CN109761800A - The method of continuous crystallisation removing oxalic acid in glyoxalic acid production process - Google Patents
The method of continuous crystallisation removing oxalic acid in glyoxalic acid production process Download PDFInfo
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- CN109761800A CN109761800A CN201811589152.4A CN201811589152A CN109761800A CN 109761800 A CN109761800 A CN 109761800A CN 201811589152 A CN201811589152 A CN 201811589152A CN 109761800 A CN109761800 A CN 109761800A
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- oxalic acid
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Abstract
The present invention relates to a kind of methods of continuous crystallisation removing oxalic acid in glyoxalic acid production process, belong to chemosynthesis technical field.This method comprises the following steps: one, the concentrate of enrichment process is continuously added to level-one forecooler, after system is cooled to 40 DEG C or less, primary crystallization device is flowed into, carries out decrease temperature crystalline；Two, enter centrifuge when the feed liquid in primary crystallization device, which continuously flows, is cooled to 35 DEG C or less and be separated by solid-liquid separation, obtain separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 1.0%, separation mother liquor enters ground tank；Three, separate mother liquor and through centrifugal pump squeeze into second level forecooler, be cooled to 10 DEG C or so it is following when, into secondary crystallizer in be cooled down twice crystallization；Four, enter centrifuge when the feed liquid in secondary crystallization device, which continuously flows, is cooled to 0 DEG C ~ -5 DEG C and be separated by solid-liquid separation, obtain separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 0.5%, separation mother liquor enters ground tank.
Description
Technical field
The present invention relates to a kind of acetaldehyde acid production process, in particular to continuous crystallisation removes in a kind of glyoxalic acid production process
The method of oxalic acid, belongs to chemosynthesis technical field.
Background technique
Glyoxalic acid is a kind of important industrial chemicals, be mainly used as cosmetics deodorant tune and fixastive, for pharmacy.Mesh
Preceding there are commonly 4 kinds of preparation methods, specifically:
1. oxalic acid electrolysis method oxalic acid aqueous solution through electroreduction, generates glyoxalic acid weak solution, then through evaporation, concentration, freezing,
Gradually concentrate is filtered, qualified product packaging is finally obtained.
2. oxidation of glyoxal glyoxal is aoxidized through air or oxygen under the action of catalyst, glyoxalic acid is generated, is then passed through
Purification purifies to obtain finished product.In addition, dichloroacetic acid and sodium methoxide are condensed to yield dimethoxyacetic acid sodium, then just generated with hydrochloric acid hydrolysis
Glyoxalic acid.
3. dichloroacetic acid method is heated in sodium methoxide and methanol investment reactor tank 40 ~ 50 DEG C, two chloroethenes is slowly added dropwise
Acid, back flow reaction 2h, condensation finish in the completed, are then cooled to room temperature, filtering, and methanol washing merges washing filtrate to get diformazan
Ethoxyacetic acid sodium methanol solution.The solution is concentrated to dryness again, 2.8 parts of hydrochloric acid are added in heating in water-bath, and stir into
Paste and hydrolysate, then be warming up to 90 DEG C, be cooled to 10 DEG C or so, filtering separates to get finished product.
4. cis-butenedioic anhydride is dissolved in formic acid by cis-butenedioic anhydride ozonisation reduction method, it is passed through ozone oxidation, is then restored and is obtained with zinc powder etc.
Glyoxalic acid.
More the most commonly used is oxidation of glyoxal, and glyoxal nitric acid oxidation method all uses batch tank raw at home at present
Production. art, number of devices is more, and employee's frequent operation, large labor intensity, working environment is poor, and product medium-height grass acid content is high, is not easy to reach
Mark, stable product quality are poor.Therefore, it is badly in need of changing defect present in current production technology, work can be improved by inventing one kind
Make environment, can be improved efficiency, improve product quality, reduces production cost, the stable industrialized production preparation side of safe operation
Method.
Summary of the invention
The purpose of the present invention is to provide a kind of method of continuous crystallisation removing oxalic acid in glyoxalic acid production process, this method
Have the advantages that oxalic acid residual volume is few, quality is stable, it is easily-controllable it is easy to operate, production capacity is big, operating cost is low etc..
The technical solution adopted by the present invention to solve the technical problems is:
The method of continuous crystallisation removing oxalic acid, this method specifically comprise the following steps: in glyoxalic acid production process
The concentrate of enrichment process is continuously added to level-one forecooler by step 1, after system is cooled to 40 DEG C or less, flows into one
Secondary crystallizer carries out decrease temperature crystalline；
Step 2 enters centrifuge when the feed liquid in primary crystallization device, which continuously flows, is cooled to 35 DEG C or less and carries out solid-liquid point
From obtaining separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 1.0%, oxalic acid recycling and reusing after washing and drying, separation is female
Liquid enters ground tank；
Step 3, the separation mother liquor in first degree crystalline equipment squeeze into second level forecooler through centrifugal pump, be cooled to 10 DEG C or so it is following
When, into secondary crystallizer in be cooled down twice crystallization；
Step 4 enters centrifuge when the feed liquid in secondary crystallization device, which continuously flows, is cooled to 0 DEG C ~ -5 DEG C and carries out solid-liquid point
From obtaining separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 0.5%, oxalic acid recycling and reusing after washing and drying, separation is female
Liquid enters ground tank.
Preferably, glyoxalic acid mass concentration is 33 ~ 36wt% after the concentrate thickening.
The primary crystallization temperature is 25 DEG C ~ 30 DEG C, and the primary crystallization time is 15 ~ 30 minutes.Further, primary crystallization
Flow control in 25L/min.
The secondary crystallization temperature is 0 DEG C ~ -5 DEG C, and the secondary crystallization time is 15 ~ 30 minutes.Further, secondary crystallization
Flow control in 20L/min.
Contained glyoxalic acid mass concentration is≤0.02% in oxalic acid after crystallizing twice.
Compared with prior art, the beneficial effects of the present invention are:
1, product quality improves significant, finished product medium-height grass acid content≤0.5%, home products mesoxalic acid real content >=1.0%；
It is detected using continuous sampling in apparatus of the present invention process of reproduction, average data can reach:
Primary crystallization mother liquor: 36.8% oxalic acid 0.97% of glyoxalic acid；
Secondary crystallization mother liquor: 37.3% oxalic acid 0.36% of glyoxalic acid.
2, glyoxalic acid while the domestic problem of crystallization when thoroughly solving 0 DEG C of following crystallization；
3, quality is stablized；
4, mitigate the labor intensity of worker, improve working environment, reduces operating cost.
In addition, the present invention is controlled using DCS, continuous feed, the process for discharging, being automatically separated improve work effect
The stability of rate and product；Mainly it is reduction of finished product medium-height grass acid content；It can prevent because being brought using calcium salt method removing oxalic acid
Production cost raising and solid waste generation.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of second level continuous crystallisation equipment of the invention,
Wherein, 1 level-one forecooler, 2 primary crystallization devices, 3 centrifuges, 4 ground tanks, 5 centrifugal pumps, 6 second level forecoolers, 7 two knots
Brilliant device.
Specific embodiment
Below by specific embodiment, technical scheme of the present invention will be further explained in detail.It should be appreciated that this hair
Bright implementation is not limited by the following examples, and the accommodation in any form made to the present invention and/or changed will all be fallen
Enter the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
Embodiment:
For the second level continuous crystallisation equipment of the method for the present invention, which connected by first degree crystalline equipment and secondary crystallization equipment
It forms, first degree crystalline equipment is identical with the composition of secondary crystallization equipment, and first degree crystalline equipment includes level-one forecooler 1, with level-one
Primary crystallization device 2, centrifuge 3 and the ground tank 4 that forecooler is sequentially connected；Ground tank piping connection centrifugal pump 5, centrifugal pump and two
Grade crystallizer second level forecooler phase 6 connect, the forecooler of secondary crystallization equipment be sequentially connected secondary crystallization device 7, centrifuge and
Ground tank.
The method of continuous crystallisation removing oxalic acid, this method comprise the concrete steps that in glyoxalic acid production process:
The concentrate that enrichment process obtains is taken, glyoxalic acid mass concentration is 33wt% ~ 36wt% in the concentrate；
Concentrate is passed through level-one forecooler 1 with the speed of about 25L per minute, through level-one forecooler be cooled to 40 DEG C hereinafter, into
Enter primary crystallization device 2 and carries out decrease temperature crystalline.Concentrate continuously flowing cooling 20 minutes or so in crystallizer, to feed liquid
When temperature≤30 DEG C, it is separated by solid-liquid separation into centrifuge 3.Isolated oxalic acid is packed after automatic washing drying, is recycled
It utilizes；Isolated mother liquor enters ground tank 4, squeezes into second level forecooler 6 through centrifugal pump 5 and continues with 20L's per minute or so
Speed, continuous pre-cooled device are cooled to material temperature≤10 DEG C, carry out salt water decrease temperature crystalline into secondary crystallization device 7.
Mother liquor continuously flowing cooling 20 minutes or so in secondary crystallization device, when feed liquid temperature≤- 3 DEG C, enters
Centrifuge is separated by solid-liquid separation.Isolated oxalic acid is packed after automatic washing drying.Obtained freezing mother liquor is centrifuged to go down
One process is handled.
Multiple sample detection, testing result in above-mentioned state Behavior of Continuous Crystallization Processes are as follows:
1, first separation mother liquor: 35.96% oxalic acid 0.98% of glyoxalic acid
Secondary separation mother liquor: 36.45% oxalic acid 0.38% of glyoxalic acid
2, first separation mother liquor: 36.21% oxalic acid 0.99% of glyoxalic acid
Secondary separation mother liquor: 36.78% oxalic acid 0.35% of glyoxalic acid
3, first separation mother liquor: 36.35% oxalic acid 0.95% of glyoxalic acid
Secondary separation mother liquor: 36.81% oxalic acid 0.37% of glyoxalic acid.
Contained glyoxalic acid mass concentration is≤0.02% in oxalic acid after crystallizing twice.
Comparative example:
Under equal conditions, batch crystallization process obtains sample data result are as follows:
1, first separation mother liquor: 32.96% oxalic acid 1.12% of glyoxalic acid
Secondary separation mother liquor: 33.45% oxalic acid 0.82% of glyoxalic acid
2, first separation mother liquor: 33.21% oxalic acid 1.16% of glyoxalic acid
Secondary separation mother liquor: 33.78% oxalic acid 0.81% of glyoxalic acid
3, first separation mother liquor: 32.35% oxalic acid 1.13% of glyoxalic acid
Secondary separation mother liquor: 32.81% oxalic acid 0.85% of glyoxalic acid.
It confirming according to testing result, stable product quality made from the method for the present invention, yield is high, and oxalic acid content is lower, this
Process is suitble to industrially scalable metaplasia to produce.
Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form
Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.
Claims (7)
1. a kind of method of continuous crystallisation removing oxalic acid in glyoxalic acid production process, it is characterised in that this method specifically includes as follows
Step:
Step 1, the concentrate that enrichment process is obtained are continuously added to level-one forecooler, after system is cooled to 40 DEG C or less, stream
Enter primary crystallization device, carries out decrease temperature crystalline；
Step 2 enters centrifuge when the feed liquid in primary crystallization device, which continuously flows, is cooled to 35 DEG C or less and carries out solid-liquid point
From obtaining separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 1.0%, oxalic acid recycling and reusing after washing and drying, separation is female
Liquid enters ground tank；
Step 3, the separation mother liquor in first degree crystalline equipment squeeze into second level forecooler through centrifugal pump, be cooled to 10 DEG C or so it is following
When, into secondary crystallizer in be cooled down twice crystallization；
Step 4 enters centrifuge when the feed liquid in secondary crystallization device, which continuously flows, is cooled to 0 DEG C ~ -5 DEG C and carries out solid-liquid point
From obtaining separation mother liquor and solid phase oxalic acid that oxalic acid content is lower than 0.5%, oxalic acid recycling and reusing after washing and drying, separation is female
Liquid enters ground tank.
2. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: should
Method carries out removing oxalic acid using second level continuous crystallisation equipment, which connected by first degree crystalline equipment and secondary crystallization equipment
It forms, first degree crystalline equipment is identical with the composition of secondary crystallization equipment, and first degree crystalline equipment includes level-one forecooler, pre- with level-one
Primary crystallization device, centrifuge and the ground tank that cooler is sequentially connected；Ground tank piping connection centrifugal pump, centrifugal pump and secondary crystallization
The second level forecooler of equipment is connected, and the forecooler of secondary crystallization equipment is sequentially connected secondary crystallization device, centrifuge and ground tank.
3. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: institute
Glyoxalic acid mass concentration is 33 ~ 36wt% in the concentrate stated.
4. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: two
Contained glyoxalic acid mass concentration is≤0.02% in oxalic acid after secondary crystallization.
5. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: institute
Stating primary crystallization temperature is 25 DEG C ~ 30 DEG C, and the primary crystallization time is 15 ~ 30 minutes.
6. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: institute
Stating secondary crystallization temperature is 0 DEG C ~ -5 DEG C, and the secondary crystallization time is 15 ~ 30 minutes.
7. the method for continuous crystallisation removing oxalic acid in glyoxalic acid production process according to claim 1, it is characterised in that: one
Subcrystalline flow control is in 25L/min, and the flow control of secondary crystallization is in 20L/min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811589152.4A CN109761800B (en) | 2018-12-25 | 2018-12-25 | Method for removing oxalic acid by continuous crystallization in glyoxylic acid production process |
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| CN201811589152.4A CN109761800B (en) | 2018-12-25 | 2018-12-25 | Method for removing oxalic acid by continuous crystallization in glyoxylic acid production process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647911A (en) * | 2020-03-27 | 2020-09-11 | 昆明理工大学 | Process for removing magnesium ions in electrolytic manganese anolyte |
| CN114684879A (en) * | 2020-12-25 | 2022-07-01 | 中核四0四有限公司 | One-pass oxalic acid oxidation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3132006A1 (en) * | 1981-08-13 | 1983-03-03 | Chemische Werke Hüls AG, 4370 Marl | Process for preparing glyoxylic acid |
| CN1740133A (en) * | 2005-09-29 | 2006-03-01 | 王金锋 | Technological process of purifying and refining glyoxylic acid |
| CN102786410A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Treating method and apparatus for reaction solution produced in synthesis of glyoxalic acid through nitric acid oxidation of glyoxal |
| CN103896761A (en) * | 2014-03-18 | 2014-07-02 | 湖北省宏源药业有限公司 | Method for composite oxidation and synthesis of glyoxalic acid |
-
2018
- 2018-12-25 CN CN201811589152.4A patent/CN109761800B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3132006A1 (en) * | 1981-08-13 | 1983-03-03 | Chemische Werke Hüls AG, 4370 Marl | Process for preparing glyoxylic acid |
| CN1740133A (en) * | 2005-09-29 | 2006-03-01 | 王金锋 | Technological process of purifying and refining glyoxylic acid |
| CN102786410A (en) * | 2012-07-26 | 2012-11-21 | 湖北省宏源药业有限公司 | Treating method and apparatus for reaction solution produced in synthesis of glyoxalic acid through nitric acid oxidation of glyoxal |
| CN103896761A (en) * | 2014-03-18 | 2014-07-02 | 湖北省宏源药业有限公司 | Method for composite oxidation and synthesis of glyoxalic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111647911A (en) * | 2020-03-27 | 2020-09-11 | 昆明理工大学 | Process for removing magnesium ions in electrolytic manganese anolyte |
| CN114684879A (en) * | 2020-12-25 | 2022-07-01 | 中核四0四有限公司 | One-pass oxalic acid oxidation method |
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| CN109761800B (en) | 2022-04-08 |
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