CN105646316A - Method for preparing acetic acid solution with low water content and high peracetic acid concentration and consecutive preparation device - Google Patents
Method for preparing acetic acid solution with low water content and high peracetic acid concentration and consecutive preparation device Download PDFInfo
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- CN105646316A CN105646316A CN201610030605.4A CN201610030605A CN105646316A CN 105646316 A CN105646316 A CN 105646316A CN 201610030605 A CN201610030605 A CN 201610030605A CN 105646316 A CN105646316 A CN 105646316A
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- C07C407/00—Preparation of peroxy compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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Abstract
The invention discloses a method for preparing an acetic acid solution with low water content and high peracetic acid concentration and a consecutive preparation device. Peracetic acid and percarbamide serve as raw materials, a peracetic acid and sulfuric acid urea aquo-complex is generated under catalysis of concentrated sulfuric acid, then an acetic acid solution of peracetic acid and the sulfuric acid urea aquo-complex are separated through a decompression short-range distillation mode, and the acetic acid solution of peracetic acid with low water content is obtained. The consecutive preparation device comprises a stirring reaction kettle (1), a mixed acid storage tank (2), a short-range distiller (3), a peracetic acid storage tank (4) and an auxiliary material storage tank (5). The raw materials react in the stirring reaction kettle (1) and then are conveyed into the mixed acid storage tank (2); material liquid in the mixed acid storage tank (2) is discharged into the short-range distiller (3), the light-component low-water-content and high-concentration peracetic acid solution is separated and flows into the peracetic acid storage tank (4), and heavy component side products are fed into the auxiliary material storage tank (5). The acetic acid solution prepared through the method is high in peracetic acid content and low in water content.
Description
Technical field
The present invention relates to the preparation of peracetic acid, particularly the synthetic method of the acetic acid solution of low water content high concentration peroxy acid and device.
Background technology
Peracetic acid is a kind of important industrial oxidation agent and Medical efficient antibacterial, and it is widely used in the sterilizing of the materials synthesis of chemical industry, the diesel fuel desulfurization of petroleum industry, the fabric bleaching of light textile industry and medicine and hygiene fields. The main preparation methods of peracetic acid has two kinds: one be by use acetic acid under sulphuric acid catalysis with H2O2Reactant aqueous solution, prepares the aqueous solution of peracetic acid after distillation; The method technological process is simple, but in the peracetic acid soln of preparation, water content is often higher than 45wt%. Another kind of method is ethyl acetate or the acetone soln by using the ethyl acetate of acetaldehyde or acetone soln to prepare peracetic acid under catalyst action with oxygen or air reaction; Peracetic acid soln prepared by the method is not moisture, but its technological process is complicated, equipment investment is huge and preparation process explosion hazard big, is not easy to large-scale production.
Some special dimension in chemical industry synthesizes, when the epoxidation reaction and Baeyer-Villiger as carried out alkene is reacted, peracetic acid is excellent oxidant. But high water content (water content is higher than 45wt%) peracetic acid soln does oxidant can cause the generating portion hydrolysis after generating of reaction target product, thus reducing the productivity of target product; Meanwhile, the by-product that hydrolysis produces can increase again the difficulty of target product purification and post processing. According to oxidation of acetaldehyde legal system peracetic acid, not only can be greatly increased process complexity and equipment investment, also can aggravate to produce danger. Therefore, the new method that production technology is simple and safe is designed and developed out, in order to produce the high concentration peroxy acid solution of low water content, have great importance and actual application value.
Summary of the invention
First technical problem that the invention solves the problems that is to provide a kind of method preparing low water content high concentration peroxy acid solution. Peracetic acid content prepared by this method is high, and water content is low.
Second technical problem that the invention solves the problems that is to provide the continuous production device of this production method.
For solving first technical problem, the technical scheme is that use excessive acetic acid is raw material with percarbamide, peracetic acid and sulfuric-urea hydrate is generated under the catalysis of concentrated sulphuric acid, then pass through the mode of decompression short-path distillation by the acetic acid solution of peracetic acid and sulfuric-urea hydrate separation, obtain the acetic acid solution of the peracetic acid of low water content. Its reaction equation is as follows:
Method of the present invention, comprises the following steps:
(1) adding in reactor by percarbamide, then mixed with acetic acid by concentrated sulphuric acid, temperature control, at 35-40 DEG C, reacts 0.5h, and in mixed liquor, solid fades away and becomes clear nitration mixture liquid. The mol ratio of preferred percarbamide, acetic acid and concentrated sulphuric acid is 1: 3-4: 0.25-0.5;
(2) the clear nitration mixture liquid being obtained by reacting distills in short-distance distiller, light component peracetic acid, acetic acid and a small amount of water flow into peracetic acid storage tank after being evaporated after interior cooling layer outer wall condenses, and heavy constituent sulfuric-urea hydrate flow to secondary material storage tank along additional thermosphere inwall. Short-distance distiller controls condition preferably: absolute pressure 1.33-6.33kPa, time of staying 2-3min, and interior cooling layer temperature is 5-15 DEG C, and additional thermosphere temperature is 40-50 DEG C.
The acetic acid solution of the peracetic acid of peracetic acid content >=25wt%, water content��2wt% is obtained by above method; The sulfuric-urea hydrate of by-product is used as phosphorus decomposing agent and produces compound fertilizer.
For solving second technical problem, the invention provides a set of continuous production device, this device includes stirred autoclave 1, nitration mixture storage tank 2, short-distance distiller 3, peracetic acid storage tank 4 and secondary material storage tank 5, and raw material inputs nitration mixture storage tank 2 after reacting in stirred autoclave 1; Putting in short-distance distiller 3 by feed liquid in nitration mixture storage tank 2, light component low water content high concentration peroxy acid solution is separated and flows into peracetic acid storage tank 4, and heavy constituent by-product is sent in pair material storage tank 5 and is taken as side-product output.
Apparatus of the present invention operating process:
(1) percarbamide adding reactor 1, add reactor 1 after being mixed with acetic acid by concentrated sulphuric acid, control reacting liquid temperature and stir after adding sulphuric acid acetic acid mixture, in mixed liquor, solid fades away and becomes clear nitration mixture liquid;
(2) clear nitration mixture liquid completely reacted in reactor 1 is conveyed into nitration mixture storage tank 2, reactor 1 proceeds the reaction of step (1); Control valve opening and the nitration mixture in nitration mixture storage tank 2 is slowly put in short-distance distiller 3, control the liquid time of staying in short-distance distiller 3;
(3) absolute pressure, additional thermosphere temperature, interior cooling layer temperature in short-distance distiller 3 is controlled, nitration mixture is heated at the additional thermosphere inwall of short-distance distiller, light component peracetic acid, acetic acid and a small amount of water flow into peracetic acid storage tank 4 after being evaporated after interior cooling layer outer wall condenses, and heavy constituent sulfuric-urea hydrate flow to secondary material storage tank 5 along additional thermosphere inwall.
Utilize the method for the invention and device can prepare the acetic acid solution of peracetic acid of high concentration low water content easily. Peracetic acid heated time in still-process is shortened to the 1/10 of common distillating method by this method, and production security is greatly improved, and active oxygen conversion ratio improves accordingly; This method avoids the introducing of water entrainment production process from raw material selection simultaneously, and the acetic acid solution water content of the peracetic acid of production, less than 2wt%, is higher than the water content of 45wt% far below traditional method;And this method considers reaction process from the economic angle of molecule, and production process does not have the three wastes to produce, two products of single step reaction, environmental protection is pollution-free.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of the acetic acid solution of continuous production low water content high concentration peroxy acid of the present invention.
Wherein 1. reactor 2. nitration mixture storage tank 3. short-distance distiller 4. peracetic acid storage tanks 5. secondary material storage tank.
Fig. 2 is thin plate chromatography comparison diagram.
Wherein thin plate (a): left point is pure 6-caprolactone, right point is sample tomographic results after peracetic acid soln peroxyester in comparative example 1; Thin plate (b): left point is pure 6-caprolactone, right point is sample tomographic results after peracetic acid soln peroxyester in embodiment 2; Developing solvent is the volume ratio 1: 1 of ethyl acetate and normal hexane.
Detailed description of the invention
Below in conjunction with embodiment, the specific embodiment of the present invention is elaborated.
Embodiment 1
The percarbamide of 290g active o content 16.5wt% is added in 2000ml reactor, being added in 540g glacial acetic acid by 98wt% concentrated sulphuric acid 75g is slowly added in reactor after mixing again, open stirring and heat mixed liquor to 40 DEG C of reaction 0.5h, obtaining water white transparency nitration mixture liquid; After completion of the reaction, nitration mixture liquid is sent into molecular still solution storage trough, Molecular regulator distillator inlet valve aperture, opening vacuum pump makes absolute pressure in molecular still be 1.33kPa, control liquid time of staying 3min in molecular still, the additional thermosphere temperature of molecular still 40 DEG C, passes into the coolant temperature 5 DEG C of interior cooling layer, nitration mixture liquid is carried out short-path distillation; The acetic acid solution obtaining peracetic acid is about 593g, sulfuric-urea hydrate is about 310g. Detecting the content of peracetic acid in peracetic acid soln according to GB GB19104-2008 and be about 37.5wt%, active oxygen conversion ratio about 97.8%, water content is lower than 1.1wt%.
Embodiment 2
The percarbamide of 290g active o content 16.5wt% is added in 2000ml reactor, being added in 600g glacial acetic acid by 98% concentrated sulphuric acid 110g is slowly added in reactor after mixing again, open stirring heating in water bath mixed liquor and react 0.5h to 38 DEG C, obtain water white transparency nitration mixture liquid; After completion of the reaction, nitration mixture liquid constant flow pump is sent into molecular still solution storage trough, Molecular regulator distillator inlet valve aperture, opening vacuum pump makes absolute pressure in molecular still be 4.33kPa, control liquid time of staying 2.5min in molecular still, the additional thermosphere temperature 45 C of molecular still, passes into the coolant temperature 10 DEG C of interior cooling layer, nitration mixture is carried out short-path distillation; The acetic acid solution obtaining peracetic acid is about 654g, sulfuric-urea hydrate is about 343g. Detecting the content of peracetic acid in peracetic acid soln according to GB GB19104-2008 and be about 33.8wt%, active oxygen conversion ratio about 97.3%, water content is lower than 1.3wt%.
Embodiment 3
The percarbamide of 290g active o content 16.5wt% is added in 2000ml reactor, being added in 720g glacial acetic acid by 98% concentrated sulphuric acid 150g is slowly added in reactor after mixing again, open stirring heating in water bath mixed liquor and react 0.5h to 35 DEG C, obtain water white transparency nitration mixture liquid; After completion of the reaction, nitration mixture liquid constant flow pump is sent into molecular still solution storage trough, Molecular regulator distillator inlet valve aperture, opening vacuum pump makes absolute pressure in molecular still be 6.33kPa, control liquid time of staying 2min in molecular still, the additional thermosphere temperature 50 C of molecular still, passes into the coolant temperature 15 DEG C of interior cooling layer, nitration mixture is carried out short-path distillation;The acetic acid solution obtaining peracetic acid is about 774g, sulfuric-urea hydrate is about 382g. Detecting the content of peracetic acid in peracetic acid soln according to GB GB19104-2008 and be about 28.5wt%, active oxygen conversion ratio about 97.1%, water content is lower than 1.1wt%.
Comparative example 1
Being slowly added into by the aqueous hydrogen peroxide solution of 300g mass fraction 30% in the nitration mixture being made up of 120g98% concentrated sulphuric acid and 180g glacial acetic acid, nitration mixture heating in water bath, to 40 DEG C, reacts 0.5h after dripping; Then 50 DEG C, 3.33kPa when decompression steam the peroxide acetate aqueous solution of preparation, obtain peroxide acetate aqueous solution and be about 450g, detect peracetic acid content 38.4wt% according to GB GB19104-2008, water content is about 52wt%, active oxygen conversion ratio 85.9%.
The peracetic acid soln of preparation in comparative example 1 and embodiment 2 is reacted according to the ratio of peracetic acid Yu Ketohexamethylene mol ratio 1.2: 1 respectively, reaction condition 45 DEG C, response time 4h; Composition in reactant liquor is carried out TLC (thin plate chromatography) detection by reaction respectively after terminating. Testing result is as shown in Figure 2. When the peracetic acid soln peroxyester that in comparative example 1 prepared by method prepares 6-caprolactone, target product productivity is low, impurity content is high; When the peracetic acid soln peroxyester that in embodiment 2 prepared by method prepares 6-caprolactone, Ketohexamethylene is almost completely converted into target product and impurity is little.
Claims (6)
1. the method for the acetic acid solution preparing low water content high concentration peroxy acid, using excessive acetic acid and percarbamide is raw material, peracetic acid and sulfuric-urea hydrate is generated under the catalysis of concentrated sulphuric acid, then pass through the mode of decompression short-path distillation by the acetic acid solution of peracetic acid and sulfuric-urea hydrate separation, obtain the acetic acid solution of the peracetic acid of low water content.
2. method according to claim 1, comprises the following steps:
(1) adding in reactor by percarbamide, then mixed with acetic acid by concentrated sulphuric acid, temperature control, at 35-40 DEG C, reacts 0.5h, and in mixed liquor, solid fades away and becomes clear nitration mixture liquid;
(2) the clear nitration mixture liquid being obtained by reacting distills in short-distance distiller, light component peracetic acid, acetic acid and a small amount of water flow into peracetic acid storage tank after being evaporated after interior cooling layer outer wall condenses, and heavy constituent sulfuric-urea hydrate flow to secondary material storage tank along additional thermosphere inwall.
3. method according to claim 2, is characterized in that the mol ratio of percarbamide, acetic acid and concentrated sulphuric acid is 1: 3-4: 0.25-0.5.
4. method according to claim 2, is characterized in that the control condition of short-distance distiller is: absolute pressure 1.33-6.33kPa, time of staying 2-3min, and interior cooling layer temperature is 5-15 DEG C, and additional thermosphere temperature is 40-50 DEG C.
5. the continuous production device realizing the described method of one of Claims 1 to 4, including stirred autoclave (1), nitration mixture storage tank (2), short-distance distiller (3), peracetic acid storage tank (4) and secondary material storage tank (5), raw material is input nitration mixture storage tank (2) after reaction in stirred autoclave (1); Feed liquid in nitration mixture storage tank (2) is put in short-distance distiller (3), light component low water content high concentration peroxy acid solution is separated and flows into peracetic acid storage tank (4), and heavy constituent by-product is sent in pair material storage tank (5).
6. the operating process of the continuous production device described in a claim 5:
(1) percarbamide adding reactor 1, add reactor 1 after being mixed with acetic acid by concentrated sulphuric acid, control reacting liquid temperature and stir after adding sulphuric acid acetic acid mixture, in mixed liquor, solid fades away and becomes clear nitration mixture liquid;
(2) clear nitration mixture liquid completely reacted in reactor 1 is conveyed into nitration mixture storage tank (2), reactor 1 proceeds the reaction of step (1); Control valve opening and the nitration mixture in nitration mixture storage tank (2) is slowly put in short-distance distiller (3), control the liquid time of staying in short-distance distiller 3;
(3) absolute pressure, additional thermosphere temperature, interior cooling layer temperature in short-distance distiller (3) is controlled, nitration mixture is heated at the additional thermosphere inwall of short-distance distiller, light component peracetic acid, acetic acid and a small amount of water flow into peracetic acid storage tank (4) after being evaporated after interior cooling layer outer wall condenses, and heavy constituent sulfuric-urea hydrate flow to secondary material storage tank (5) along additional thermosphere inwall.
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| CN201610030605.4A CN105646316B (en) | 2016-01-19 | 2016-01-19 | A kind of method and continuous production device of the acetic acid solution preparing low water content high concentration peroxy acid |
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| CN201610030605.4A CN105646316B (en) | 2016-01-19 | 2016-01-19 | A kind of method and continuous production device of the acetic acid solution preparing low water content high concentration peroxy acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503540A (en) * | 2017-09-14 | 2019-03-22 | 黎明化工研究设计院有限责任公司 | A kind of method preparing 6-caprolactone and its continuous production device |
| CN110204524A (en) * | 2019-06-19 | 2019-09-06 | 黎明化工研究设计院有限责任公司 | A set of caprolactone synthesizer for having temp auto-controlled ability and its application method |
| CN112479963A (en) * | 2020-12-24 | 2021-03-12 | 武汉致远天合化工有限公司 | Method and device for preparing peroxyacetic acid |
| CN115669662A (en) * | 2022-11-21 | 2023-02-03 | 成都科宏达科技有限公司 | Low-irritation stable monoperoxyacetic acid disinfectant and preparation method thereof |
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| EP1016657A1 (en) * | 1998-12-15 | 2000-07-05 | Akzo Nobel N.V. | Method for producing peracetic acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503540A (en) * | 2017-09-14 | 2019-03-22 | 黎明化工研究设计院有限责任公司 | A kind of method preparing 6-caprolactone and its continuous production device |
| CN109503540B (en) * | 2017-09-14 | 2023-05-05 | 黎明化工研究设计院有限责任公司 | Method for preparing epsilon-caprolactone and continuous production device thereof |
| CN110204524A (en) * | 2019-06-19 | 2019-09-06 | 黎明化工研究设计院有限责任公司 | A set of caprolactone synthesizer for having temp auto-controlled ability and its application method |
| CN112479963A (en) * | 2020-12-24 | 2021-03-12 | 武汉致远天合化工有限公司 | Method and device for preparing peroxyacetic acid |
| CN112479963B (en) * | 2020-12-24 | 2024-05-21 | 武汉致远天合化工有限公司 | Method and device for preparing peroxyacetic acid |
| CN115669662A (en) * | 2022-11-21 | 2023-02-03 | 成都科宏达科技有限公司 | Low-irritation stable monoperoxyacetic acid disinfectant and preparation method thereof |
| CN115669662B (en) * | 2022-11-21 | 2024-04-30 | 成都科宏达科技有限公司 | Low-irritation-stability unitary peroxyacetic acid disinfectant and preparation method thereof |
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