CN105669424A - Glyoxalic acid and preparation method thereof - Google Patents
Glyoxalic acid and preparation method thereof Download PDFInfo
- Publication number
- CN105669424A CN105669424A CN201610121053.8A CN201610121053A CN105669424A CN 105669424 A CN105669424 A CN 105669424A CN 201610121053 A CN201610121053 A CN 201610121053A CN 105669424 A CN105669424 A CN 105669424A
- Authority
- CN
- China
- Prior art keywords
- acid
- preparation
- parts
- quality
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/147—Saturated compounds having only one carboxyl group and containing —CHO groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a glyoxalic acid and a preparation method thereof. The technical scheme is as follows: the preparation method comprises the following steps: adding 100 parts by mass of 40 wt% glyoxal water solution, 10-20 parts by mass of 30 wt% hydrochloric acid solution and 10-25 parts by mass of 5-20 wt% nitrous acid water solution into a reaction kettle, heating to 45-55 DEG C while stirring, and adding 0.12-0.62 part by mass of sodium nitrate to obtain an initiation system; introducing oxygen into the initiation system with air stone at 55-65 DEG C under normal pressure while stirring, and meanwhile, uniformly and dropwisely adding 30-40 parts by mass of 30-45 wt% nitric acid into the initiation system; heating to 75-85 DEG C while stirring, and keeping the temperature for 1-2 hours; and adding 1-4 parts by mass of 30-45 wt% nitric acid, and continuing keeping the temperature for 1-2 hours, thereby obtaining the glyoxalic acid. The preparation method has the characteristics of low nitric acid consumption, low oxynitride discharge amount and high yield, and is beneficial to industrial production.
Description
Technical field
The invention belongs to organic acid technology field. It is specifically related to a kind of oxoethanoic acid and its preparation method.
Technical background
Oxoethanoic acid is a kind of important industrial chemicals and intermediate, and the application in fields such as medicine, agricultural chemicals, spices, papermaking, foodstuff additive and biological chemistries constantly expands. It is mainly used at present in the production of Broad spectrum antibiotics amoxycilline Trihydrate bp, cefaparole, antihypertensive drug atenolol USP 23, spices vanillin food grade,1000.000000ine mesh, cosmetics additive wallantoin and pesticide intermediate. Present stage reports that the method preparing oxoethanoic acid has: oxalic dialdehyde nitric acid oxidation method; Oxalic dialdehyde precious metal catalyst dioxygen oxidation method; Oxalic dialdehyde electrooxidation method; Oxalic dialdehyde hydrogen peroxide oxidation method; Oxalic dialdehyde sodium hypochlorite oxidization; Oxalic dialdehyde dichloroacetate method; Oxyacetic acid enzymatic oxidation method; Acid by electrolytic reduction of oxalic method etc.
Oxalic dialdehyde nitric acid oxidation method is the most general method of current industrial production oxoethanoic acid, and the method is with oxalic dialdehyde for raw material, and nitric acid is oxygenant, and reaction conditions is gentle, and technique is simple.
But still there are some drawbacks in oxalic dialdehyde nitric acid oxidation method:
A) using a large amount of nitric acid etc. to have the oxygenant of severe corrosive, environment is had pollution by the oxynitride produced in production process;
B) after oxidizing reaction, oxalic dialdehyde residual volume is higher, and is difficult in later stage Ex-all;
C) be oxidized oxalic dialdehyde selectivity not high, cause oxoethanoic acid product rate to decline.
Summary of the invention
The present invention is intended to overcome prior art defect, it is intended that provides a kind of and can reduce nitric acid usage quantity, reduces nitrogen oxide emission, is beneficial to suitability for industrialized production and carry oxoethanoic acid and its preparation method of high yield.
For achieving the above object, the technical solution used in the present invention is:
Step one, by the concentration of 100 parts of quality be the glyoxal water solution of 40wt%, the nitrous acid aqueous solution of the concentration of 10 ~ 20 parts of quality to be the hydrochloric acid soln of 30wt% and the concentration of 10 ~ 25 parts of quality be 5 ~ 20wt% add in reactor, under agitation, it is warming up to 45 ~ 55 DEG C, add the Sodium Nitrite of 0.12 ~ 0.62 part of quality again, obtain initiator system.
Step 2,55 ~ 65 DEG C, under normal pressure and agitation condition, Bubbled stone is adopted to lead to into oxygen to described initiator system, evenly drip to described initiator system simultaneously add 30 ~ concentration of 40 parts of quality is the nitric acid of 30 ~ 45wt%, drips that to add the time be 1 ~ 3 hour, obtains oxidation system.
Step 3, under agitation, described oxidation system is warming up to 75 ~ 85 DEG C, it is incubated 1 ~ 2 hour; Then the concentration adding 1 ~ 4 part of quality is the nitric acid of 30 ~ 45wt%, continues insulation 1 ~ 2 hour, obtained oxoethanoic acid.
It is described that to lead to the oxygen flow into oxygen be 0.01 ~ 0.04wt/min; The purity of oxygen is 99.99%.
Described nitrous acid aqueous solution is the nitrous acid aqueous solution that the nitrogen peroxide discharged in produces tartronic process is only absorbed by the water and formed.
The material of described Bubbled stone is the one in silicon carbide, silicon nitride, pottery.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
The present invention adopts nitric acid and atmospheric oxygen simultaneously as oxygenant, considerably reduces nitric acid or the usage quantity of other severe corrosive oxygenants, reduces the loss to plant and instrument, reduce discharged nitrous oxides and later stage environmental treatment cost and to the pollution of environment.
The present invention adopts Bubbled stone to improve the transformation efficiency of nitric acid service efficiency and oxidizing reaction, reduce in glyoxylic acid solution oxalic dialdehyde content, successfully solve the problem that later stage oxalic dialdehyde is difficult, and improve the product rate of oxoethanoic acid, greatly reduce the content of by product oxalic acid. In addition, owing to adopting the logical oxygen of normal pressure, so without the need to airtight and withstand voltage reactor, whole reaction unit has simply, economic and safe advantage, it is beneficial to suitability for industrialized production.
The made oxoethanoic acid of the present invention is after testing: oxalic dialdehyde residual quantity is 0.02 ~ 0.04wt%, oxalic dialdehyde transformation efficiency be 99.6 ~ 99.9%; Oxoethanoic acid content is 24.7 ~ 25.3wt%, and the molar yield of oxoethanoic acid is 87.9 ~ 89.0%.
Therefore, the present invention have that nitric acid usage quantity is low, nitrogen oxide emission is few, product rate height and be beneficial to the feature of suitability for industrialized production.
Embodiment
Below in conjunction with this embodiment, the invention will be further described, not to the restriction of its protection domain.
For avoiding repetition, first by as follows for the relevant technical parameter Unify legislation of this embodiment, embodiment repeats no more:
It is described that to lead to the oxygen flow into oxygen be 0.01 ~ 0.04wt/min; The purity of oxygen is 99.99%.
Described nitrous acid aqueous solution is the nitrous acid aqueous solution that the nitrogen peroxide discharged in produces tartronic process is only absorbed by the water and formed.
Embodiment 1
A kind of oxoethanoic acid and its preparation method. Described in the present embodiment, preparation method is:
Step one, by the concentration of 100 parts of quality be the glyoxal water solution of 40wt%, the nitrous acid aqueous solution of the concentration of 10 ~ 15 parts of quality to be the hydrochloric acid soln of 30wt% and the concentration of 10 ~ 15 parts of quality be 5 ~ 20wt% add in reactor, under agitation, it is warming up to 45 ~ 50 DEG C, add the Sodium Nitrite of 0.12 ~ 0.32 part of quality again, obtain initiator system.
Step 2,55 ~ 65 DEG C, under normal pressure and agitation condition, Bubbled stone is adopted to lead to into oxygen to described initiator system, evenly drip to described initiator system simultaneously add 30 ~ concentration of 35 parts of quality is the nitric acid of 30 ~ 45wt%, drips that to add the time be 1 ~ 3 hour, obtains oxidation system.
Step 3, under agitation, described oxidation system is warming up to 75 ~ 80 DEG C, it is incubated 1 ~ 2 hour; Then the concentration adding 1 ~ 3 part of quality is the nitric acid of 30 ~ 45wt%, continues insulation 1 ~ 2 hour, obtained oxoethanoic acid.
The made oxoethanoic acid of the present embodiment is after testing: oxalic dialdehyde residual quantity is 0.03 ~ 0.04wt%, oxalic dialdehyde transformation efficiency be 99.6 ~ 99.8%;Oxoethanoic acid content is 24.7 ~ 25.1wt%, and the molar yield of oxoethanoic acid is 88.1 ~ 88.9%.
Embodiment 2
A kind of oxoethanoic acid and its preparation method. Described in the present embodiment, preparation method is:
Step one, by the concentration of 100 parts of quality be the glyoxal water solution of 40wt%, the nitrous acid aqueous solution of the concentration of 13 ~ 17 parts of quality to be the hydrochloric acid soln of 30wt% and the concentration of 10 ~ 25 parts of quality be 15 ~ 20wt% add in reactor, under agitation, it is warming up to 48 ~ 53 DEG C, add the Sodium Nitrite of 0.32 ~ 0.52 part of quality again, obtain initiator system.
Step 2,55 ~ 65 DEG C, under normal pressure and agitation condition, Bubbled stone is adopted to lead to into oxygen to described initiator system, evenly drip to described initiator system simultaneously add 33 ~ concentration of 37 parts of quality is the nitric acid of 30 ~ 45wt%, drips that to add the time be 1 ~ 3 hour, obtains oxidation system.
Step 3, under agitation, described oxidation system is warming up to 78 ~ 82 DEG C, it is incubated 1 ~ 2 hour; Then the concentration adding 1.5 ~ 3.5 parts of quality is the nitric acid of 30 ~ 45wt%, continues insulation 1 ~ 2 hour, obtained oxoethanoic acid.
The made oxoethanoic acid of the present embodiment is after testing: oxalic dialdehyde residual quantity is 0.02 ~ 0.04wt%, oxalic dialdehyde transformation efficiency be 99.6 ~ 99.9%; Oxoethanoic acid content is 24.8 ~ 25.0wt%, and the molar yield of oxoethanoic acid is 87.9 ~ 88.7%.
Embodiment 3
A kind of oxoethanoic acid and its preparation method. Described in the present embodiment, preparation method is:
Step one, by the concentration of 100 parts of quality be the glyoxal water solution of 40wt%, the nitrous acid aqueous solution of the concentration of 15 ~ 20 parts of quality to be the hydrochloric acid soln of 30wt% and the concentration of 20 ~ 25 parts of quality be 5 ~ 20wt% add in reactor, under agitation, it is warming up to 50 ~ 55 DEG C, add the Sodium Nitrite of 0.42 ~ 0.62 part of quality again, obtain initiator system.
Step 2,55 ~ 65 DEG C, under normal pressure and agitation condition, Bubbled stone is adopted to lead to into oxygen to described initiator system, evenly drip to described initiator system simultaneously add 35 ~ concentration of 40 parts of quality is the nitric acid of 30 ~ 45wt%, drips that to add the time be 1 ~ 3 hour, obtains oxidation system.
Step 3, under agitation, described oxidation system is warming up to 80 ~ 85 DEG C, it is incubated 1 ~ 2 hour; Then the concentration adding 2 ~ 4 parts of quality is the nitric acid of 30 ~ 45wt%, continues insulation 1 ~ 2 hour, obtained oxoethanoic acid.
The made oxoethanoic acid of the present embodiment is after testing: oxalic dialdehyde residual quantity is 0.03 ~ 0.04wt%, oxalic dialdehyde transformation efficiency be 99.6 ~ 99.8%; Oxoethanoic acid content is 24.9 ~ 25.3wt%, and the molar yield of oxoethanoic acid is 88.4 ~ 89.0%.
This embodiment compared with prior art has following positively effect:
This embodiment adopts nitric acid and atmospheric oxygen simultaneously as oxygenant, considerably reduce nitric acid or the usage quantity of other severe corrosive oxygenants, reduce the loss of plant and instrument, reduce discharged nitrous oxides and later stage environmental treatment cost and to the pollution of environment.
This embodiment adopts Bubbled stone to improve the transformation efficiency of nitric acid service efficiency and oxidizing reaction, reduce in glyoxylic acid solution oxalic dialdehyde content, successfully solve the problem that later stage oxalic dialdehyde is difficult, and improve the product rate of oxoethanoic acid, greatly reduce the content of by product oxalic acid. In addition, owing to adopting the logical oxygen of normal pressure, so without the need to airtight and withstand voltage reactor, whole reaction unit has simply, economic and safe advantage, it is beneficial to suitability for industrialized production.
The made oxoethanoic acid of this embodiment is after testing: oxalic dialdehyde residual quantity is 0.02 ~ 0.04wt%, oxalic dialdehyde transformation efficiency be 99.6 ~ 99.9%;Oxoethanoic acid content is 24.7 ~ 25.3wt%, and the molar yield of oxoethanoic acid is 87.9 ~ 89.0%.
Therefore, this embodiment have that nitric acid usage quantity is low, nitrogen oxide emission is few, product rate height and be beneficial to the feature of suitability for industrialized production.
Claims (5)
1. the preparation method of an oxoethanoic acid, it is characterised in that described preparation method comprises the following steps:
Step one, by the concentration of 100 parts of quality be the glyoxal water solution of 40wt%, the nitrous acid aqueous solution of the concentration of 10～20 parts of quality to be the hydrochloric acid soln of 30wt% and the concentration of 10～25 parts of quality be 5～20wt% add in reactor, under agitation, it is warming up to 45～55 DEG C, add the Sodium Nitrite of 0.12～0.62 part of quality again, obtain initiator system;
Step 2,55～65 DEG C, under normal pressure and agitation condition, Bubbled stone is adopted to lead to into oxygen to described initiator system, evenly drip to described initiator system simultaneously add 30～concentration of 40 parts of quality is the nitric acid of 30～45wt%, drips that to add the time be 1～3 hour, obtains oxidation system;
Step 3, under agitation, described oxidation system is warming up to 75～85 DEG C, it is incubated 1～2 hour; Then the concentration adding 1～4 part of quality is the nitric acid of 30～45wt%, continues insulation 1～2 hour, obtained oxoethanoic acid.
2. the preparation method of oxoethanoic acid according to claim 1, it is characterised in that described to lead to the oxygen flow into oxygen be 0.01～0.04wt/min; The purity of oxygen is 99.99%.
3. the preparation method of oxoethanoic acid according to claim 1, it is characterised in that described nitrous acid aqueous solution is the nitrous acid aqueous solution that the nitrogen peroxide discharged in produces tartronic process is only absorbed by the water and formed.
4. the preparation method of oxoethanoic acid according to claim 1, it is characterised in that the material of described Bubbled stone is the one in silicon carbide, silicon nitride, pottery.
5. an oxoethanoic acid, it is characterised in that described oxoethanoic acid is the oxoethanoic acid prepared by the preparation method of oxoethanoic acid according to any one of Claims 1 to 4 item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610121053.8A CN105669424A (en) | 2016-03-03 | 2016-03-03 | Glyoxalic acid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610121053.8A CN105669424A (en) | 2016-03-03 | 2016-03-03 | Glyoxalic acid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105669424A true CN105669424A (en) | 2016-06-15 |
Family
ID=56307827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610121053.8A Pending CN105669424A (en) | 2016-03-03 | 2016-03-03 | Glyoxalic acid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105669424A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187738A (en) * | 2016-07-06 | 2016-12-07 | 湖北省宏源药业科技股份有限公司 | A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid |
| CN109678693A (en) * | 2018-12-25 | 2019-04-26 | 兄弟科技股份有限公司 | A kind of glyoxalic acid continuous oxidation technique |
| WO2020243907A1 (en) * | 2019-06-04 | 2020-12-10 | Rhodia Operations | A method of oxidizing glycolaldehyde using nitric acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129441A (en) * | 1974-08-23 | 1976-03-12 | Nippon Synthetic Chem Ind | Guriokishirusanno seizohoho |
| CN101965326A (en) * | 2008-01-25 | 2011-02-02 | 科莱恩特种精细化学品法国公司 | Process of preparation of glyoxylic acid aqueous solution |
| CN103360238A (en) * | 2012-04-06 | 2013-10-23 | 北京石油化工学院 | Continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and process thereof |
| CN104649884A (en) * | 2013-11-21 | 2015-05-27 | 曾舟华 | Method and production device of preparing glyoxylic acid through catalytic oxidization of glyoxal by air with nitrogen oxide under normal pressure |
-
2016
- 2016-03-03 CN CN201610121053.8A patent/CN105669424A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129441A (en) * | 1974-08-23 | 1976-03-12 | Nippon Synthetic Chem Ind | Guriokishirusanno seizohoho |
| CN101965326A (en) * | 2008-01-25 | 2011-02-02 | 科莱恩特种精细化学品法国公司 | Process of preparation of glyoxylic acid aqueous solution |
| CN103360238A (en) * | 2012-04-06 | 2013-10-23 | 北京石油化工学院 | Continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and process thereof |
| CN104649884A (en) * | 2013-11-21 | 2015-05-27 | 曾舟华 | Method and production device of preparing glyoxylic acid through catalytic oxidization of glyoxal by air with nitrogen oxide under normal pressure |
Non-Patent Citations (1)
| Title |
|---|
| 张克峰: "乙醛酸制备及纯化技术", 《现代化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187738A (en) * | 2016-07-06 | 2016-12-07 | 湖北省宏源药业科技股份有限公司 | A kind of method that carbon nanotube loaded noble metal catalyst prepares glyoxalic acid |
| CN109678693A (en) * | 2018-12-25 | 2019-04-26 | 兄弟科技股份有限公司 | A kind of glyoxalic acid continuous oxidation technique |
| WO2020243907A1 (en) * | 2019-06-04 | 2020-12-10 | Rhodia Operations | A method of oxidizing glycolaldehyde using nitric acid |
| CN113891872A (en) * | 2019-06-04 | 2022-01-04 | 罗地亚经营管理公司 | Method for oxidizing glycolaldehyde using nitric acid |
| US11753362B2 (en) | 2019-06-04 | 2023-09-12 | Rhodia Operations | Method of oxidizing glycolaldehyde using nitric acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105669424A (en) | Glyoxalic acid and preparation method thereof | |
| TWI255811B (en) | Process for the production of acrylic acid | |
| CN107148415A (en) | The method for preparing glyceric acid carbonic ester | |
| CN104003865A (en) | Method for catalytic oxidation of 1,2-propylene glycol at normal pressure | |
| CN101574656A (en) | Nanometer cobalt ion-doped titanic anhydride catalyst and preparation method thereof | |
| CN111672530B (en) | Preparation method of CuCo-N/C nano catalyst and application of CuCo-N/C nano catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propylene glycol | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN104478647A (en) | Method for preparing hexane by catalyzing biomass in water phase | |
| CN113426490A (en) | Method for preparing mercury-free catalyst by adding dichloroethane | |
| CN104311405A (en) | Preparation method of benzaldehyde | |
| EA202091358A1 (en) | METHOD FOR OBTAINING GRANULAR CATALYST FOR OXIDATION PROCESSES | |
| CN103739479A (en) | Method for preparing sodium gluconate through catalytic oxidation of glucose by using gold catalyst | |
| CN108530318B (en) | Method for synthesizing adiponitrile | |
| EP3042721A1 (en) | Oxidation catalyst for furfural compounds and applying method thereof | |
| CN110860297B (en) | Preparation method of Cu-Ag/La @ HAP catalyst and application of catalyst in preparation of lactic acid by catalytic oxidation of 1, 2-propanediol | |
| CN104549257A (en) | Catalyst for treating organic small molecule wastewater and preparation method of catalyst | |
| KR101726502B1 (en) | Method for forming furfural | |
| CN102976384A (en) | Production method for polyaluminum chloride | |
| CN112898225A (en) | Synthesis method of 1, 2-benzisothiazolin-3-ketone | |
| CN102259024A (en) | Nano Au catalyst for glucose oxidation and preparation and use method thereof | |
| CN108047026B (en) | Method for preparing glyoxylic acid by catalytic oxidation reaction extraction of glyoxal | |
| CN114591170B (en) | Method for preparing glyoxylate by oxidizing glycolate | |
| CN105709840A (en) | Method for producing palladium catalysts | |
| CN107445828B (en) | Method for synthesizing glyoxylic acid esters | |
| CN110845303A (en) | Method for improving glucose hydrogenation efficiency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160615 |
|
| WD01 | Invention patent application deemed withdrawn after publication |