CN104892400B - Catalyze and synthesize oxalic acid intermittent reaction and continuous reaction rectification group technology - Google Patents
Catalyze and synthesize oxalic acid intermittent reaction and continuous reaction rectification group technology Download PDFInfo
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- CN104892400B CN104892400B CN201510294499.6A CN201510294499A CN104892400B CN 104892400 B CN104892400 B CN 104892400B CN 201510294499 A CN201510294499 A CN 201510294499A CN 104892400 B CN104892400 B CN 104892400B
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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
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses one and catalyze and synthesize oxalic acid intermittent reaction and continuous reaction rectification group technology, specifically comprise the following steps that (1) uses double batch still switch forms counter septum formula reactive distillation column to carry out continuous feed.(2) dimethyl oxalate and water enter batch reactor initial reaction, and equilibrium conversion reaches 50%～60%.(3) reactant liquor continuously enters conversion zone on the left of the tower of next door (b district) from upper feeding mouth, normal-temperature water charging aperture from b district continuously enters in tower, the methyl alcohol generated in course of reaction is discharged by tower top continuously, discharge due to methyl alcohol, react the direction to generating oxalic acid to carry out, until dimethyl oxalate all hydrolyzes, conversion ratio is up to more than 99.5%.Synthetic reaction, product Separation & Purification are realized in a tower by partition wall type reactive distillation column, simplify existing technological process, save energy consumption and investment.The present invention has without adding additional catalyst, reaction rate is fast, conversion ratio is high, water to ester ratio is low, product separates simple, the features such as energy consumption is low.
Description
Technical field
The invention belongs to the preparing technical field of oxalic acid, be specifically related to one and catalyze and synthesize oxalic acid intermittent reaction with the most anti-
Answer rectifying group technology.
Background technology
Oxalic acid is a kind of important Organic Chemicals, is widely used in medicine, weaving, organic synthesis, rare earth element
The industry such as refined and leather, also can be used for synthetic dyestuffs intermediate and purify hardware, prepare catalyst, synthesis of oxalic acid
The aspects such as the reagent of derivative, the intermediate of synthesis of chemicals and some necessity.
At present, the method for the main production oxalic acid of domestic employing has sodium formate method and nitric acid oxidation method, and these two kinds of methods are not
Only production cost is high and can seriously pollute environment.Change accordingly although both approaches has all been done by most enterprise
Enter, but the level of entirety is the highest.In recent years, along with the continuous extension of oxalic acid application, the demand of oxalic acid is also being held
Increase continuously.So developing, raw material is easy to get, low cost, technique oxalic acid production technology simple, free of contamination is significant.
In recent years, along with gas chemical industry and the high speed development of C1 chemical industry, by " CO oxidative coupling prepares oxalate, hydrolyzes system further
Oxalic acid " process route is paid close attention to the most widely, is also that the oxalic acid generally acknowledged in the world prepares new way.
The reaction of oxalic acid is prepared in dialkyl oxalate hydrolysis mainly following three kinds:
1. dibutyl oxalate hydrolysis:
(COOC4H9)2+2H2O(COOH)2+2C4H9OH
2. diethy-aceto oxalate hydrolysis:
(COOC2H5)2+2H2O(COOH)2+2C2H5OH
3. dimethyl oxalate hydrolysis:
(COOCH3)2+2H2O(COOH)2+2CH3OH
Dialkyl oxalate hydrolysis is prepared oxalic acid and be can be selected for three of the above method, but with dibutyl oxalate and diethy-aceto oxalate
Comparing, dimethyl oxalate is the minimum a kind of material best with water-soluble of dialkyl oxalate Middle molecule size, this characteristic
Make it prepare raw material as oxalic acid, technological process has its unrivaled superiority.The methyl alcohol boiling point generated after reaction
Low, separate from system the most at a lower temperature.Therefore, to be more suitable for the production of oxalic acid former for dimethyl oxalate
Material.At present, the technical study of hydrolysis dimethyl oxalate is less, and key reaction device is hydrolysis reactor or batch reactor, but
This technique respond time length, need to add other catalyst and conversion ratio is low, water to ester ratio is high, subsequent product purify and separate
The shortcomings such as complicated, energy consumption is high.
Partition wall type reaction rectification technique is the concept that reactive distillation is applied to next door tower, has concentrated next door tower and reaction essence
Evaporate the advantage of tower technology, be a kind of to realize reaction and carry out with separating-purifying simultaneously, realize energy and couple thus reach energy-conservation purpose
Complex technology.In addition, partition wall type reactive distillation tower technology is also on the basis of ensureing original high conversion, significantly
Save equipment investment.
Summary of the invention
The technical problem to be solved in the present invention is: the deficiency existed for prior art, it is provided that one catalyzes and synthesizes grass
Acid intermittent reaction and continuous reaction rectification group technology, have without add additional catalyst, reaction rate is fast, conversion ratio is high,
Water to ester ratio is low, product separates simple, the features such as energy consumption is low.
For solving above-mentioned technical problem, the technical scheme is that
One catalyzes and synthesizes oxalic acid intermittent reaction and continuous reaction rectification group technology, specifically comprises the following steps that
(1) dimethyl oxalate and water enter in batch reactor B1, carry out initial reaction at 55 ~ 65 DEG C, react 3 ~ 4h
Reach poised state；
(2) reactant liquor obtained in step (1) continuously enters conversion zone b district, normal-temperature water on the left of the tower of next door from upper feeding mouth
Continuously entering in tower from lower charging aperture, the methyl alcohol generated in course of reaction is continuously separated and distillates by tower top, promotes entering of positive reaction
OK；The water of the continuous extraction in bottom, rectifying section d district excess on the right side of the tower of next door, and loop back charging under conversion zone b district on the left of the tower of next door
Mouth charging, the tower reactor continuous extraction oxalic acid solution containing a small amount of methyl alcohol, obtain oxalate product through evaporative crystallization；
(3) carrying out with step (2) simultaneously, feed intake in batch still B2, reaction condition is identical with step (1)；
(4) in B1 after reactant liquor charging, it is switched to be fed by reactant liquor in B2, thus alternately provides even for next door tower
Continuous charging.
That loads in the tower of next door is filler or column plate, and its operation pressure is normal pressure, and reflux ratio is 0.5～3.
Total mol ratio 8～11:1 of water and dimethyl oxalate, wherein in batch reactor water and dimethyl oxalate mole
Ratio 3～5:1, on the left of the tower of next door under conversion zone b district the dimethyl oxalate in the water of charging aperture and batch reactor mol ratio 5～
6:1。
Advantages of the present invention and good effect be:
Use the technique that combines with reactive distillation of intermittent reaction and equipment synthesis of oxalic acid, by oxalic acid diformazan in reactive distillation
The methyl alcohol generated in ester and water course of reaction is discharged continuously, promotes the carrying out of positive reaction, by intermittent reaction and successive reaction essence
Evaporating group technology can make dimethyl oxalate react completely under the conditions of relatively low water to ester ratio, and reaction conversion ratio is up to more than 99.5%.Tower
Top obtains highly purified methyl alcohol, and this methyl alcohol can directly recycle, and the oxalic acid that hydrolysis generates has autocatalysis, instead
Answer process without adding other catalyst, the complex operations such as separation and the recycling that can avoid catalyst.This technique is adopted simultaneously
Continuous feed is carried out, it is achieved dimethyl oxalate converts completely, reduces reaction water ester with double batch still switch forms counter septum towers
In ratio, and next door tower, the water of side take-off part can effectively reduce the energy consumption of the evaporative crystallization reacting follow-up oxalate product.Adopt
Partition wall type reactive distillation column hydrolysis, product Separation & Purification are completed in a rectifying column, enormously simplify work
Process flow, saves energy consumption and investment.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that oxalic acid technique is prepared in intermittent reaction and continuous reaction rectification combination.
In figure: B1 and B2 is batch reactor, RD is that (wherein a district is next door tower rectifying to partition wall type continuous reaction rectification tower
Section, b district is conversion zone on the left of the tower of next door, and c district is next door tower stripping section, and d district is rectifying section on the right side of the tower of next door, and e is that next door tower is right
Side stripping section).
Detailed description of the invention
The present invention is expanded on further below in conjunction with accompanying drawing 1 and specific embodiment.
Continuous reaction rectification hydrolysis dimethyl oxalate prepares the device of the process employing of oxalic acid as shown in Figure 1: this dress
Put and mainly include batch reactor and partition wall type reactive distillation column.
Embodiment 1
Water and dimethyl oxalate 5:1 dispensing in molar ratio, enters in batch reactor, carries out initial reaction at 65 DEG C,
Feeding to next door rectifying column after reaction 3h, the reactant liquor in batch still continuously enters the reaction zone (b of next door tower RD from upper feeding mouth
District), the normal-temperature water of corresponding proportion (total water to ester ratio 10:1 of whole technique) charging aperture from reaction zone (b district) enters in tower, tower
The methyl alcohol generated in course of reaction is discharged by top continuously, the rectification zone continuous extraction in (d district) bottom part water, tower reactor on the right side of the tower of next door
Extraction oxalic acid and excessive water and very small amount methyl alcohol continuously, design parameter is as follows:
(1) batch reactor volume is 10m3, reaction temperature is 65 DEG C (± 1 DEG C).
(2) partition wall type reactive distillation column tower diameter 800mm, rectifying section (a district) 6m, left side conversion zone (b district) 12m, stripping section
(c district) 4m；Right side rectifying section (d district) 6m, right side stripping section (e district) 5m.
(3) the reactant liquor air speed (LHSV0.5m/(.h)) of partition wall type reactive distillation column.
(4) partition wall type reactive distillation column reflux ratio controls is 4.
(5) partition wall type reactive distillation column overhead temperatures is 65 DEG C (± 1 DEG C), bottom temperature 108 DEG C (± 1 DEG C).
Partition wall type reactive distillation column overhead methanol content >=99.8% (mass fraction), tower reactor methanol content≤0.1%, oxalic acid
Dimethyl ester conversion ratio >=99.8%.
Embodiment 2
Water and dimethyl oxalate 4:1 dispensing in molar ratio, enters in batch reactor, carries out initial reaction at 60 DEG C,
Feeding to next door rectifying column after about 4h, the reactant liquor in batch still continuously enters the reaction zone (b of next door tower RD from upper feeding mouth
District), the normal-temperature water of corresponding proportion (total water to ester ratio 10:1 of whole technique) charging aperture from reaction zone (b district) enters in tower, tower
The methyl alcohol generated in course of reaction is discharged by top continuously, the rectification zone continuous extraction in (d district) bottom part water, tower reactor on the right side of the tower of next door
Extraction oxalic acid and excessive water and very small amount methyl alcohol continuously, design parameter is as follows:
(1) batch reactor volume is 10m3, reaction temperature is 60 DEG C (± 1 DEG C).
(2) partition wall type reactive distillation column tower diameter 800mm, rectifying section (a district) 6m, left side conversion zone (b district) 12m, stripping section
(c district) 4m；Right side rectifying section (d district) 6m, right side stripping section (e district) 5m.
(3) reaction liquid hourly space velocity (LHSV) (LHSV) 0.4m of partition wall type reactive distillation column/(m .h).
(4) partition wall type reactive distillation column reflux ratio controls is 3.
(5) partition wall type reactive distillation column overhead temperatures is 65 DEG C (± 1 DEG C), bottom temperature 106 DEG C (± 1 DEG C).
Partition wall type reactive distillation column overhead methanol content >=99.6% (mass fraction), tower reactor methanol content≤0.2%, oxalic acid
Dimethyl ester conversion ratio >=99.5%.
Embodiment 3
Water and dimethyl oxalate 5:1 dispensing in molar ratio, enters in batch reactor, carries out initial reaction at 65 DEG C,
Feeding to next door rectifying column after reaction 3h, the reactant liquor in batch still continuously enters the reaction zone (b of next door tower RD from upper feeding mouth
District), the normal-temperature water of corresponding proportion (total water to ester ratio 11:1 of whole technique) charging aperture from reaction zone (b district) enters in tower, tower
The methyl alcohol generated in course of reaction is discharged by top continuously, the rectification zone continuous extraction in (d district) bottom part water, tower reactor on the right side of the tower of next door
Extraction oxalic acid and excessive water and very small amount methyl alcohol continuously, design parameter is as follows:
(1) batch reactor volume is 10m3, reaction temperature is 65 DEG C (± 1 DEG C).
(2) partition wall type reactive distillation column tower diameter 800mm, rectifying section (a district) 6m, left side conversion zone (b district) 12m, stripping section
(c district) 6m；Right side rectifying section (d district) 6m, right side stripping section (e district) 5m.
(3) the reactant liquor air speed (LHSV0.4m/(.h)) of partition wall type reactive distillation column.
(4) partition wall type reactive distillation column reflux ratio controls is 3.
(5) partition wall type reactive distillation column overhead temperatures is 65 DEG C (± 1 DEG C), bottom temperature 107 DEG C (± 1 DEG C).
Partition wall type reactive distillation column overhead methanol content >=99.8% (mass fraction), tower reactor methanol content≤0.05%, grass
Dimethyl phthalate conversion ratio >=99.6%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (2)
1. one kind catalyzes and synthesizes oxalic acid intermittent reaction and continuous reaction rectification group technology, it is characterised in that: specifically comprise the following steps that
(1) dimethyl oxalate and water enter in batch reactor B1, carry out initial reaction at 55～65 DEG C, and reaction 3～4h reaches
To poised state；
(2) reactant liquor obtained in step (1) continuously enters conversion zone b district on the left of the tower of next door from upper feeding mouth, normal-temperature water under
Charging aperture continuously enters in tower, and the methyl alcohol generated in course of reaction is continuously separated and distillates by tower top, promotes the carrying out of positive reaction；Every
The water of rectifying section (d district) the continuous extraction in bottom excess on the right side of wall tower, and loop back on the left of the tower of next door charging aperture under conversion zone b district and enter
Material, the tower reactor continuous extraction oxalic acid solution containing a small amount of methyl alcohol, obtain oxalate product through evaporative crystallization；
(3) carrying out with step (2) simultaneously, feed intake in batch still B2, reaction condition is identical with step (1)；
(4), in batch reactor B1 after reactant liquor charging, it is switched to be fed by reactant liquor in batch still B2, is the most alternately
Next door tower provides continuous feed；
That loads in the tower of next door is filler or column plate, and its operation pressure is normal pressure, and reflux ratio is 0.5～3.
Oxalic acid intermittent reaction and the continuous reaction rectification group technology of catalyzing and synthesizing the most according to claim 1, its feature exists
In total mol ratio 8～11:1 of water and dimethyl oxalate, wherein in batch reactor water and dimethyl oxalate mol ratio 3～
5:1, the mol ratio 5～6:1 of the dimethyl oxalate in the water of charging aperture and batch reactor under conversion zone b district on the left of the tower of next door.
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| CN201510294499.6A CN104892400B (en) | 2015-06-02 | 2015-06-02 | Catalyze and synthesize oxalic acid intermittent reaction and continuous reaction rectification group technology |
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| CN104892400B true CN104892400B (en) | 2016-09-07 |
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| CN106957223B (en) * | 2017-04-24 | 2019-11-26 | 上海华峰新材料研发科技有限公司 | A method of purifying C4~C6 dicarboxylic acid monomer from adipic acid by-product mixed dibasic acid |
| CN110357771A (en) * | 2018-04-09 | 2019-10-22 | 中国石化扬子石油化工有限公司 | A kind of partition tower process of methyl lactate hydrolysis rectifying |
| CN110713437B (en) * | 2019-10-29 | 2021-06-08 | 福州大学 | Device and method for preparing oxalic acid by hydrolyzing oxalate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263082A (en) * | 2000-01-06 | 2000-08-16 | 天津大学 | Method for preparing oxalic acid by using diethyl oxalate |
| CN102001938A (en) * | 2009-08-28 | 2011-04-06 | 上海焦化有限公司 | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FI87191C (en) * | 1990-01-09 | 1992-12-10 | Kemira Oy | Process for the production of oxalic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263082A (en) * | 2000-01-06 | 2000-08-16 | 天津大学 | Method for preparing oxalic acid by using diethyl oxalate |
| CN102001938A (en) * | 2009-08-28 | 2011-04-06 | 上海焦化有限公司 | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid |
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