CN103360238A - Continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and process thereof - Google Patents
Continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and process thereof Download PDFInfo
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- CN103360238A CN103360238A CN 201210098542 CN201210098542A CN103360238A CN 103360238 A CN103360238 A CN 103360238A CN 201210098542 CN201210098542 CN 201210098542 CN 201210098542 A CN201210098542 A CN 201210098542A CN 103360238 A CN103360238 A CN 103360238A
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Abstract
The invention relates to a continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen, which comprises an extraction tower, an oxidization reactor, a nitric acid regeneration tower, a gas-liquid separation tower and a dilute nitric acid concentration tower. The process disclosed by the invention is as follows: glyoxal and an oxidizing agent, namely molecular oxygen, are continuously fed; nitric acid is used as the catalyst; the extraction temperature of the extraction tower is 80-120 DEG C; the temperature of the oxidization reactor is controlled in a sectionalized manner; and the detail structure and the process are seen in the specification. The continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and the process thereof disclosed by the invention have the advantages that because separation between a glyoxal oxidative product and the catalyst, namely nitric acid, is realized in an extracting manner, continuous operation of the oxidization process can be realized; furthermore, the oxygen source of the oxidizing agent, namely molecular oxygen, is industrial oxygen or air; abundant and cheap sources can be obtained; nitric acid is recycled; the cost of raw materials is reduced; furthermore, the emission problem of waste acid and waste gas is avoided.
Description
Technical field
The present invention relates to field of chemical engineering, specifically, relate to make catalyzer with nitric acid, by the technique of molecular oxygen oxidation glyoxal preparation oxoethanoic acid.
Background technology
Oxoethanoic acid is the simplest ketone acid, and the character of aldehyde and acid is arranged, and Industrial products are generally 40%, 50%, 60% aqueous solution or high-purity crystal, are a kind of important industrial chemicals and biochemical reagents.Main application is preparation vanillin food grade,1000.000000ine mesh, vanirone and wallantoin; Also can be used for preparing the medicine intermediates such as D-pHPG, phydroxybenzeneactamide, p-hydroxyphenylaceticacid, 4-Hydroxyphenyl hydantoin; Also can be used for preparing 2-hydroxyl PHOSPHONACETIC (a kind of corrosion inhibiting and descaling agent).
Industrial main employing oxalic dialdehyde nitric acid oxidation method, oxalic dialdehyde Ozonation and acid by electrolytic reduction of oxalic method are produced oxoethanoic acid at present.Rear two kinds of method power consumptions are high, and nitric acid oxidation method needs to consume a large amount of nitric acid owing to adopting nitric acid to make oxygenant.
Patent CN 1634847 A and patent CN 101965326 A all mention and adopt nitrogen oxide or nitric acid to make catalyzer, realize molecular oxygen oxidation glyoxal preparation oxoethanoic acid, but all do not relate to how to make oxalic dialdehyde oxidation products and the continuous separates such as catalyst oxidation nitrogen or nitric acid from, therefore can't realize operate continuously.
Summary of the invention
The object of the invention is to overcome weak point of the prior art, device and the technique thereof of a kind of operate continuously by molecular oxygen oxidation glyoxal preparation oxoethanoic acid are provided.
The objective of the invention is to be achieved through the following technical solutions: operate continuously is by the device of molecular oxygen oxidation glyoxal preparation oxoethanoic acid, and this device comprises extraction tower, oxidation reactor, nitric acid regenerator column, gas-liquid separation tower and rare nitric acid concentration tower; Wherein, oxidation reactor adopts tubular type cross-flow reactor, and oxalic dialdehyde is from axially entering reactor, and nitric acid enters reactor and oxalic dialdehyde mixing afterreaction step by step from side line; On the nitric acid regenerator column limit, connect a gas-liquid separation tower, reduce objectionable impurities discharged nitrous oxides in the waste gas; Extraction tower and gas-liquid separation tower install baffle plate or filler additional, to improve gas-liquid separation efficient; Extraction tower and nitric acid regenerator column inside install sparger additional, and the gas-liquid that helps to enter in the container evenly distributes; Install filler additional in the nitric acid regenerator column, to improve gas-liquid mixed efficient in the nitric acid regenerator column; The steam that draw on rare nitric acid concentration tower top returns the recycle of nitric acid regenerator column after cooling.
Technique of the present invention, this raw materials technology oxalic dialdehyde and the continuously feeding of oxidizer molecule oxygen, the mole proportioning of oxalic dialdehyde and molecular oxygen is 2.0 ~ 0.2:1, nitric acid is made catalyzer, the extraction tower extraction temperature is 80 ~ 120 ℃, oxidation reactor adopts sectional temperature-controlled, the higher reaction of leading portion oxalic dialdehyde concentration is more violent, need add water coolant temperature is controlled at 20 ~ 40 ℃ of intervals, back segment oxalic dialdehyde and concentration of nitric acid are all lower, for accelerating speed of reaction, impel the oxalic dialdehyde complete oxidation, suitably improve temperature of reaction, maintain 40 ~ 60 ℃ of intervals; The glyoxal water solution mass concentration that enters oxidation reactor is 40 ~ 10%, the nitric acid mass concentration is 10 ~ 40%, nitric acid and oxalic dialdehyde the mole proportioning be 0.6 ~ 1.2:1, the nitric acid mass concentration that enters oxidation reactor is 10 ~ 60%, nitric acid is constantly consumed in oxidation reactor, but nitrate reductase product nitrogen oxide at extraction tower with after the oxalic dialdehyde oxidation products separates, water-oxygen system in the nitric acid regenerator column is oxidized to nitric acid again again, return to again oxidation reactor after rare nitric acid is concentrated and participate in oxidizing reaction, nitric acid constantly is reduced and reoxidizes and is able to recycle in the whole technical process.
But the present invention has designed the technique that a kind of oxidation oxalic dialdehyde of operate continuously is produced oxoethanoic acid, and the raw material that this technique adopts is glyoxal water solution, and oxygenant is pure oxygen or air; Product is aqueous glyoxylic acid, and by product is mainly oxalic acid.In continuous operation process, the effect of nitric acid is to serve as catalyzer and provide sour environment for reaction, behind oxalic dialdehyde and the nitric acid reaction, residue nitric acid and nitrate reductase product (oxynitride) can (be mainly oxoethanoic acid by rare gas element extracting and oxalic dialdehyde oxidation products, also have a small amount of by product oxalic acid) separate, nitrogen oxide can be regenerated as nitric acid by absorbing oxygen in water-oxygen system, and is recycled.
In this continuous oxygen metallization processes, oxalic dialdehyde and nitric acid react in reactor, and reacted mixture oxoethanoic acid, nitrogen oxide, unreacted nitric acid and a small amount of by product oxalic acid etc. are sent in the extraction tower immediately and separated.The oxalic dialdehyde oxidation products aqueous solution is collected in the extraction tower bottom.Nitric acid decomposes in extraction tower becomes oxynitride, is gone out by the extracting band of gas with original nitrogen oxide, is regenerated as together nitric acid in the nitric acid regenerator column in water-oxygen system.Participate in the oxalic dialdehyde oxidizing reaction in the regeneration nitric acid Returning oxidation reactor, therefore nitric acid be able to recycle.
It is aqueous glyoxylic acid and a small amount of oxalic acid that the liquid main component is collected in the extraction tower bottom, and oxalic acid can leach by crystallisation by cooling, namely gets the product aqueous glyoxylic acid.By product oxalic acid can be further purified and obtain qualified commercial chemicals.
The liquid of drawing at the bottom of the nitric acid regenerator column is mainly rare nitric acid, and it is further concentrated that rare nitric acid is sent to rare nitric acid concentration tower, the directly Returning oxidation reactor re-using of nitric acid after concentrated.The steam at nitric acid concentration tower top returns the top recycle of nitric acid regenerator column after cooling.
The present invention compared with prior art has following advantage:
Among the present invention owing to adopting the extracting mode to realize separating of oxalic dialdehyde oxidation products and catalyzer nitric acid, thereby so that this oxidising process can realize operate continuously, add that oxidizer molecule oxygen of the present invention is that industrial oxygen or air are done oxygen source, abundant and cheap and easy to get source is arranged, nitric acid is recycled, not only reduce raw materials cost, and avoided the emission problem of spent acid waste gas.
Description of drawings
Fig. 1 is that operate continuously of the present invention is by the device schematic diagram of molecular oxygen oxidation glyoxal preparation oxoethanoic acid;
Major equipment title of the present invention is: 1, extraction tower, 2, oxidation reactor, 3, nitric acid regenerator column, 4, gas-liquid separation tower, 5, rare nitric acid concentration tower.
Embodiment
The below enumerates 2 embodiment, the present invention is further specified, but the present invention is not limited to these embodiment.
Embodiment 1
The mole proportioning of oxalic dialdehyde and molecular oxygen is 1.30:1, nitric acid is made catalyzer, nitric acid and oxalic dialdehyde mole proportioning 0.90:1, extraction tower 1 extraction temperature is 90 ~ 100 ℃, the glyoxal water solution 0.038L/hr of 20% mass concentration and 40% mass concentration nitric acid 0.017L/hr slowly add the oxidation reactor hybrid reaction, the oxidation reactor front-end temperature is controlled at 35 ~ 40 ℃, and the back segment temperature is controlled at 50 ~ 55 ℃.Air joins the nitric acid regenerator column with the 12.6L/hr flow velocity.The nitric acid of regeneration re-uses after concentrated.Product is isolated nitric acid and oxynitride at 90-100 ℃ with the nitrogen extracting, and nitrogen flow rate is 8.4L/hr, obtains the water white transparency aqueous solution, and main component is oxoethanoic acid and a small amount of oxalic acid.After the stable reaction operation, collect operation 4hr products therefrom, the product of collection is cooled to 0 ℃ and leaves standstill 24hr, has the oxalic acid crystal to separate out, and obtains oxalic acid 2.1g after the separation, and the product aqueous glyoxylic acid, contains oxoethanoic acid 42.2g.Be 95.4% according to oxalic dialdehyde inlet amount oxoethanoic acid yield.
Embodiment 2
The mole proportioning of oxalic dialdehyde and molecular oxygen is 1.15:1, nitric acid is made catalyzer, nitric acid and oxalic dialdehyde the mole proportioning be 0.80:1, extraction tower (1) extraction temperature is 90 ~ 100 ℃, the glyoxal water solution 0.034L/hr of 25% mass concentration and 35% mass concentration nitric acid 0.021L/hr slowly add the oxidation reactor hybrid reaction, the oxidation reactor front-end temperature is controlled at 35 ~ 40 ℃, and the back segment temperature is controlled at 50 ~ 55 ℃.Oxygen joins the nitric acid regenerator column with the 3.3L/hr flow velocity.The nitric acid of regeneration re-uses after concentrated.Product is isolated nitric acid and oxynitride at 90 ~ 100 ℃ with the nitrogen extracting, and nitrogen flow rate is 6.3L/hr, obtains the water white transparency aqueous solution, and main component is oxoethanoic acid and a small amount of oxalic acid.After the stable reaction operation, collect operation 4hr products therefrom, the product of collection is cooled to 0 ℃ and leaves standstill 24hr, has the oxalic acid crystal to separate out, and obtains oxalic acid 3.1g after the separation, and the product aqueous glyoxylic acid, contains oxoethanoic acid 47.5g.Be 94.8% according to oxalic dialdehyde inlet amount oxoethanoic acid yield.
Claims (2)
1. operate continuously be is characterized in that by the device of molecular oxygen oxidation glyoxal preparation oxoethanoic acid: this device comprises extraction tower (1), oxidation reactor (2), nitric acid regenerator column (3), gas-liquid separation tower (4) and rare nitric acid concentration tower (5); Wherein, oxidation reactor (2) adopts tubular type cross-flow reactor, and oxalic dialdehyde is from axially entering reactor, and nitric acid enters reactor and oxalic dialdehyde mixing afterreaction step by step from side line; On nitric acid regenerator column (3) limit, connect a gas-liquid separation tower, reduce objectionable impurities discharged nitrous oxides in the waste gas; Extraction tower (1) and gas-liquid separation tower (4) install baffle plate or filler additional, to improve gas-liquid separation efficient; Extraction tower (1) and nitric acid regenerator column (3) inside install sparger additional, and the gas-liquid that helps to enter in the container evenly distributes; The nitric acid regenerator column installs filler additional in (3), to improve gas-liquid mixed efficient in the nitric acid regenerator column; The steam that draw on rare nitric acid concentration tower (5) top returns the recycle of nitric acid regenerator column after cooling.
2. operate continuously according to claim 1 is by the technique of molecular oxygen oxidation glyoxal preparation oxoethanoic acid, it is characterized in that: this raw materials technology oxalic dialdehyde and the continuously feeding of oxidizer molecule oxygen, the mole proportioning of oxalic dialdehyde and molecular oxygen is 2.0 ~ 0.2:1, nitric acid is made catalyzer, extraction tower (1) extraction temperature is 80 ~ 120 ℃, oxidation reactor (2) adopts sectional temperature-controlled, the higher reaction of leading portion oxalic dialdehyde concentration is more violent, need add water coolant temperature is controlled at 20 ~ 40 ℃ of intervals, back segment oxalic dialdehyde and concentration of nitric acid are all lower, for accelerating speed of reaction, impel the oxalic dialdehyde complete oxidation, suitably improve temperature of reaction, maintain 40 ~ 60 ℃ of intervals; The glyoxal water solution mass concentration that enters oxidation reactor is 40 ~ 10%, the nitric acid mass concentration is 10 ~ 40%, nitric acid and oxalic dialdehyde the mole proportioning be 0.6 ~ 1.2:1, the nitric acid mass concentration that enters oxidation reactor is 10 ~ 60%, nitric acid is constantly consumed in oxidation reactor, but nitrate reductase product nitrogen oxide is after extraction tower and oxalic dialdehyde oxidation products vapor-liquid separation (4), water-oxygen system in nitric acid regenerator column (3) is oxidized to nitric acid again again, return to again oxidation reactor behind rare nitric acid concentrated (5) and participate in oxidizing reaction, nitric acid constantly is reduced and reoxidizes and is able to recycle in the whole technical process.
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| CN 201210098542 CN103360238A (en) | 2012-04-06 | 2012-04-06 | Continuously operated device for preparing glyoxylic acid by oxidizing glyoxal through molecular oxygen and process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105669424A (en) * | 2016-03-03 | 2016-06-15 | 武汉科技大学 | Glyoxalic acid and preparation method thereof |
| CN107673965A (en) * | 2017-11-15 | 2018-02-09 | 广东玖翼化工有限公司 | A kind of technique of oxidizing process production glyoxalic acid |
| CN108003008A (en) * | 2017-12-10 | 2018-05-08 | 天津市职业大学 | A kind of method for aoxidizing glyoxal water solution production glyoxalic acid |
| CN109896949A (en) * | 2017-12-10 | 2019-06-18 | 天津市职业大学 | A kind of method that catalysis oxidation glyoxal prepares glyoxalic acid |
-
2012
- 2012-04-06 CN CN 201210098542 patent/CN103360238A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104649884B (en) * | 2013-11-21 | 2017-03-22 | 黄冈银河阿迪药业有限公司 | Method and production device of preparing glyoxylic acid through catalytic oxidization of glyoxal by air with nitrogen oxide under normal pressure |
| CN105669424A (en) * | 2016-03-03 | 2016-06-15 | 武汉科技大学 | Glyoxalic acid and preparation method thereof |
| CN107673965A (en) * | 2017-11-15 | 2018-02-09 | 广东玖翼化工有限公司 | A kind of technique of oxidizing process production glyoxalic acid |
| CN108003008A (en) * | 2017-12-10 | 2018-05-08 | 天津市职业大学 | A kind of method for aoxidizing glyoxal water solution production glyoxalic acid |
| CN109896949A (en) * | 2017-12-10 | 2019-06-18 | 天津市职业大学 | A kind of method that catalysis oxidation glyoxal prepares glyoxalic acid |
| CN108003008B (en) * | 2017-12-10 | 2020-07-21 | 天津市职业大学 | Method for producing glyoxylic acid by oxidizing aqueous solution of glyoxal |
| CN109896949B (en) * | 2017-12-10 | 2021-10-08 | 内蒙古天宇达生物科技有限公司 | Method for preparing glyoxylic acid by catalytic oxidation of glyoxal |
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Application publication date: 20131023 |