimethyl carbonate and ethyl alcohol transesterification prepare methyl ethyl carbonate etc., mostly use homogeneous solvable basic catalyst greatly, but for
The report of dimethyl oxalate and various alcohol (higher alcohols such as ethyl alcohol, propyl alcohol, butanol) transesterification synthesis of oxalate is few.
Summary of the invention
The purpose of the present invention is to provide a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, which uses one
The efficient solid base catalyst catalysis dimethyl oxalate of kind and various alcohol transesterification synthesis of oxalate.It should be synthesized by transesterification path
The production technology of oxalate, synthesis path is short, and process flow is simple, has great meaning to extensive, inexpensive production oxalate
Justice.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the technique are urged using a kind of efficient solid base catalyst
Change dimethyl oxalate and various alcohol and different oxalates, including one-step synthesis method oxalate reactional equation are synthesized by ester exchange reaction
Formula is as follows:
CH3OOCCOOCH3+2 ROH→ROOCCOOR + 2 CH3OH(1)；
Wherein ROH can be the various higher alcohols such as ethyl alcohol, propyl alcohol, butanol；
For preparing dimethyl oxalate and ethyl alcohol transesterification prepares diethy-aceto oxalate:
Catalytic distillation device uses dimethyl oxalate and ethyl alcohol for raw material, and reaction generates diethy-aceto oxalate and methanol the mass ratio of the material
For 1:2, the ethyl alcohol steamed is recycled；Reaction equation is as follows:
CH3OOCCOOCH3+2 CH3CH2OH→CH3CH2OOCCOOCH2CH3 + 2 CH3OH (2)；
Reaction kettle rectifier unit uses reaction raw materials for dimethyl oxalate and excess ethyl alcohol mixture, stirs in heating and vigorous magnetic
It mixes down, reacting material mixture and catalyst sufficiently react in reaction kettle, and the methanol of generation gradually isolates system, make oxalic acid
Dimethyl ester fully reacting obtains high-purity oxalic acid diethylester, when catalyst is solid catalyst, after reaction, filters while hot,
Solid catalyst is recycled；After reaction when catalyst is homogeneous catalyst, decrease temperature crystalline, catalyst washing separation.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the catalysis essence for preparing diethy-aceto oxalate
Evaporate technique, diethy-aceto oxalate production technology, comprising: raw material dimethyl oxalate and alcohol mixture are preheated by metering pump P-1
After device V-1 preheating, into the first reactive distillation column T1；Raw material dimethyl oxalate and alcohol mixture are in the first reactive distillation column
The catalyst member in portion reacts, and in the first reactive distillation column, dimethyl oxalate is sufficiently reacted with ethyl alcohol, dimethyl oxalate
It is consumed significantly, the first obtained mixture includes complete ethyl alcohol, diethy-aceto oxalate and the first of methyl ethyl oxalate, a small amount of unreacted
Alcohol；The light component that first reactive distillation column top of tower comes out is only methanol, and high purity methanol essence is obtained after the condensation of E-1 condenser
Product；First reactive distillation column bottom come out heavy constituent are as follows: methyl ethyl oxalate, diethy-aceto oxalate and small part dimethyl oxalate and
Ethyl alcohol enters the preheating of V-3 preheating can and is pumped into the second reactive distillation column T2 by P-3 metering pump again after condensing via condenser E-2, together
When feed ethanol by metering pump P-2 preheated device V-2 preheating after, into the second reactive distillation column T2；Second reactive distillation column tower
The light component that top comes out is only methanol, obtains high purity methanol fine work after the condensation of E-3 condenser；Second reactive distillation tower reactor
The heavy constituent that bottom comes out are as follows: diethy-aceto oxalate and ethyl alcohol enter compression rectification tower T3 after condensing via condenser E-4；With reaction
Object diethy-aceto oxalate significantly generates and methanol steams, and reacts and carries out toward positive reaction direction；Into the component of compression rectification tower T3
It being separated under high pressure, light component ethyl alcohol comes back to the first reactive distillation column of T1 after the condensation of E-5 condenser and participates in reaction,
A large amount of diethy-aceto oxalate is condensed through E-6 condenser, obtains the diethy-aceto oxalate fine work of high-purity.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the technique used catalyst are a kind of more function
The compound basic matterial of energy, catalyst carrier are to load one or more metallic elements with mesoporous and microcellular structure molecular sieve
As active component；Its usage amount is the 0.3%~5% of the total mass of raw material.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the feed ethanol and dimethyl oxalate rub
You beat liquid feedstock than 1:1-20:1, with metering pump pump, and preheating can V1 temperature is 40-100 DEG C, while beating liquid with metering pump pump
The charging of body feed ethanol, preheating can V2 temperature are 25-60 DEG C.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, produces the device of diethy-aceto oxalate, comprising:
The first reactive distillation column of T1, the first reactive distillation column of T1 centre have from top to bottom spaced apart catalyst inlet, raw material grass
Dimethyl phthalate and ethyl alcohol import are connected on the tower body of the first reactive distillation column of T1 with T3 compression rectification column overhead portion with one
First charging aperture, the tower top of the first reactive distillation column of T1 have the with the tower bottom of the first discharge port and the first reactive distillation column of T1
Two discharge ports；The second reactive distillation column of T2, have among the second reactive distillation column from top to bottom spaced apart catalyst inlet,
Feed ethanol import has a second charging aperture being connected with the second discharge port on second reactive distillation column, and second instead
Answer the tower top of rectifying column that there is the 4th discharge port with the tower bottom of third discharge port and the second reactive distillation column of T2；T3 compression rectification
Tower, has a third feed inlet being connected with the 4th discharge port on compression rectification tower, and the top of tower of compression rectification tower has
There is the tower bottom of the 5th discharge port and compression rectification tower that there is the 6th discharge port.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, it is former in the first reactive distillation column T1
Material dimethyl oxalate and ethyl alcohol react under the effect of the catalyst, obtain the first mixture；The weight of first mixture tower bottom
Component (predominantly methyl ethyl oxalate, diethy-aceto oxalate and ethyl alcohol) is beaten through condenser E-2 condensation and feed ethanol pump, and the two is simultaneously
Be pumped into the second reactive distillation column of T2 secondary response again, the recombination of T2 tower bottom be divided into diethy-aceto oxalate and ethyl alcohol through condenser E-4 condense into
Enter T3 separation, the light component ethyl alcohol of T3 tower top returns again to the first reactive distillation column of T1.In dimethyl oxalate by fully reacting
In the case where, as methanol is constantly isolated system, ethyl alcohol is further consumed, and final T1 and T2 tower top obtains pure first
Alcohol, T3 tower bottom obtain pure diethy-aceto oxalate.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, in the tower of first reactive distillation column of T1
Pressure is 1MPa~5MPa, and tower top temperature is 40 DEG C~70 DEG C, and column bottom temperature is 78 DEG C~185 DEG C；The T2 first reacts essence
The tower pressure interior force for evaporating tower is the MPa of 1MPa~5, and tower top temperature is 40 DEG C~70 DEG C, and column bottom temperature is 78 DEG C~185 DEG C；Pressurization essence
The tower pressure interior force for evaporating tower T3 is 1MPa~15MPa, and tower top temperature is 78 DEG C~90 DEG C, and column bottom temperature is 180 DEG C~185 DEG C；When
When diethy-aceto oxalate content reaches 75% or more, T2 reactor bottom is to T3 compression rectification tower feed liquor.
The partition of a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the reactor and rectifying column is set
The ratio between cross-sectional area of cross-sectional area and side line section for making fore-running section is set to as 1:1-3:1.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, the number of plates of the fore-running section are 1~30
Block, the side line section number of plates are 1~30 piece, and the number of plates of public rectifying section is 1~30 piece, the number of plates of public stripping section is 1~
30 pieces；The first reactive distillation column of T1, the first reactive distillation column of T2, T3 compression rectification tower are plate column, packed tower or board-like-filler
Mixing column.
A kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, it is described with ethyl alcohol and dimethyl oxalate mole
It is raw material than 1:1-20:1, ester exchange reaction is carried out under basic catalyst existence condition, prepares diethy-aceto oxalate, reaction kettle
Middle charging feedstock and catalyst, the agitating and heating 0.5-10 h at 78-180 DEG C, the catalyst amount account for total mass of raw material
0.1-3 wt%。
Detailed description of the invention
Fig. 1 is catalytic rectification process flow diagram；
Fig. 2 is reaction kettle rectification process flow diagram.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention is using multi-functional compound basic matterial as catalyst dimethyl oxalate and various alcohol (ethyl alcohol, propyl alcohol, fourth
The higher alcohols such as alcohol) transesterification synthesis high-purity oxalic acid ester production technology.Specific reaction equation is as follows:
CH3OOCCOOCH3+2 ROH→ROOCCOOR+ 2 CH3OH ... (3)
Wherein ROH can be the various higher alcohols such as ethyl alcohol, propyl alcohol, butanol.
The reaction is using the loading type alkali metal oxide with mesoporous and microcellular structure carrier as catalyst, by oxalic acid diformazan
Ester and various alcohol (ROH is the various higher alcohols such as ethyl alcohol, propyl alcohol, butanol) are raw material transesterification synthesis high-purity oxalic acid ester, and alkalinity is urged
Agent is completely insoluble in reaction raw materials and product, can be by filtering removal while hot.
The oxalate production technology of protection: by dimethyl oxalate and various alcohol, (ROH is the various height such as ethyl alcohol, propyl alcohol, butanol
Carbon alcohol) it is raw material transesterification synthesis of oxalate, with dimethyl oxalate and ethyl alcohol transesterification respectively in catalytic rectifying tower and reaction kettle
For rectifying.
The diethy-aceto oxalate production technology of protection, comprising: raw material dimethyl oxalate and alcohol mixture are passed through by metering pump P-1
After preheater V-1 preheating, into the first reactive distillation column T1.Raw material dimethyl oxalate and alcohol mixture are in the first reactive distillation
Catalyst member in the middle part of tower reacts, and in the first reactive distillation column, dimethyl oxalate is sufficiently reacted with ethyl alcohol, oxalic acid two
Methyl esters is consumed significantly, the first obtained mixture include the complete ethyl alcohol of methyl ethyl oxalate, a small amount of unreacted, diethy-aceto oxalate and
Methanol.The light component that first reactive distillation column top of tower comes out is only methanol, obtains high purity methanol after the condensation of E-1 condenser
Fine work.The heavy constituent that first reactive distillation column bottom comes out are as follows: methyl ethyl oxalate, diethy-aceto oxalate and small part dimethyl oxalate
The second reactive distillation column T2 is pumped by P-3 metering pump again via the preheating of V-3 preheating can is entered after condenser E-2 condensation with ethyl alcohol,
After feed ethanol is by the preheated device V-2 preheating of metering pump P-2 simultaneously, into the second reactive distillation column T2.Second reactive distillation column
The light component that top of tower comes out is only methanol, obtains high purity methanol fine work after the condensation of E-3 condenser.Second reactive distillation column
The heavy constituent that bottom comes out are as follows: diethy-aceto oxalate and ethyl alcohol enter vacuum rectification tower T3 after condensing via condenser E-4.With anti-
It answers that object diethy-aceto oxalate significantly generates and methanol steams, reacts and carried out toward positive reaction direction.Into the group of vacuum rectification tower T3
Divide and separated under high pressure, light component ethyl alcohol comes back to the first reactive distillation column of T1 after the condensation of E-5 condenser and participates in instead
It answers, a large amount of diethy-aceto oxalate is condensed through E-6 condenser, obtains the diethy-aceto oxalate fine work of high-purity.
The method that the present invention produces diethy-aceto oxalate, Fig. 1 are catalytic rectification process flow diagram；Reaction raw materials are oxalic acid
Dimethyl ester and alcohol mixture, the two enter the first reactive distillation column of T1 together, and dimethyl oxalate and ethanol synthesis are abundant, finally
Obtained product is diethy-aceto oxalate and methanol.When the synthesis technology reactive distillation carries out, product is extracted without solvent
Separation, enormously simplifies the process flow of conventional diethyl oxalate synthesis, while multicomponent can be made disposably to separate, and separates
Purity is high.
The technique that the present invention produces diethy-aceto oxalate has the following attached technical characteristic subtracted:
The technique used catalyst is a kind of multi-functional compound basic matterial, and catalyst carrier is with mesoporous and microcellular structure
Molecular sieve loads one or more metallic elements as active component.Catalyst performance stabilised, using 5000h, there is no inactivations
Phenomenon, usage amount are the 0.3%~5% of the total mass of raw material.
The feed ethanol and dimethyl oxalate molar ratio 1:1-20:1 beat liquid feedstock, preheating can V1 with metering pump pump
Temperature is 40-100 DEG C, while playing the charging of liquid charging stock ethyl alcohol with metering pump pump, and preheating can V2 temperature is 25-60 DEG C.
The device of present invention production diethy-aceto oxalate, comprising: the first reactive distillation column of T1, first reactive distillation column of T1
Centre has spaced apart catalyst inlet, raw material dimethyl oxalate and ethyl alcohol import from top to bottom, and the T1 first reacts
There is a first charging aperture being connected with T3 vacuum rectification tower top of tower, first reactive distillation of T1 on the tower body of rectifying column
The tower top of tower has the second discharge port with the tower bottom of the first discharge port and the first reactive distillation column of the T1；T2 second reacts essence
Tower is evaporated, there is from top to bottom spaced apart catalyst inlet, feed ethanol import among second reactive distillation column, it is described
There is a second charging aperture being connected with second discharge port on second reactive distillation column, second reactive distillation column
Tower top has the 4th discharge port with the tower bottom of third discharge port and the second reactive distillation column of the T2；T3 vacuum rectification tower, institute
Stating has a third feed inlet being connected with the 4th discharge port, the top of tower of the vacuum rectification tower in vacuum rectification tower
Tower bottom with the 5th discharge port and the vacuum rectification tower has the 6th discharge port.
An example according to the present invention, in the first reactive distillation column T1, raw material dimethyl oxalate and ethyl alcohol are being catalyzed
It reacts under the action of agent, obtains the first mixture；Heavy constituent (the predominantly methyl ethyl oxalate, grass of first mixture tower bottom
Diethyl phthalate and ethyl alcohol) it is beaten through condenser E-2 condensation and feed ethanol pump, the two is pumped into the second reactive distillation column of T2 again simultaneously
Reaction, T2 tower bottom recombination be divided into diethy-aceto oxalate and ethyl alcohol through condenser E-4 condensation enter T3 decompression separation, light group of T3 tower top
Ethyl alcohol is divided to return again to the first reactive distillation column of T1.In the case where dimethyl oxalate is by fully reacting, as methanol is by constantly
System is isolated, ethyl alcohol is further consumed, and final T1 and T2 tower top obtains pure methanol, and T3 tower bottom obtains pure diethy-aceto oxalate.
The tower pressure interior force of first reactive distillation column of T1 is 1MPa~5MPa, and tower top temperature is 40 DEG C~70 DEG C, tower bottom
Temperature is 78 DEG C~185 DEG C；The tower pressure interior force of first reactive distillation column of T2 be 1MPa~5MPa, tower top temperature be 40 DEG C~
70 DEG C, column bottom temperature is 78 DEG C~185 DEG C；The tower pressure interior force of the vacuum rectification tower T3 is 1MPa~15MPa, and tower top temperature is
78 DEG C~90 DEG C, column bottom temperature is 180 DEG C~185 DEG C；When diethy-aceto oxalate content reaches 75% or more, T2 reactor bottom
To T3 vacuum rectification tower feed liquor.
The partition of heretofore described reactor and rectifying column is arranged to make the cross-sectional area of the fore-running section and the side
The ratio between cross-sectional area of line segment is 1:1-3:1.
The number of plates of fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, the number of plates of public rectifying section is 1~
30 pieces, the number of plates of public stripping section is 1~30 piece.
The first reactive distillation column of T1, the first reactive distillation column of T2, T3 vacuum rectification tower are plate column, packed tower in the present invention
Or board-like-filler mixing column.
The diethy-aceto oxalate production technology of protection, including using ethyl alcohol and dimethyl oxalate molar ratio 1:1-20:1 as raw material,
Ester exchange reaction is carried out under basic catalyst existence condition, prepares diethy-aceto oxalate, it is characterized in that being packed into reaction kettle former
Material and catalyst, the agitating and heating 0.5-10 h at 78-180 DEG C, the catalyst amount account for the 0.1-3 of total mass of raw material
wt%。
Fig. 2 reaction kettle rectification process flow diagram；The method that the present invention produces diethy-aceto oxalate is schemed second is that reaction raw materials
For dimethyl oxalate and excess ethyl alcohol mixture, heating under vigorous magnetic stirring, reacting material mixture and catalyst exist
Sufficiently reaction makes dimethyl oxalate fully reacting in reaction kettle, obtains high-purity oxalic acid diethylester, when catalyst is solid catalyst
When, it after reaction, filters while hot, solid catalyst is recycled；After reaction when catalyst is homogeneous catalyst, cooling
Crystallization, catalyst washing separation.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Embodiment 1
Using ethyl alcohol and dimethyl oxalate as raw material, it is 1:2 that reaction, which generates diethy-aceto oxalate and methanol the mass ratio of the material, is steamed
Ethyl alcohol recycle.
Catalyst is alkalinity composite material 15%CaO-5% Cr2O3-3%La2O3/ Zn-meso-Y, dosage are total mass of raw material
The ratio between cross-sectional area of the 3% of sum, fore-running section and side line section is 1:1.
Operating condition is as follows:
First reactive distillation column T1: tower diameter 1000mm；Tower height 19000mm；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；1 MPa of tower pressure interior force；60 DEG C of tower top temperature；The column bottom temperature of public stripping section
160℃；180 DEG C of the column bottom temperature of side line section.
Second reactive distillation column T2: tower diameter 1000mm；Tower height 19000mm；It is public rectifying section, fore-running section, side line section, public
The number of plates of stripping section is respectively 10,20,30,15；1 MPa of tower pressure interior force；60 DEG C of tower top temperature；The tower bottom temperature of public stripping section
160 DEG C of degree；180 DEG C of the column bottom temperature of side line section.
Vacuum rectification tower T3: tower diameter 3000mm；Tower height 40000mm；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；2 MPa of tower pressure interior force；160 DEG C of tower top temperature, the column bottom temperature of public stripping section
180℃；185 DEG C of the column bottom temperature of side line section.
The charging of first reactive distillation column T1 and tower reactor composition result are as shown in the table
Influence of the different total raw material mass flows of table 1 to T1 the first reactive distillation column tower bottom each component mass fraction
As can be seen from Table 1, in the case where tower reactor heating amount is certain, total feed has larger shadow to Liquid-vapor two-phase flow amount in tower
It rings, while influencing residence time of the reaction mass in tower, and then influence reaction and the separating effect of tower.With total feed
Increase, when charging rate increases to 3000kg/h from 2500kg/h, tower reactor composition mass fraction is almost unchanged, and charging rate mentions again
There is decreasing trend in height, diethy-aceto oxalate mass fraction, this is because the liquid with the increase of charging rate, in reactive distillation column
Body flow rate constantly increases.When inlet amount increase to a certain extent when, material is too short in reactive distillation dwell time in the tower, react into
Row is insufficient.Consider that charging rate is too small, and equipment capacity is small, and energy consumption is big, and increased production cost from industrial point of view,
Comprehensively considering 3000kg/h is optimal total raw material mass flow.
Embodiment 2
Under the operating condition of embodiment 1, when total raw material mass flow is 3000kg/h, change T3 vacuum rectification tower reflux ratio,
Each liquid phase composition mass fraction variation is as shown in table 2.
The influence that the different reflux ratios of table 2 change each liquid phase component mass fraction of T3 vacuum rectification tower
As can be seen from Table 2, with the increase of reflux ratio, the mass fraction of ethyl alcohol is held essentially constant after reducing, oxalic acid diethyl
The mass fraction of ester is held essentially constant after increasing, and when reflux ratio is greater than 3, each liquid phase composition mass fraction is almost unchanged.It is former
Because being after reflux ratio reaches certain value, the composition of kettle liquid reflux has reached balance.But excessive reflux ratio will also result in dress
Treating capacity reduction is set, it is therefore, reflux ratio control is best 3 when rectifying.
Embodiment 3
Under the operating condition of embodiment 2, when total raw material mass flow is 3000kg/h, change the pressure of T3 vacuum rectification tower,
Each liquid phase composition mass fraction variation is as shown in table 3.
The influence that 3 different pressures of table change each liquid phase component mass fraction of T3 vacuum rectification tower
From table 3 it can be seen that with being held essentially constant after ethyl alcohol reduction in each liquid phase composition of the raising of reaction pressure, oxalic acid two
The mass fraction of ethyl ester is held essentially constant after increasing, the reason is that the boiling-point difference of ethyl alcohol and diethy-aceto oxalate increases under lower pressure
Add, ethyl alcohol and diethy-aceto oxalate are more easier to separate.But when pressure is higher than 3 MPa, respectively composition is held essentially constant, due to height
Pressure is higher for equipment requirement, can greatly increase input cost, therefore 3 MPa are the optimum condition of the distillation process.
Embodiment 4
In a kettle, it is packed into the ethyl alcohol and dimethyl oxalate raw material of molar ratio 20:1, makes catalyst 15%CaO-5% by oneself
Cr2O3-3%La2O3/ Zn-meso-Y additional amount is 3 wt% of total mass of raw material, reacts 3h at 78 DEG C, is sampled into chromatography, knot
Fruit is as shown in table 4.
The conversion ratio of 4 kettle of table reaction dimethyl oxalate in preparation
From table 4, it can be seen that in 15%CaO-5% Cr2O3-3%La2O3Under/Zn-meso-Y catalysts conditions, catalyst is urged
Change active composite catalyzing rectifying, kettle reaction is closed system, and reaction product and reactant mix, and end reaction reaches dynamic
Balance, final dimethyl oxalate conversion ratio are 95%.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester, which is characterized in that the technique uses a kind of efficient
Solid base catalyst is catalyzed dimethyl oxalate and various alcohol and synthesizes different oxalates, including one-step synthesis method by ester exchange reaction
Oxalate reaction equation is as follows:
CH3OOCCOOCH3+2 ROH→ROOCCOOR + 2 CH3OH(1)；
Wherein ROH can be the various higher alcohols such as ethyl alcohol, propyl alcohol, butanol；
For preparing dimethyl oxalate and ethyl alcohol transesterification prepares diethy-aceto oxalate:
Catalytic distillation device uses dimethyl oxalate and ethyl alcohol for raw material, and reaction generates diethy-aceto oxalate and methanol the mass ratio of the material
For 1:2, the ethyl alcohol steamed is recycled；Reaction equation is as follows:
CH3OOCCOOCH3+2 CH3CH2OH→CH3CH2OOCCOOCH2CH3 + 2 CH3OH (2)；
Reaction kettle rectifier unit uses reaction raw materials for dimethyl oxalate and excess ethyl alcohol mixture, stirs in heating and vigorous magnetic
It mixes down, reacting material mixture and catalyst sufficiently react in reaction kettle, and the methanol of generation gradually isolates system, make oxalic acid
Dimethyl ester fully reacting obtains high-purity oxalic acid diethylester, when catalyst is solid catalyst, after reaction, filters while hot,
Solid catalyst is recycled；After reaction when catalyst is homogeneous catalyst, decrease temperature crystalline, catalyst washing separation.
2. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that described
Prepare the catalytic rectification process of diethy-aceto oxalate, diethy-aceto oxalate production technology, comprising: raw material dimethyl oxalate and ethyl alcohol are mixed
After object is closed by the preheated device V-1 preheating of metering pump P-1, into the first reactive distillation column T1；Raw material dimethyl oxalate and ethyl alcohol are mixed
Catalyst member of the object in the middle part of the first reactive distillation column is closed to react, in the first reactive distillation column, dimethyl oxalate with
Ethyl alcohol sufficiently reacts, and dimethyl oxalate is consumed significantly, and the first obtained mixture includes that methyl ethyl oxalate, a small amount of unreacted are complete
Ethyl alcohol, diethy-aceto oxalate and methanol；The light component that first reactive distillation column top of tower comes out is only methanol, through E-1 condenser
High purity methanol fine work is obtained after condensation；The heavy constituent that first reactive distillation column bottom comes out are as follows: methyl ethyl oxalate, oxalic acid diethyl
Ester and small part dimethyl oxalate and ethyl alcohol enter the preheating of V-3 preheating can and are pumped again by P-3 metering pump after condensing via condenser E-2
Enter the second reactive distillation column T2, while after feed ethanol is preheated by the preheated device V-2 of metering pump P-2, into the second reactive distillation
Tower T2；The light component that second reactive distillation column top of tower comes out is only methanol, obtains high purity methanol after the condensation of E-3 condenser
Fine work；The heavy constituent that second reactive distillation column bottom comes out are as follows: diethy-aceto oxalate and ethyl alcohol enter after condensing via condenser E-4
Compression rectification tower T3；As reactant diethy-aceto oxalate significantly generates and methanol steams, reacts and carried out toward positive reaction direction；Into
The component for entering compression rectification tower T3 is separated under high pressure, and light component ethyl alcohol comes back to T1 the after the condensation of E-5 condenser
One reactive distillation column participates in reaction, and a large amount of diethy-aceto oxalate is condensed through E-6 condenser, obtains the diethy-aceto oxalate essence of high-purity
Product.
3. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that the work
Skill used catalyst is a kind of multi-functional compound basic matterial, catalyst carrier be with mesoporous and microcellular structure molecular sieve,
One or more metallic elements are loaded as active component；Its usage amount is the 0.3%~5% of the total mass of raw material.
4. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that described
Feed ethanol and dimethyl oxalate molar ratio 1:1-20:1 beat liquid feedstock with metering pump pump, and preheating can V1 temperature is 40-100
DEG C, while the charging of liquid charging stock ethyl alcohol is played with metering pump pump, preheating can V2 temperature is 25-60 DEG C.
5. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that production
The device of diethy-aceto oxalate, comprising: the first reactive distillation column of T1, the first reactive distillation column of T1 centre, which has, is from top to bottom spaced cloth
Catalyst inlet, raw material dimethyl oxalate and the ethyl alcohol import set have one and T3 on the tower body of the first reactive distillation column of T1
The tower top of the connected first charging aperture in compression rectification column overhead portion, the first reactive distillation column of T1 has the first discharge port and T1 first
The tower bottom of reactive distillation column has the second discharge port；The second reactive distillation column of T2, have among the second reactive distillation column by up to
Under spaced apart catalyst inlet, feed ethanol import, have on second reactive distillation column and be connected with the second discharge port
A second charging aperture, the tower top of the second reactive distillation column has the tower bottom of third discharge port and the second reactive distillation column of T2 tool
There is the 4th discharge port；There is on compression rectification tower T3 compression rectification tower a third being connected with the 4th discharge port to feed
Mouthful, the top of tower of compression rectification tower has the 6th discharge port with the tower bottom of the 5th discharge port and compression rectification tower.
6. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 5, which is characterized in that described
In first reactive distillation column T1, raw material dimethyl oxalate and ethyl alcohol react under the effect of the catalyst, obtain the first mixing
Object；The heavy constituent (predominantly methyl ethyl oxalate, diethy-aceto oxalate and ethyl alcohol) of first mixture tower bottom through condenser E-2 condensation and
Feed ethanol pump is beaten, and the two is pumped into the second reactive distillation column of T2 secondary response again simultaneously, T2 tower bottom recombinate be divided into diethy-aceto oxalate with
Ethyl alcohol enters T3 separation through condenser E-4 condensation, and the light component ethyl alcohol of T3 tower top returns again to the first reactive distillation column of T1；
In the case where dimethyl oxalate is by fully reacting, as methanol is constantly isolated system, ethyl alcohol is further disappeared
Consumption, final T1 and T2 tower top obtain pure methanol, and T3 tower bottom obtains pure diethy-aceto oxalate.
7. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 6, which is characterized in that described
The tower pressure interior force of the first reactive distillation column of T1 be 1MPa~5MPa, tower top temperature be 40 DEG C~70 DEG C, column bottom temperature be 78 DEG C~
185℃；The tower pressure interior force of first reactive distillation column of T2 is the MPa of 1MPa~5, and tower top temperature is 40 DEG C~70 DEG C, tower bottom temperature
Degree is 78 DEG C~185 DEG C；The tower pressure interior force of compression rectification tower T3 is 1MPa~15MPa, and tower top temperature is 78 DEG C~90 DEG C, tower bottom
Temperature is 180 DEG C~185 DEG C；When diethy-aceto oxalate content reaches 75% or more, T2 reactor bottom is to T3 compression rectification tower
Feed liquor.
8. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that described
The partition of reactor and rectifying column is arranged to make the ratio between cross-sectional area of the cross-sectional area of fore-running section and side line section for 1:1-3:1.
9. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 8, which is characterized in that described
The number of plates of fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, and the number of plates of public rectifying section is 1~30 piece, public
The number of plates of stripping section is 1~30 piece altogether；The first reactive distillation column of T1, the first reactive distillation column of T2, T3 compression rectification tower are plate
Formula tower, packed tower or board-like-filler mixing column.
10. a kind of technique by transesterification path synthesis of oxalic acid symmetrical ester according to claim 1, which is characterized in that institute
It states using ethyl alcohol and dimethyl oxalate molar ratio 1:1-20:1 as raw material, it is anti-that transesterification is carried out under basic catalyst existence condition
It answers, prepares diethy-aceto oxalate, charging feedstock and catalyst in reaction kettle, the agitating and heating 0.5-10 h at 78-180 DEG C, institute
State the 0.1-3 wt% that catalyst amount accounts for total mass of raw material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
| CN110613946A (en) * | 2019-10-25 | 2019-12-27 | 福州大学 | Backpack reaction rectification equipment for synthesizing diethyl oxalate and process thereof |
| CN112961057A (en) * | 2021-02-08 | 2021-06-15 | 浙江联盛化学股份有限公司 | Method for continuously producing diethyl oxalate |
| CN113651691A (en) * | 2021-09-15 | 2021-11-16 | 河北工业大学 | Method for preparing asymmetric oxalate through catalytic rectification |
| CN114292182A (en) * | 2021-12-14 | 2022-04-08 | 沈阳化工大学 | Method for synthesizing efficient catalyst from alkyl oxalate |
| CN114773188A (en) * | 2022-04-11 | 2022-07-22 | 山东新和成维生素有限公司 | Continuous recovery method of methyl cardiate residual liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712564A (en) * | 2010-01-20 | 2012-10-03 | 宇部兴产株式会社 | Process for production of diaryl oxalate |
-
2018
- 2018-07-03 CN CN201810715366.5A patent/CN109081779A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712564A (en) * | 2010-01-20 | 2012-10-03 | 宇部兴产株式会社 | Process for production of diaryl oxalate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511138A (en) * | 2019-09-24 | 2019-11-29 | 河北广润化工有限公司 | A kind of production technology of symmetrical oxalate |
| CN110613946A (en) * | 2019-10-25 | 2019-12-27 | 福州大学 | Backpack reaction rectification equipment for synthesizing diethyl oxalate and process thereof |
| CN112961057A (en) * | 2021-02-08 | 2021-06-15 | 浙江联盛化学股份有限公司 | Method for continuously producing diethyl oxalate |
| CN113651691A (en) * | 2021-09-15 | 2021-11-16 | 河北工业大学 | Method for preparing asymmetric oxalate through catalytic rectification |
| CN114292182A (en) * | 2021-12-14 | 2022-04-08 | 沈阳化工大学 | Method for synthesizing efficient catalyst from alkyl oxalate |
| CN114773188A (en) * | 2022-04-11 | 2022-07-22 | 山东新和成维生素有限公司 | Continuous recovery method of methyl cardiate residual liquid |
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