CN1039409C - Process for purifying aqueous glyoxal solution by solvent extraction - Google Patents
Process for purifying aqueous glyoxal solution by solvent extraction Download PDFInfo
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- CN1039409C CN1039409C CN94103371A CN94103371A CN1039409C CN 1039409 C CN1039409 C CN 1039409C CN 94103371 A CN94103371 A CN 94103371A CN 94103371 A CN94103371 A CN 94103371A CN 1039409 C CN1039409 C CN 1039409C
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- solvent
- extraction
- formaldehyde
- glyoxal
- water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to new technology for purifying a glyoxal water solution by a solvent extraction method. The present invention has the main preparation steps that C<5>-C<10> alcohol, chlorobenzene, ethyl benzene, xylene, ether, etc. are mixed as an extraction solvent and are put in a thick glyoxal water solution; at room temperature, multi-stage counter-current extraction is carried out to remove impurities such as formaldehyde, etc. in the glyoxal water solution; in the technology, the extraction solvent can be circularly used after regeneration treatment. A solvent extraction method has the advantages of continuous operation, short operation period and high production efficiency. Since the operation is carried out under normal temperature conditions, energy consumption is greatly reduced. By the technology of control operation, glyoxal which is highly purified is obtained.
Description
The present invention relates to a kind of purifying aqueous glyoxal solution by solvent extraction method of using, belong to chemical technology field.
In the glyoxal water solution that copper scale catalysis makes, outside oxalic dialdehyde, also contain 5-7% formaldehyde by aqueous glycol solution, impurity such as 3-5% ethylene glycol, its purifying require to reducing formaldehyde content to 0.2%, and ethanol content is reduced to 1%.Existing purification process is the method for steam distillation, through four towers and then to the reactor distillation, can remove formaldehyde and part ethylene glycol about 70% earlier.The shortcoming of this method is the energy consumption height, and in the operational cycle long (needing 15 hours approximately), it is not enough that formaldehyde is removed the degree of depth.And, increased the decolouring burden in the subsequent treatment process because long-time distillation makes oxalic dialdehyde product liquid color and luster not good.
The objective of the invention is to design a kind of method with purifying aqueous glyoxal solution by solvent extraction, just with the steam distillation in the solvent extration replacement prior art, from glyoxal water solution, remove formaldehyde, and remove ethylene glycol on a small quantity and reduce solution acidity.But the solvent extration operate continuously, the operational cycle is short, the production efficiency height, this method is to operate under normal temperature condition in addition, thereby energy consumption can reduce greatly.Another object of the present invention is by control extracting operation technology, obtains highly purified oxalic dialdehyde.
Content of the present invention is: the purifying aqueous glyoxal solution by solvent extraction method comprises following each step:
(1) preparation extraction solvent: is 1 with thinner with volume ratio with extraction agent: 0-3: 7 ratio is mixed mutually, and wherein extraction agent is for being selected from C
5-C
10Alcohols (comprising its positive isomer) in any, thinner wherein is to be selected from any in chlorobenzene, ethylbenzene, dimethylbenzene, butyl ether or the isoamyl acetate;
(2) extraction of formaldehyde in the multi-stage counter current extraction process, realizing the extraction solvent of above-mentioned preparation to glyoxal water solution, extraction solvent: the volume ratio of thick glyoxal water solution is 2-5: 1, service temperature is: 15 ℃～40 ℃, the solvent phase and the residence time of water-soluble liquid phase in every grade of mixing section are 15-30 minute;
(3) with the water-soluble liquid phase of the above-mentioned second step gained, decolour, obtain pure oxalic dialdehyde product liquid with activated carbon;
(4) with above-mentioned second the step gained solvent phase, in mole ratio is oxalic dialdehyde: formaldehyde: the ratio of urea=1: 1.8: 1, produce the 2D resin and become a pair product, use the ammonia scrubbing solvent again, remove residual formaldehyde, promptly obtain regenerated solvent after washing solvent at last with water, return the above-mentioned the first step, multiplexing as extraction solvent.
Core of the present invention is with the steam distillation method in the solvent extraction method replacement prior art, to remove the formaldehyde impurity in the glyoxal water solution.Extraction agent is capable of circulation multiplexing after manipulation of regeneration in this technology, because selected extraction solvent is a low water solubility, so its circulation loss amount is very little, and treated the producing of the formaldehyde that is extracted (a small amount of oxalic dialdehyde is arranged simultaneously) paid product.
Used extraction system is made up of extraction agent and thinner, and extraction agent mainly plays extraction, and thinner mainly adds for viscosity and the proportion that reduces extraction system, and it also can have certain influence to extraction process certainly.
The index of screening extraction system has two: one, the percentage extraction ρ formaldehyde of PARA FORMALDEHYDE PRILLS(91,95), the 2nd, formaldehyde and oxalic dialdehyde separating effect, β represents with separation factor, this is its selectivity that extracts formaldehyde.In addition, also to consider its toxicity and other rerum natura and economy etc.
The present invention C
5-C
10Alcohols be extraction agent, just comprising, isomer having 11 kinds altogether, as being example with the octanol, then comprise n-Octanol, isooctyl alcohol and second octanol.
Thinner comprises chlorobenzene, ethylbenzene, dimethylbenzene, butyl ether, amyl acetate-n.
Extraction agent: thinner (V/V) is 1: 0-3: 7
Along with the reduction of extraction agent content, the extraction partition ratio of formaldehyde is linear and descends in this extraction system, formaldehyde and oxalic dialdehyde separation degree then be the index trend of rising.
The renovation process of extraction solvent is that from solvent phase, one step of employing is combined into the 2D resin and reclaims oxalic dialdehyde and formaldehyde, uses the ammoniacal liquor rinse solvent then, to remove residual formaldehyde, washes solvent at last with water, makes solvent reclamation multiplexing.
Embodiments of the invention are as follows: embodiment 1
Aqueous phase liquid: the actual material of factory (oxalic dialdehyde 42.77% formaldehyde 6.3% acidity 0.79%)
Organic phase: 50% isooctyl alcohol+50% dimethylbenzene
Organic phase: water=3: 1, every grade of two-phase was mixed 15 minutes
(25-30 ℃) carries out actually operating at ambient temperature, and after 10 grades of extractions, residual formaldehyde is 0.21% in the extraction raffinate, and glyoxal content is 41.31%, and glyoxal content is 1.82% in the organic phase.Embodiment 2
Aqueous phase liquid: the actual material of factory (oxalic dialdehyde 42.77% formaldehyde 6.3% acidity 0.79%)
Organic phase: 60% isooctyl alcohol+40% dimethylbenzene
Compare: 3.5: 1, two-phase mixing time 20 minutes
Room temperature: through 8 grades of extractions, formaldehyde content reduces to 0.12% in the raffinate, and glyoxal content is 42.79%, organic phase
Middle glyoxal content is 2.60% embodiment 3
Aqueous phase liquid: the actual material of factory (oxalic dialdehyde 42.77% formaldehyde 6.3% acidity 0.79%)
Organic phase: 100% dissident's alcohol
Compare: 3: 1, two-phase mixing time 25 minutes
Room temperature: through 10 grades of extractions, formaldehyde content reduces to 0.1% in the aqueous residue of collection back.
Claims (1)
1, a kind of purifying aqueous glyoxal solution by solvent extraction method is characterized in that this method comprises following each step:
(1) preparation extraction solvent: is 1 with thinner with volume ratio with extraction agent: 0-3: 7 ratio is mixed mutually, and wherein extraction agent is for being selected from C
5-C
10Alcohols in any, thinner wherein is to be selected from any in chlorobenzene, ethylbenzene, dimethylbenzene, butyl ether or the isoamyl acetate;
(2) extraction of formaldehyde in the multi-stage counter current extraction process, realizing the extraction solvent of above-mentioned preparation to glyoxal water solution, extraction solvent: the volume ratio of thick glyoxal water solution is 2-5: 1, service temperature is 15 ℃～40 ℃, and the solvent phase and the residence time of water-soluble liquid phase in every grade of mixing section are 15-30 minute;
(3) with the water-soluble liquid phase of the above-mentioned second step gained, after decolouring with activated carbon, obtain pure oxalic dialdehyde product liquid;
(4) with above-mentioned second the step gained solvent phase, in mole ratio is oxalic dialdehyde: formaldehyde: the ratio of urea=1: 1.8: 1, produce the 2D resin and become a pair product, use the ammonia scrubbing solvent again, remove residual formaldehyde, promptly obtain regenerated solvent after washing solvent at last with water, return the above-mentioned the first step, multiplexing as extraction solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103371A CN1039409C (en) | 1994-04-01 | 1994-04-01 | Process for purifying aqueous glyoxal solution by solvent extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94103371A CN1039409C (en) | 1994-04-01 | 1994-04-01 | Process for purifying aqueous glyoxal solution by solvent extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1096508A CN1096508A (en) | 1994-12-21 |
| CN1039409C true CN1039409C (en) | 1998-08-05 |
Family
ID=5031029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94103371A Expired - Fee Related CN1039409C (en) | 1994-04-01 | 1994-04-01 | Process for purifying aqueous glyoxal solution by solvent extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039409C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2855171B1 (en) * | 2003-05-22 | 2005-08-05 | Clariant | METHOD FOR SEPARATING A GLYOXAL DIACETAL FROM A RAW MIXTURE CONTAINING IT BY LIQUID-LIQUID EXTRACTION AGAINST CURRENT |
| CN111606788B (en) * | 2020-05-27 | 2023-03-17 | 杭州富阳永星化工有限公司 | Post-treatment system and post-treatment method for preparing glyoxal through catalytic oxidation of ethylene glycol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860656A (en) * | 1972-06-08 | 1975-01-14 | Union Carbide Corp | Purification of glyoxal |
| US4006189A (en) * | 1973-06-13 | 1977-02-01 | Veba Chemie Ag | Process for purifying glyoxal |
-
1994
- 1994-04-01 CN CN94103371A patent/CN1039409C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860656A (en) * | 1972-06-08 | 1975-01-14 | Union Carbide Corp | Purification of glyoxal |
| US4006189A (en) * | 1973-06-13 | 1977-02-01 | Veba Chemie Ag | Process for purifying glyoxal |
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| Publication number | Publication date |
|---|---|
| CN1096508A (en) | 1994-12-21 |
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