CN1021812C - Technology for producing oxalic acid by oxidation of glycol - Google Patents
Technology for producing oxalic acid by oxidation of glycol Download PDFInfo
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- CN1021812C CN1021812C CN 88105413 CN88105413A CN1021812C CN 1021812 C CN1021812 C CN 1021812C CN 88105413 CN88105413 CN 88105413 CN 88105413 A CN88105413 A CN 88105413A CN 1021812 C CN1021812 C CN 1021812C
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- nitric acid
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- oxalic acid
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- acid
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Abstract
The present invention relates to a new technology for preparing oxalic acid by oxidizing ethylene glycol. The technology has the characteristics that 1, a continuous circulation reaction technology is designed and adopted, increases available oxygen in the reaction process, enhances reaction propelling power and greatly reduces production cost; 2, oxidizing media are sulfuric acid, nitric acid and a water mixture, and the ratio of nitric acid to ethylene glycol is smaller than 3; 3, reaction liquid can be reused many times, and the yield can be more than 90 %.
Description
Aspects such as oxalic acid is synthetic at medicine, chemical industry, the industry of system grass, textile industry, metallurgical industry, building industry and daily-use chemical industry all have been widely used.
PREPARATION OF OXAlIC ACID adopts formate method, glucose oxidase method and ethylene glycol oxidation usually.Formate method and glucose method all exist the raw material anxiety, pollution reaches the cost problem of higher more greatly.
Producing oxalic acid by oxidation of glycol, a kind of method are in nitric acid and sulfuric acid blended oxidizing medium, under reduced pressure carry out, but the essential V that uses
2O
5Deng catalyzer.A kind of method is to use the mixture of nitric acid, sulfuric acid and water to make oxidizing medium, reacts under the condition of pressurization, as United States Patent (USP) 3678107; Above method is all had relatively high expectations to appointed condition.Another kind of safer and easily method be with nitric acid, sulfuric acid and water as reaction medium, under normal pressure, carry out oxidizing reaction, as: Japan speciallys permit 49-24047, United States Patent (USP) 3691232 etc.In reaction process, liquid oxygen carrier catalyst decomposes is that available oxygen is participated in reaction, produces a large amount of oxynitrides simultaneously, the effusion reaction system.In order to guarantee enough available oxygens, must increase the feed ratio of this material when feeding intake, require nitric acid: ethylene glycol 〉=3, so just make that the consumption of nitric acid is bigger, usage ratio of equipment is on the low side, and scale of investment, process cost and energy consumption are greatly increased.
The present invention designs and adopted is equipped with as shown in Figure 1 the technology of recycle gas absorption unit continuously, can effectively address the above problem.
The oxynitride that produces in the reactor 1 enters absorption unit 4 with gaseous phase, this absorption unit can be the gas absorber of membrane absorber, packing tower, tray column or other type, liquid material in the reactor 1 by water cooler 3, enters absorption unit 4 through recycle pump 2 after the cooling.In absorption unit, produce the chemical absorption reaction, the oxynitrides of 20-90% is absorbed by liquid material, and Returning reactor 1 decomposes once more, emits available oxygen and oxynitride, and above-mentioned decomposition, absorption process circulation are continuously carried out.So just increase the available oxygen in the reaction system greatly, reduced the consumption of oxidizing medium.Therefore, in the present invention, at nitric acid: ethylene glycol＜3 o'clock, at 50-100 ℃ of oxidation ethylene glycol oxalic acid, its yield is more than 90%.Reduce the ratio of nitric acid and ethylene glycol, reduced the consumption of the consumption and the nitric acid of oxidizing medium, improved plant factor.Oxidizing medium of the present invention is sulfuric acid, nitric acid and water, and its proportioning is sulfuric acid 20-60%, nitric acid 20-60%, water 20-50%.(nitric acid: ethylene glycol is mol ratio)
Example one
101 reactors are installed agitator, continuously the recycle gas absorption unit.Add 97% sulfuric acid 3500g, 65% nitric acid 3850g, water 2650g is heated with stirring to 80 ℃.Dripped 96% ethylene glycol 900g in 2 hours, the control reacting liquid temperature is at 80-85 ℃ during dropping.After ethylene glycol dropwises, keep reacting liquid temperature, continued stirring reaction 4 hours at 80-85 ℃.In the entire reaction, through tail gas (No, the No of recycle gas absorption unit discharge continuously
2), after the air distribution, water absorbs, and can get rare nitric acid, is used to prepare oxidizing medium.After the reaction solution cooling, separate out crystal.Centrifugation gets oxalic acid 1530g, and yield 90% gets the oxalic acid elaboration behind the water recrystallization.
Example two
101 reactors are installed agitator, and the recycle gas absorption unit adds 97% sulfuric acid 3500g continuously, 65% nitric acid 3850g, and water 2650g is heated with stirring to 80 ℃, drips 96% ethylene glycol 900g in 2 hours, and the control reacting liquid temperature is at 80-85 ℃ during dropping.After ethylene glycol dropwises, keep reacting liquid temperature, continued stirring reaction 4 hours, in the entire reaction, by tail gas (No, the No of continuous recycle gas absorption unit discharge at 80-85 ℃
2), after the air distribution, the mother liquor that use-case one separates behind the oxalic acid absorbs.After the reaction solution cooling, separate out crystal.Centrifugation gets oxalic acid 1530g, yield 90%.Get the oxalic acid elaboration behind the water recrystallization.
Example three
101 reactors are installed agitator, continuously the recycle gas absorption unit.Absorb in the mother liquor adding reactor of tail gas being used in the example two, add into 65% nitric acid 1100g, sulfuric acid 8g is heated to 80 ℃, drips 96% oxalic acid 900g in 2 hours, and the control reacting liquid temperature is at 80-85 ℃ during dropping.After ethylene glycol dropwises, keep reacting liquid temperature, continued stirring reaction 4 hours at 80-85 ℃.Mother liquor in the reaction behind the discharging tail gas use-case two separation oxalic acid absorbs.After the reaction solution cooling, centrifugation is separated out crystal and is got oxalic acid, 1598g, productive rate 94%.The water recrystallization gets pure product.
The nitrogenous tail gas that discharges when reacting among the present invention uses the mother liquor behind the separation oxalic acid to absorb, and makes Recycling Mother Solution apply mechanically.Mother liquor can make nitric acid content reach 15-30% after absorbing tail gas.
Claims (1)
1, producing oxalic acid by oxidation of glycol novel method, wherein oxidizing medium is sulfuric acid, nitric acid and water, the liquid material that it is characterized in that reactor 1 passes through water cooler 3 through recycle pump 2, enter absorption unit 4 after the cooling, absorb behind the gas of autoreactor 1 directly Returning reactor 1 in absorption unit 4, reacting material ratio is: nitric acid: ethylene glycol＜3 (mol ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105413 CN1021812C (en) | 1988-05-23 | 1988-05-23 | Technology for producing oxalic acid by oxidation of glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105413 CN1021812C (en) | 1988-05-23 | 1988-05-23 | Technology for producing oxalic acid by oxidation of glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1038091A CN1038091A (en) | 1989-12-20 |
| CN1021812C true CN1021812C (en) | 1993-08-18 |
Family
ID=4833607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105413 Expired - Fee Related CN1021812C (en) | 1988-05-23 | 1988-05-23 | Technology for producing oxalic acid by oxidation of glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021812C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108976230A (en) * | 2018-06-18 | 2018-12-11 | 东莞市联洲知识产权运营管理有限公司 | A method of dolasetron mesilate key intermediate is prepared based on graphene activation |
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1988
- 1988-05-23 CN CN 88105413 patent/CN1021812C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1038091A (en) | 1989-12-20 |
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| CF01 | Termination of patent right due to non-payment of annual fee |