CN104892400A - Intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid - Google Patents

Intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid Download PDF

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CN104892400A
CN104892400A CN201510294499.6A CN201510294499A CN104892400A CN 104892400 A CN104892400 A CN 104892400A CN 201510294499 A CN201510294499 A CN 201510294499A CN 104892400 A CN104892400 A CN 104892400A
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reaction
tower
oxalic acid
water
next door
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CN104892400B (en
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邱挺
周丽华
黄智贤
李玲
王红星
杨臣
叶长燊
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Fuzhou University
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Fuzhou University
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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
    • 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
    • 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 Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses an intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid. The process particularly comprises the following steps: (1) continuously feeding materials into a reactive dividing-wall rectification tower in a double batch reactor switching mode; (2) enabling dimethyl oxalate and water to enter a batch reactor to react primarily, wherein the equilibrium conversion rate reaches 50%-60%; and (3) continuously feeding reaction solution into a left-side reaction section ( zone b) of the reactive dividing-wall rectification tower from an upper feeding opening, continuously feeding normal-temperature water into the reactive dividing-wall rectification tower from a lower feeding opening of the zone b, and continuously discharging methyl alcohol produced in the reaction process from the tower top, wherein due to the discharging of methyl alcohol, the reaction proceeds to production of oxalic acid until dimethyl oxalate is completely hydrolyzed and the conversion rate can reach 99.5% or above. By virtue of the reactive dividing-wall rectification tower, the synthesis reaction and product separation and purification are implemented in the same tower, the existing process flow is simplified, and energy consumption and investment can be lowered. The intermittent reaction-continuous reaction rectification combined process for catalytic synthesis of oxalic acid has the characteristics of no addition of extra additives, high reaction speed, high conversion rate, low water-ester ratio, simple product separation operation, low energy consumption and the like.

Description

Catalyze and synthesize oxalic acid rhythmic reaction and continuous reaction rectification combination process
Technical field
The invention belongs to the preparing technical field of oxalic acid, be specifically related to one and catalyze and synthesize oxalic acid rhythmic reaction and continuous reaction rectification combination process.
Background technology
Oxalic acid is a kind of important Organic Chemicals, be widely used in the industry such as the refining and leather of medicine, weaving, organic synthesis, rare earth element, also can be used for the aspect such as synthetic dyestuff intermediate and purification hardware, Kaolinite Preparation of Catalyst, synthesis of oxalic acid derivative, the intermediate of synthesis of chemicals and the reagent of 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 not only production cost are high but also can seriously contaminate environment.Although corresponding improvement has all been done to these two kinds of methods by most enterprise, the level of entirety is still not high.In recent years, along with the continuous expansion of oxalic acid Application Areas, the demand of oxalic acid is also increasing constantly.So develop, raw material is easy to get, cost is low, technique is simple, free of contamination oxalic acid production technique is significant.In recent years, along with the high speed development of gas chemical industry and C1 chemical industry, by " CO oxidative coupling prepares barkite, further hydrolysis oxalic acid processed ", operational path is paid close attention to just widely, is also that the oxalic acid of generally acknowledging in the world prepares new way.
The reaction that oxalic acid is prepared in dialkyl oxalate hydrolysis mainly contains following three kinds:
1. dibutyl oxalate hydrolysis:
(COOC 4H 9) 2+2H 2O (COOH) 2+2C 4H 9OH
2. oxalic acid diethyl ester hydrolysis:
(COOC 2H 5) 2+2H 2O (COOH) 2+2C 2H 5OH
3. dimethyl oxalate hydrolysis:
(COOCH 3)2+2H 2O (COOH)2+2CH 3OH
More than the optional use of oxalic acid three kinds of methods are prepared in dialkyl oxalate hydrolysis, but compare with oxalic acid diethyl ester with dibutyl oxalate, dimethyl oxalate is a kind of material that dialkyl oxalate Middle molecule size is minimum and water-soluble is best, this characteristic makes it as the raw materials of oxalic acid, and technical process has its unrivaled superiority.The methyl alcohol boiling point generated after reaction is low, easily separates from system at a lower temperature.Therefore, dimethyl oxalate is more suitable for the raw materials for production as oxalic acid.At present, the technical study of hydrolysis dimethyl oxalate is less, the shortcomings such as principal reaction device is hydrolysis reactor or batch reactor, and the time is long but this technique responds, need to add that other catalyzer and low conversion rate, water to ester ratio are high, subsequent product is purified with separate complex, energy consumption high.
Partition wall type reaction rectification technique is concept reactive distillation being applied to next door tower, has concentrated the advantage of next door tower and reactive distillation tower technology, is that a kind of realization response and separating-purifying carry out simultaneously, realize Energy Coupling thus reach the complex technology of energy-conservation object.In addition, partition wall type reactive distillation tower technology also, on the basis ensureing original high conversion, significantly saves facility investment.
Summary of the invention
The technical problem to be solved in the present invention is: the deficiency existed for prior art, provide one and catalyze and synthesize oxalic acid rhythmic reaction and continuous reaction rectification combination process, have without the need to adding additional catalyst, speed of reaction is fast, transformation efficiency is high, water to ester ratio is low, product separation is simple, the features such as energy consumption is low.
For solving the problems of the technologies described above, technical scheme of the present invention is:
One catalyzes and synthesizes oxalic acid rhythmic reaction and continuous reaction rectification combination process, and concrete steps are as follows:
(1) dimethyl oxalate and water enter in batch reactor B1, at 55 ~ 65 DEG C, carry out initial reaction, and reaction 3 ~ 4h reaches equilibrium state;
(2) reaction solution obtained in step (1) enters conversion zone b district on the left of the tower of next door continuously from upper feeding mouth, and normal-temperature water enters in tower continuously from lower opening for feed, and the methyl alcohol generated in reaction process is continuously separated and distillates by tower top, promotes the carrying out of positive reaction; The water that on the right side of the tower of next door, the continuous extraction in bottom, rectifying section d district is excessive, and to loop back on the left of the tower of next door throat-fed under conversion zone b district, the continuous extraction of tower reactor, containing the oxalic acid solution of a small amount of methyl alcohol, obtains oxalate product through evaporative crystallization;
(3) carry out with step (2), feed intake in batch still B2, reaction conditions is identical with step (1) simultaneously;
(4) in B1 after reaction solution charging, be switched to by reaction solution charging in B2, thus alternately for next door tower provides continuously feeding.
That loads in the tower of next door is filler or column plate, and its working pressure is normal pressure, and reflux ratio is 0.5 ~ 3.
Total mol ratio 8 ~ 11:1 of water and dimethyl oxalate, wherein the mol ratio 3 ~ 5:1 of water and dimethyl oxalate in batch reactor, the mol ratio 5 ~ 6:1 of the dimethyl oxalate on the left of the tower of next door under conversion zone b district in the water of opening for feed and batch reactor.
Advantage of the present invention and positively effect are:
The technique adopting rhythmic reaction to combine with reactive distillation and equipment synthesis of oxalic acid, in reactive distillation, the methyl alcohol generated in dimethyl oxalate and water reaction process is discharged continuously, promote the carrying out of positive reaction, can make dimethyl oxalate complete reaction under lower water to ester ratio condition by rhythmic reaction and continuous reaction rectification combination process, reaction conversion ratio can reach more than 99.5%.Tower top obtains highly purified methyl alcohol, and this methyl alcohol can directly be recycled, and the oxalic acid that hydrolysis reaction generates has self-catalysis, reaction process without the need to adding other catalyzer, the complex operations such as can avoid the separation of catalyzer and recycle.This technique adopts two batch still switch forms counter septum tower to carry out continuously feeding simultaneously, realize dimethyl oxalate to transform completely, reduce reaction water to ester ratio, and in next door tower, the water of side take-off part effectively can reduce the energy consumption of the evaporative crystallization reacting follow-up oxalate product.Hydrolysis reaction, product separation and purification complete by the partition wall type reactive distillation column adopted in a rectifying tower, enormously simplify technical process, save energy consumption and investment.
Accompanying drawing explanation
Fig. 1 is that rhythmic reaction and continuous reaction rectification combine the schematic flow sheet preparing oxalic acid technique.
In figure: B1 and B2 is batch reactor, RD is partition wall type continuous reaction rectification tower (wherein a district is next door tower rectifying section, and 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 stripping section on the right side of the tower of next door).
Embodiment
The present invention is set forth further below in conjunction with accompanying drawing 1 and specific embodiment.
Continuous reaction rectification hydrolysis dimethyl oxalate prepares the device of the processing method employing of oxalic acid as shown in Figure 1: this device mainly comprises batch reactor and partition wall type reactive distillation column.
Embodiment 1
Water and dimethyl oxalate be 5:1 batching in molar ratio, enter in batch reactor, initial reaction is carried out at 65 DEG C, to next door rectifying tower charging after reaction 3h, reaction solution in batch still enters the reaction zone (b district) of next door tower RD continuously from upper feeding mouth, the normal-temperature water of corresponding proportion (total water to ester ratio 10:1 of whole technique) enters in tower from opening for feed reaction zone (b district), the methyl alcohol generated in reaction process is discharged by tower top continuously, (d district) bottom, rectification zone continuous extraction part water on the right side of the tower of next door, tower reactor continuous extraction oxalic acid and excessive water and minute quantity methyl alcohol, design parameter is as follows:
(1) batch reactor volume is 10m 3, temperature of reaction 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 reaction solution air speed (LHSV0.5m3/ (.h)) of partition wall type reactive distillation column.
(4) partition wall type reactive distillation column control of reflux ratio 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% (massfraction), tower reactor methanol content≤0.1%, dimethyl oxalate transformation efficiency >=99.8%.
Embodiment 2
Water and dimethyl oxalate be 4:1 batching in molar ratio, enter in batch reactor, initial reaction is carried out at 60 DEG C, to next door rectifying tower charging after about 4h, reaction solution in batch still enters the reaction zone (b district) of next door tower RD continuously from upper feeding mouth, the normal-temperature water of corresponding proportion (total water to ester ratio 10:1 of whole technique) enters in tower from opening for feed reaction zone (b district), the methyl alcohol generated in reaction process is discharged by tower top continuously, (d district) bottom, rectification zone continuous extraction part water on the right side of the tower of next door, tower reactor continuous extraction oxalic acid and excessive water and minute quantity methyl alcohol, design parameter is as follows:
(1) batch reactor volume is 10m 3, temperature of reaction 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 solution hourly space velocity (LHSV) 0.4m3/ (m3.h) of partition wall type reactive distillation column.
(4) partition wall type reactive distillation column control of reflux ratio 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% (massfraction), tower reactor methanol content≤0.2%, dimethyl oxalate transformation efficiency >=99.5%.
Embodiment 3
Water and dimethyl oxalate be 5:1 batching in molar ratio, enter in batch reactor, initial reaction is carried out at 65 DEG C, to next door rectifying tower charging after reaction 3h, reaction solution in batch still enters the reaction zone (b district) of next door tower RD continuously from upper feeding mouth, the normal-temperature water of corresponding proportion (total water to ester ratio 11:1 of whole technique) enters in tower from opening for feed reaction zone (b district), the methyl alcohol generated in reaction process is discharged by tower top continuously, (d district) bottom, rectification zone continuous extraction part water on the right side of the tower of next door, tower reactor continuous extraction oxalic acid and excessive water and minute quantity methyl alcohol, design parameter is as follows:
(1) batch reactor volume is 10m 3, temperature of reaction 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 reaction solution air speed (LHSV0.4m3/ (.h)) of partition wall type reactive distillation column.
(4) partition wall type reactive distillation column control of reflux ratio 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% (massfraction), tower reactor methanol content≤0.05%, dimethyl oxalate transformation efficiency >=99.6%.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.

Claims (3)

1. catalyze and synthesize oxalic acid rhythmic reaction and a continuous reaction rectification combination process, it is characterized in that: concrete steps are as follows:
(1) dimethyl oxalate and water enter in batch reactor B1, at 55 ~ 65 DEG C, carry out initial reaction, and reaction 3 ~ 4h reaches equilibrium state;
(2) reaction solution obtained in step (1) enters conversion zone b district on the left of the tower of next door continuously from upper feeding mouth, and normal-temperature water enters in tower continuously from lower opening for feed, and the methyl alcohol generated in reaction process is continuously separated and distillates by tower top, promotes the carrying out of positive reaction; The water that on the right side of the tower of next door, the continuous extraction in bottom, rectifying section d district is excessive, and to loop back on the left of the tower of next door throat-fed under conversion zone b district, the continuous extraction of tower reactor, containing the oxalic acid solution of a small amount of methyl alcohol, obtains oxalate product through evaporative crystallization;
(3) carry out with step (2), feed intake in batch still B2, reaction conditions is identical with step (1) simultaneously;
(4) in B1 after reaction solution charging, be switched to by reaction solution charging in B2, thus alternately for next door tower provides continuously feeding.
2. according to claim 1ly catalyze and synthesize oxalic acid rhythmic reaction and continuous reaction rectification combination process, it is characterized in that: in the tower of next door filling be filler or column plate, its working pressure is normal pressure, and reflux ratio is 0.5 ~ 3.
3. according to claim 1ly catalyze and synthesize oxalic acid rhythmic reaction and continuous reaction rectification combination process, it is characterized in that: total mol ratio 8 ~ 11:1 of water and dimethyl oxalate, the wherein mol ratio 3 ~ 5:1 of water and dimethyl oxalate in batch reactor, the mol ratio 5 ~ 6:1 of the dimethyl oxalate on the left of the tower of next door under conversion zone b district in the water of opening for feed and batch reactor.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106957223A (en) * 2017-04-24 2017-07-18 上海华峰新材料研发科技有限公司 A kind of method that C4 ~ C6 dicarboxylic acid monomers are purified 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
CN110713437A (en) * 2019-10-29 2020-01-21 福州大学 Device and method for preparing oxalic acid by hydrolyzing oxalate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991010637A1 (en) * 1990-01-09 1991-07-25 Kemira Oy A process for preparing oxalic acid
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991010637A1 (en) * 1990-01-09 1991-07-25 Kemira Oy A process for preparing oxalic acid
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106957223A (en) * 2017-04-24 2017-07-18 上海华峰新材料研发科技有限公司 A kind of method that C4 ~ C6 dicarboxylic acid monomers are purified 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
CN110713437A (en) * 2019-10-29 2020-01-21 福州大学 Device and method for preparing oxalic acid by hydrolyzing oxalate
CN110713437B (en) * 2019-10-29 2021-06-08 福州大学 Device and method for preparing oxalic acid by hydrolyzing oxalate

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