CN105503685B - A kind of method and its device for preparing anhydrous peroxyacetic acid solution - Google Patents
A kind of method and its device for preparing anhydrous peroxyacetic acid solution Download PDFInfo
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- CN105503685B CN105503685B CN201610030797.9A CN201610030797A CN105503685B CN 105503685 B CN105503685 B CN 105503685B CN 201610030797 A CN201610030797 A CN 201610030797A CN 105503685 B CN105503685 B CN 105503685B
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Abstract
The invention discloses a kind of method and its device for preparing anhydrous peroxyacetic acid solution, percarbamide and excessive acetic acid generate Peracetic acid, water and urea admixture under sulfuric acid catalysis；Distillating mixture, steam obtains anhydrous peroxyacetic acid acetic acid steam after sulfuric acid absorption moisture, and steam obtains the acetic acid solution of anhydrous peroxyacetic acid after cooling；Sulfuric acid generates fluid sulphuric acid urea hydrate with urea reaction, stays in a kettle..Described device includes reactor (1), rectifying drying tower (2), cooling tower (3), vacuum plant (4), tower bottom is dried at the top of reactor (1) with rectifying to connect, there are concentrated sulfuric acid charge door and steam (vapor) outlet at the top of rectifying drying tower, steam (vapor) outlet is connected with cooling tower, and cooling tower is connected with vacuum plant.This method compares oxidation of acetaldehyde legal system anhydrous peroxyacetic acid solution, and technological process is simple, equipment investment is few, safe and environment friendly and pollution-free, with important actual application value.
Description
Technical field
The present invention relates to the preparation method of Peracetic acid, the method and apparatus of anhydrous peroxyacetic acid solution is particularly prepared.
Background technology
Peracetic acid is a kind of important industrial oxidation agent and Medical efficient bactericide, is widely used in chemical industry
Materials synthesis, the diesel fuel desulfurization of petroleum industry, the sterilizing of the fabric bleaching of light textile industry and medicine and hygiene fieldses.Peroxide
The main preparation methods of acetic acid have two kinds：One kind be by using acetic acid under sulphuric acid catalysis with H2O2It is prepared by reactant aqueous solution,
The aqueous solution of Peracetic acid can be obtained through distillation；It is another be by using acetaldehyde under catalyst action with oxygen reaction system
Standby anhydrous peroxyacetic acid organic solution.
Acetic acid hydrogen peroxide sulfuric acid catalysis method can be with quality of production concentration 10%-55% peroxide acetate aqueous solution.Patent text
Offer disclosed in the A1 of the EP 1016657 and A1 of US 2002177732 that technics comparing is simple, equipment investment is few, production security compared with
Height, but peroxide acetate aqueous solution can only be prepared.
Acetaldehyde air/oxygen oxidizing process can produce anhydrous peroxyacetic acid solution, but this method device therefor is complicated, investment
Greatly, safety coefficient requires high；The acetaldehyde list peracetic acid ester produced simultaneously in production process is the explosive compound of Thermo-sensitive, blast danger
It is dangerous higher；If suppressing the formation of acetaldehyde list peracetic acid ester with acidic catalyst, the later stage needs heavy metal acidic catalyst
It is removed, otherwise influences anhydrous peroxyacetic acid stability of solution.
In terms of chemical industry synthesis, made of the peracetic acid soln of high-moisture (water content is higher than 45wt% under normal circumstances)
When oxidant carries out epoxidation reaction and the Baeyer-Villiger reactions of alkene, the presence of water can cause target product to generate
After occur partial hydrolysis, so as to reduce yield；Meanwhile, hydrolysate can increase the difficulty of product purification and post processing again.Therefore,
Prepare anhydrous high concentration peroxy acid solution has important value in terms of chemical industry synthesis.Seek safe efficient, cheap, environmentally friendly
The approach of anhydrous peroxyacetic acid solution is prepared, is conducive to expanding Peracetic acid application field, reduction Peracetic acid production cost.
The content of the invention
The invention solves the problems that first problem be to provide a kind of method for preparing anhydrous peroxyacetic acid solution.
The invention solves the problems that second technical problem be to provide a kind of device for preparing anhydrous peroxyacetic acid solution.
The technical scheme of the method for the invention is：Percarbamide and excessive acetic acid generate peroxide second under sulfuric acid catalysis
Acid, water and urea admixture；Distillating mixture, steam obtains anhydrous peroxyacetic acid acetic acid steam after sulfuric acid absorption moisture, steams
Vapour obtains the acetic acid solution of anhydrous peroxyacetic acid after cooling；Sulfuric acid generates fluid sulphuric acid urea hydrate with urea reaction, stays
In a kettle..Its specific reaction equation is as follows：
The method of the invention, comprises the following steps：
(1) percarbamide and acetic acid are added in reactor according to mol ratio 1: 1-5 and is mixed into slurry, according to mixed slurry
0-2 times of quality adds organic solvent；Control system pressure is in 1.33-41.33kPa, and temperature is at 40-55 DEG C.Organic solvent can
To be the low boiling point solvents such as dichloromethane, dichloroethanes, chloroform, acetone, ethyl acetate.
(2) concentrated sulfuric acid is preheated to 40-55 DEG C, then added according to the ratio of sulfuric acid and percarbamide mol ratio 1: 1-2
At the top of rectifying drying tower, the concentrated sulfuric acid forms liquid film between the filler of rectifying drying tower, absorbs the peroxide distilled out from reactor
Moisture content in acetic acid, acetic acid, organic vapor, enters in reactor after concentrated sulfuric acid water suction and participates in catalysis and given birth to urea reaction
Into fluid sulphuric acid urea hydrate；Rise to tower top anhydrous peroxyacetic acid and acetic acid steam it is condensed after obtain anhydrous peroxide second
The organic solution of acid.
The present invention can react generation Peracetic acid and by-product liquid sulphur using acetic acid and percarbamide under sulfuric acid catalysis
The principle of uraturia element hydrate, fairly simple, easily can prepare anhydrous peroxyacetic acid organic solution, and by-product sulfuric-urea
Hydrate.This method raw material percarbamide, acetic acid and the concentrated sulfuric acid are cheap and easy to get.Principal product anhydrous peroxyacetic acid solution purposes
Extensively, added value is high, remarkable in economical benefits.Accessory substance sulfuric-urea hydrate can be used as the original for preparing sulfonic acid ammonia and production composite fertilizer
Material.This method compares oxidation of acetaldehyde legal system anhydrous peroxyacetic acid solution, and technological process is simple, equipment throwing is less, safe,
And it is environment friendly and pollution-free, therefore with important actual application value.
To solve second technical problem, the present invention provides a kind of device for preparing anhydrous peroxyacetic acid solution, the device
Including reactor 1, rectifying drying tower 2, cooling tower 3, vacuum plant 4, the top of reactor 1 is dried tower bottom with rectifying and connected, essence
Evaporating at the top of drying tower has concentrated sulfuric acid charge door and steam (vapor) outlet, and steam (vapor) outlet is connected with cooling tower, and cooling tower connects with vacuum plant
It is logical.
After above-mentioned steps, fluid sulphuric acid urea hydrate, remaining acetic acid, You Jirong are contained in the bottoms material of reactor 1
Agent, Peracetic acid and a small amount of water, further processing cycle can be utilized by the following method：When the concentrated sulfuric acid of necessary amount is from rectifying
The top of drying tower is all added after reactor 1, and the bottoms material in reactor 1 is transported in recirculating still 5, heat cycles kettle 5
The acetic acid in material, organic solvent, the Peracetic acid of residual and a small amount of water is set to steam and enter the middle part of rectifying drying tower 2,
Remaining fluid sulphuric acid urea hydrate is used as accessory substance by the pump housing and exported in recirculating still 5.
Additional equipment is：The bottom discharge mouthful of reactor 1 is connected with its top feed mouthful of recirculating still 5, the steaming of recirculating still 5
The tower body of vapor outlet connection rectifying drying tower 2, discharging opening is arranged at the bottom of recirculating still 5.
Face that the inside of device of the present invention is all to be contacted with reaction solution or steam (including filling out in rectifying drying tower
Material) it is glass surface, enamel face or inert plastic face etc., plastics can be polypropylene, polytetrafluoroethylene (PTFE) etc..
Brief description of the drawings
Fig. 1 is the schematic diagram that anhydrous peroxyacetic acid solution containment is prepared described in patent of the present invention.
Wherein：1- reactors, 2- rectifying drying towers, 3- cooling towers, 4- vacuum plants, 5- recirculating stills
Embodiment
The embodiment to the present invention elaborates with reference to embodiments.
Embodiment 1
The percarbamide of 190g active o contents 16.5% and 600g acetic acid are mixed into add after slurry and done with rectifying
In the 2000ml reactors of dry tower.Water-ring vacuum pump is opened, by absolute pressure control in system in 1.33-11.33kPa.Will
Slurry in reactor is heated to 50 DEG C, and now glass is filled out in the acetic acid gentle boil in reactor and pre- thermal rectification drying tower
Material.98% concentrated sulfuric acid that 200g is preheated into 50 DEG C under suction function is slow from rectifying drying column overhead instillation packing area.
The concentrated sulfuric acid that packing area declines, which contacts with the mixed vapour risen and absorbs the moisture content in steam, releases heat, the mixing after dehydration
Steam is further up to after tower top, and condensation obtains the acetic acid solution of anhydrous peroxyacetic acid in condenser pipe.Dense sulphur after water suction
Acid is sunk down into reactor as catalyst and reaction raw material.The circulation rate that above procedure passes through 55 DEG C of circulating hot waters of control
With the aperture of sulfuric acid inlet valve, control steam production is added dropwise flux matched with the concentrated sulfuric acid.Finally, anhydrous peroxide is obtained by the method
The acetic acid solution 626g of acetic acid, sulfuric acid monohydrate urea liquid 353g.The second of Peracetic acid is detected according to national standard GB19104-2008
The mass fraction of Peracetic acid is 22.8%, active oxygen conversion rate 93.9% in acid solution.
Embodiment 2
The percarbamide of 190g active o contents 16.5%, 120g acetic acid and 620g ethyl acetate are mixed into after slurry
It is added in the 2000ml reactors with rectifying drying tower.System pressure is controlled in 11.33-31.33kPa.In reactor
Slurry is heated to 45 DEG C, under suction function that the concentrated sulfuric acids of 100g 98% for being preheated to 45 DEG C is slow from rectifying drying column overhead
Instill packing area.Moisture content releasing heat in the concentrated sulfuric acid that packing area declines is contacted with the mixed vapour risen and absorbs steam
Amount, mixed vapour after dehydration is further up to after tower top, and condensation obtains anhydrous peroxyacetic acid solution in condenser pipe, absorbs water
The concentrated sulfuric acid sink down into reactor as catalyst and reaction raw material.Above procedure is followed by 50 DEG C of circulating hot waters of control
The aperture of ring speed and sulfuric acid inlet valve, control steam production is added dropwise flux matched with the concentrated sulfuric acid.Anhydrous mistake is obtained by the method
The ethyl acetate solution 750g of fluoroacetic acid, fluid sulphuric acid urea hydrate 262g.The mass fraction of Peracetic acid in acetic acid solution
For 19.4%, active oxygen conversion rate 95.7%.
Embodiment 3
The percarbamide of 190g active o contents 16.5%, 240g acetic acid and 430g acetone are mixed into after slurry and added
Into the 2000ml reactors with rectifying drying tower.Control system pressure 21.33-41.33kPa.By the slurry in reactor
It is heated to 40 DEG C.Slow instilled from rectifying drying column overhead of 98% concentrated sulfuric acid that 150g is preheated into 40 DEG C under suction function is filled out
Expect area.Above procedure by controlling the circulation rate of 45 DEG C of circulating hot waters and the aperture of sulfuric acid inlet valve, control steam production with
The concentrated sulfuric acid is added dropwise flux matched.Finally, the acetone acetic acid mixed solution 694g of anhydrous peroxyacetic acid, liquid sulfur are obtained by the method
Uraturia element hydrate 311g.The quality of Peracetic acid in the acetic acid solution of Peracetic acid is detected according to national standard GB 19104-2008
Fraction is 21.1%, active oxygen conversion rate 96.2%.
Claims (9)
1. a kind of method for preparing anhydrous peroxyacetic acid solution, percarbamide and excessive acetic acid generate peroxide second under sulfuric acid catalysis
Acid, water and urea admixture；Distillating mixture, steam obtains anhydrous peroxyacetic acid acetic acid steam after sulfuric acid absorption moisture, steams
Vapour obtains the acetic acid solution of anhydrous peroxyacetic acid after cooling；Sulfuric acid generates fluid sulphuric acid urea hydrate with urea reaction, stays
In a kettle.；
Comprise the following steps：
(1) percarbamide and acetic acid are added in reactor according to mol ratio 1: 1-5 and is mixed into slurry, according to mixed slurry quality
0-2 times add organic solvent；Control system pressure is in 1.33-41.33kPa, and temperature is at 40-55 DEG C；
(2) concentrated sulfuric acid is preheated to 40-55 DEG C, then adds rectifying according to the ratio of sulfuric acid and percarbamide mol ratio 1: 1-2
At the top of drying tower, the concentrated sulfuric acid forms liquid film between the filler of rectifying drying tower, absorb distilled out from reactor Peracetic acid,
Moisture in acetic acid, organic vapor, enters in reactor after concentrated sulfuric acid water suction and participates in catalysis and generate liquid with urea reaction
Body sulfuric-urea hydrate；Rise to tower top anhydrous peroxyacetic acid and acetic acid steam it is condensed after obtain anhydrous peroxyacetic acid
Organic solution.
2. the method according to claim 1 for preparing anhydrous peroxyacetic acid solution, it is characterized in that organic solvent is dichloromethane
Alkane, dichloroethanes, chloroform, acetone or ethyl acetate.
3. the method for preparing anhydrous peroxyacetic acid solution according to one of claim 1~2, when necessary amount the concentrated sulfuric acid from
The top of rectifying drying tower is all added after reactor (1), and the bottoms material in reactor (1) is transported in recirculating still (5), plus
Thermal cycle kettle (5) steams acetic acid, organic solvent, the Peracetic acid of residual and a small amount of water in material and enters rectifying drying
Remaining fluid sulphuric acid urea hydrate is used as accessory substance by the pump housing and exported in the middle part of tower (2), recirculating still (5).
4. a kind of device of one of claims 1 to 3 methods described, including reactor (1), rectifying drying tower (2), cooling tower
(3) dry tower bottom with rectifying at the top of, vacuum plant (4), reactor (1) to connect, have concentrated sulfuric acid charging at the top of rectifying drying tower
Mouth and steam (vapor) outlet, steam (vapor) outlet are connected with cooling tower, and cooling tower is connected with vacuum plant.
5. device according to claim 4, contacted it is characterized in that the inside of described device is all with reaction solution or steam
Face is glass surface, enamel face or inert plastic face.
6. device according to claim 5, it is characterized in that the plastics are polypropylene or polytetrafluoroethylene (PTFE).
7. device according to claim 4, it is characterized in that also include recirculating still (5), the bottom discharge mouthful of reactor (1) with
Its top feed mouthful connection of recirculating still (5), the tower body of the steam (vapor) outlet connection rectifying drying tower (2) of recirculating still (5), recirculating still
(5) discharging opening is arranged at bottom.
8. device according to claim 7, contacted it is characterized in that the inside of described device is all with reaction solution or steam
Face is glass surface, enamel face or inert plastic face.
9. device according to claim 8, it is characterized in that the plastics are polypropylene or polytetrafluoroethylene (PTFE).
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| CN111825589A (en) * | 2019-04-17 | 2020-10-27 | 上海朴颐化学科技有限公司 | Method for preparing anhydrous peroxyacetic acid solution by using microchannel reactor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016657A1 (en) * | 1998-12-15 | 2000-07-05 | Akzo Nobel N.V. | Method for producing peracetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FI112363B (en) * | 2001-04-04 | 2003-11-28 | Kemira Chemicals Oy | Process for the preparation of peracetic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1016657A1 (en) * | 1998-12-15 | 2000-07-05 | Akzo Nobel N.V. | Method for producing peracetic acid |
Non-Patent Citations (1)
| Title |
|---|
| The development and evaluation of a continuous flow process for the lipase-mediated oxidation of alkenes;Charlotte Wiles等;《Beilstein Journal of Organic Chemistry》;20091231;第5卷(第27期);1-12 * |
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