CN105646316B - A kind of method and continuous production device of the acetic acid solution preparing low water content high concentration peroxy acid - Google Patents
A kind of method and continuous production device of the acetic acid solution preparing low water content high concentration peroxy acid Download PDFInfo
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- CN105646316B CN105646316B CN201610030605.4A CN201610030605A CN105646316B CN 105646316 B CN105646316 B CN 105646316B CN 201610030605 A CN201610030605 A CN 201610030605A CN 105646316 B CN105646316 B CN 105646316B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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 kind of methods and continuous production device of the acetic acid solution preparing low water content high concentration peroxy acid, the use of excessive acetic acid and percarbamide is raw material, Peracetic acid and sulfuric-urea hydrate are generated under the catalysis of the concentrated sulfuric acid, then the acetic acid solution of Peracetic acid and sulfuric-urea hydrate separation are obtained into the acetic acid solution of the Peracetic acid of low water content by way of depressurizing short-path distillation.Continuous production device includes that 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 input nitration mixture storage tank (2) in stirred autoclave (1) after reaction；Feed liquid in nitration mixture storage tank (2) is put into short-distance distiller (3), light component low water content high concentration peroxy acid solution is detached and is flowed into Peracetic acid storage tank (4), and heavy constituent by-product is sent into secondary material storage tank (5).Peracetic acid content prepared by this method is high, and water content is low.
Description
Technical field
The present invention relates to the preparations of Peracetic acid, the especially synthesis of the acetic acid solution of low water content high concentration peroxy acid
Method and device.
Background technology
Peracetic acid is a kind of important industrial oxidation agent and Medical efficient fungicide, it is widely used in chemical industry
Materials synthesis, petroleum industry diesel fuel desulfurization, the fabric bleaching of light textile industry and the sterilizing of medicine and hygiene fields.It crosses
There are two types of the main preparation methods of fluoroacetic acid：One is by using acetic acid under concentrated sulfuric acid catalyst with H2O2Reactant aqueous solution, warp
The aqueous solution of Peracetic acid is made after distillation；This method technological process is simple, but water content in the peracetic acid soln prepared
Often higher than 45wt%.Another method be by using acetaldehyde ethyl acetate or acetone soln under the action of catalyst with oxygen
Gas or air reaction prepare the ethyl acetate or acetone soln of Peracetic acid；Peracetic acid soln prepared by this method is not aqueous,
But its technological process is complicated, equipment investment is huge and preparation process explosion hazard is big, is not easy to large-scale production.
Certain special dimensions in chemical industry synthesis, epoxidation reaction and the Baeyer-Villiger for such as carrying out alkene are anti-
At once, Peracetic acid is excellent oxidant.But high water content (water content is higher than 45wt%) peracetic acid soln aoxidizes
Agent can cause to react target product generation partial hydrolysis after generating, to reduce the yield of target product；Meanwhile hydrolyzing production
Raw by-product can increase the difficulty of target product purification and post-processing again.According to oxidation of acetaldehyde legal system Peracetic acid, not only
Process complexity and equipment investment can be greatly increased, it is dangerous also to aggravate production.Therefore, simple production process is designed and developed out
And the new method of safety has great importance and actually answers to produce the high concentration peroxy acid solution of low water content
With value.
Invention content
The invention solves first technical problem be to provide and a kind of preparing low water content high concentration peroxy acid solution
Method.Peracetic acid content prepared by this method is high, and water content is low.
The invention solves second technical problem be to provide the continuous production device of the production method.
To solve first technical problem, the technical scheme is that the use of excessive acetic acid and percarbamide being former material
Material generates Peracetic acid and sulfuric-urea hydrate under the catalysis of the concentrated sulfuric acid, then will by way of depressurizing short-path distillation
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.It is anti-
Answer equation as follows：
Method of the present invention, includes the following steps：
(1) percarbamide is added in reaction kettle, then mixes the concentrated sulfuric acid with acetic acid, temperature control is at 35-40 DEG C, reaction
0.5h, solid, which fades away, in mixed liquor becomes clear nitration mixture liquid.It is preferred that mole of percarbamide, acetic acid and the concentrated sulfuric acid
Than being 1: 3-4: 0.25-0.5；
(2) clear nitration mixture liquid obtained by the reaction distills in short-distance distiller, light component Peracetic acid, acetic acid and
A small amount of water flows into Peracetic acid storage tank after being evaporated after the condensation of interior cooling layer outer wall, and heavy constituent sulfuric-urea hydrate is along outer
Heating layer inner wall flow to secondary material storage tank.The preferable control condition of short-distance distiller is：Absolute pressure 1.33-6.33kPa, when stop
Between 2-3min, interior cooling layer temperature be 5-15 DEG C, additional thermosphere temperature be 40-50 DEG C.
The acetic acid that the Peracetic acid of Peracetic acid content >=25wt%, water content≤2wt% are obtained by above method is molten
Liquid；The sulfuric-urea hydrate of by-product is used as phosphorus decomposing agent production composite fertilizer.
To solve second technical problem, the present invention provides a set of continuous production device, which includes that stirring is anti-
Kettle 1, nitration mixture storage tank 2, short-distance distiller 3, Peracetic acid storage tank 4 and secondary material storage tank 5, raw material is answered to be reacted in stirred autoclave 1
Input nitration mixture storage tank 2 afterwards；Feed liquid in nitration mixture storage tank 2 is put into short-distance distiller 3, light component low water content high concentration peroxide second
Acid solution is detached and is flowed into Peracetic acid storage tank 4, and heavy constituent by-product is sent into secondary material storage tank 5 and by defeated as byproduct
Go out.
Apparatus of the present invention operating process：
(1) reaction kettle 1 is added in percarbamide, reaction kettle 1 is added after the concentrated sulfuric acid is mixed with acetic acid, adds sulfuric acid acetic acid
Reacting liquid temperature is controlled after mixed liquor and is stirred, and solid, which fades away, in mixed liquor becomes clear nitration mixture liquid；
(2) clear nitration mixture liquid completely reacted in reaction kettle 1 is conveyed into nitration mixture storage tank 2, continue in reaction kettle 1 into
The reaction of row step (1)；Nitration mixture in nitration mixture storage tank 2 is slowly put into short-distance distiller 3 by control valve opening, and control liquid exists
Residence time in short-distance distiller 3；
(3) absolute pressure, additional thermosphere temperature, interior cooling layer temperature in short-distance distiller 3 are controlled, nitration mixture is in short-path distillation
The additional thermosphere inner wall of device is heated, and light component Peracetic acid, acetic acid and a small amount of water condense after being evaporated in interior cooling layer outer wall
Peracetic acid storage tank 4 is flowed into afterwards, and heavy constituent sulfuric-urea hydrate flow to secondary material storage tank 5 along additional thermosphere inner wall.
The second of the Peracetic acid of high concentration low water content can be easily prepared using the method for the invention and device
Acid solution.Heated time of the Peracetic acid in distillation process is shorten to the 1/10 of common distillating method by this method, production peace
Full property greatly improves, and active oxygen conversion rate accordingly improves；This method avoids production process from raw material selection simultaneously
The acetic acid solution water content of the introducing of middle water entrainment, the Peracetic acid of production is less than 2wt%, is higher than far below conventional method
The water content of 45wt%；And this method considers reaction process from the economic angle of molecule, and production process does not have three wastes production
It is raw, two products of single step reaction, green pollution-free.
Description of the drawings
Fig. 1 is the schematic device of the acetic acid solution of continuous production low water content high concentration peroxy acid of the present invention.
The secondary material storage tank of 4. Peracetic acid storage tank of wherein 1. reaction kettle 2. nitration mixture storage tank, 3. short-distance distiller 5..
Fig. 2 is thin plate chromatography comparison diagram.
Wherein thin plate (a)：Left point is pure 6-caprolactone, after right point is peracetic acid soln peroxyester in comparative example 1
Sample tomographic results；Thin plate (b)：Left point is pure 6-caprolactone, after right point is peracetic acid soln peroxyester in embodiment 2
Sample tomographic results；Solvent is the volume ratio 1: 1 of ethyl acetate and n-hexane.
Specific implementation mode
It elaborates with reference to embodiments to the specific implementation mode of the present invention.
Embodiment 1
The percarbamide of 290g active o contents 16.5wt% is added in 2000ml reactors, then by the 98wt% concentrated sulfuric acids
75g is added in 540g glacial acetic acids and is slowly added in reactor after mixing, opens and stirs and heat mixed liquor to 40 DEG C of reaction 0.5h,
Obtain water white transparency nitration mixture liquid；After completion of the reaction, nitration mixture liquid is sent into molecular still solution storage trough, adjusts molecular distillation
Device feeds valve opening, and opening vacuum pump makes absolute pressure in molecular still be 1.33kPa, and control liquid is in molecular still
Residence time 3min, 40 DEG C of the additional thermosphere temperature of molecular still are passed through 5 DEG C of the coolant temperature of interior cooling layer, by mixed acid liquid
Body carries out short-path distillation；Obtain acetic acid solution about 593g, the sulfuric-urea hydrate about 310g of Peracetic acid.According to national standard GB
The content that 19104-2008 detects Peracetic acid in peracetic acid soln is about 37.5wt%, active oxygen conversion rate about 97.8%,
Water content is less than 1.1wt%.
Embodiment 2
The percarbamide of 290g active o contents 16.5wt% is added in 2000ml reactors, then by 98% concentrated sulfuric acid
110g is added in 600g glacial acetic acids and is slowly added in reactor after mixing, opens stirring and heating water bath mixed liquor is reacted to 38 DEG C
0.5h obtains water white transparency nitration mixture liquid；After completion of the reaction, nitration mixture liquid is pumped into the storage of molecular still solution with constant current
Slot adjusts molecular still and feeds valve opening, and opening vacuum pump makes absolute pressure in molecular still be 4.33kPa, controls liquid
Body residence time 2.5min in molecular still, the additional thermosphere temperature 45 C of molecular still, is passed through the cooling of interior cooling layer
Nitration mixture is carried out short-path distillation by 10 DEG C of liquid temperature；Obtain the acetic acid solution about 654g of Peracetic acid, sulfuric-urea hydrate about
343g.Content according to Peracetic acid in national standard GB 19104-2008 detection peracetic acid solns is about 33.8wt%, active oxygen
Conversion ratio about 97.3%, water content are less than 1.3wt%.
Embodiment 3
The percarbamide of 290g active o contents 16.5wt% is added in 2000ml reactors, then by 98% concentrated sulfuric acid
150g is added in 720g glacial acetic acids and is slowly added in reactor after mixing, opens stirring and heating water bath mixed liquor is reacted to 35 DEG C
0.5h obtains water white transparency nitration mixture liquid；After completion of the reaction, nitration mixture liquid is pumped into the storage of molecular still solution with constant current
Slot adjusts molecular still and feeds valve opening, and opening vacuum pump makes absolute pressure in molecular still be 6.33kPa, controls liquid
Body residence time 2min in molecular still, the additional thermosphere temperature 50 C of molecular still, is passed through the coolant liquid of interior cooling layer
Nitration mixture is carried out short-path distillation by 15 DEG C of temperature；Obtain the acetic acid solution about 774g of Peracetic acid, sulfuric-urea hydrate about
382g.Content according to Peracetic acid in national standard GB 19104-2008 detection peracetic acid solns is about 28.5wt%, active oxygen
Conversion ratio about 97.1%, water content are less than 1.1wt%.
Comparative example 1
The aqueous hydrogen peroxide solution of 300g mass fractions 30% is slowly added by 98% concentrated sulfuric acids of 120g and 180g ice
In the nitration mixture of acetic acid composition, nitration mixture heating water bath reacts 0.5h to 40 DEG C after dripping；Then in 50 DEG C, 3.33kPa conditions
It is lower to depressurize the peroxide acetate aqueous solution for steaming preparation, peroxide acetate aqueous solution about 450g is obtained, according to national standard GB 19104-2008
Detect Peracetic acid content 38.4wt%, water content about 52wt%, active oxygen conversion rate 85.9%.
By the peracetic acid soln prepared in comparative example 1 and embodiment 2 respectively according to Peracetic acid and cyclohexanone molar ratio
1.2: 1 ratio is reacted, 45 DEG C of reaction condition, reaction time 4h；Ingredient in reaction solution is carried out respectively after reaction
TLC (thin plate chromatography method) is detected.Testing result is as shown in Figure 2.The peracetic acid soln that in comparative example 1 prepared by method aoxidizes hexamethylene
When ketone prepares 6-caprolactone, target product low yield, impurity content are high；The peracetic acid soln oxygen that in embodiment 2 prepared by method
When change cyclohexanone prepares 6-caprolactone, cyclohexanone almost all is converted into target product and impurity is seldom.
Claims (6)
1. a kind of method for the acetic acid solution preparing low water content high concentration peroxy acid, is using excessive acetic acid and percarbamide
Raw material generate Peracetic acid and sulfuric-urea hydrate under the catalysis of the concentrated sulfuric acid, then pass through the side of decompression short-path distillation
Formula by the acetic acid solution of Peracetic acid and sulfuric-urea hydrate separation, obtain Peracetic acid content >=wt25%, water content≤
The acetic acid solution of the Peracetic acid of 2wt%.
2. according to the method described in claim 1, including the following steps：
(1) percarbamide being added in reaction kettle, then mixes the concentrated sulfuric acid with acetic acid, temperature control reacts 0.5h at 35-40 DEG C,
Solid, which fades away, in mixed liquor becomes clear nitration mixture liquid；
(2) clear nitration mixture liquid obtained by the reaction distills in short-distance distiller, light component Peracetic acid, acetic acid and a small amount of
Water be evaporated after in interior cooling layer outer wall condensation after flow into Peracetic acid storage tank, heavy constituent sulfuric-urea hydrate is along external heat
Layer inner wall flow to secondary material storage tank.
3. according to the method described in claim 2, it is characterized in that the molar ratio of percarbamide, acetic acid and the concentrated sulfuric acid is 1: 3-4:
0.25-0.5。
4. according to the method described in claim 2, it is characterized in that the control condition of short-distance distiller is：Absolute pressure 1.33-
6.33kPa, residence time 2-3min, interior cooling layer temperature are 5-15 DEG C, and additional thermosphere temperature is 40-50 DEG C.
5. a kind of continuous production device for realizing one of Claims 1 to 4 the method, 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 reaction in stirred autoclave (1)
Input nitration mixture storage tank (2) afterwards；Feed liquid in nitration mixture storage tank (2) is put into short-distance distiller (3), light component low water content high concentration
Peracetic acid soln is detached and is flowed into Peracetic acid storage tank (4), and heavy constituent by-product is sent into secondary material storage tank (5).
6. a kind of method that continuous production device using described in claim 5 is produced：
(1) reaction kettle (1) is added in percarbamide, reaction kettle (1) is added after the concentrated sulfuric acid is mixed with acetic acid, adds sulfuric acid acetic acid
Reacting liquid temperature is controlled after mixed liquor and is stirred, and solid, which fades away, in mixed liquor becomes clear nitration mixture liquid；
(2) clear nitration mixture liquid completely reacted in reaction kettle (1) is conveyed into nitration mixture storage tank (2), continued in reaction kettle (1)
Carry out the reaction of step (1)；Nitration mixture in nitration mixture storage tank (2) is slowly put into short-distance distiller (3) by control valve opening, is controlled
Residence time of the liquid in short-distance distiller (3)；
(3) absolute pressure, additional thermosphere temperature, interior cooling layer temperature in control short-distance distiller (3), nitration mixture is in short-distance distiller
Additional thermosphere inner wall is heated, light component Peracetic acid, acetic acid and a small amount of water be evaporated after in interior cooling layer outer wall condensation after
Peracetic acid storage tank (4) is flowed into, heavy constituent sulfuric-urea hydrate flow to secondary material storage tank (5) along additional thermosphere inner wall.
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| 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 |
| 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 |
| 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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| EP1016657B1 (en) * | 1998-12-15 | 2002-01-30 | Akzo Nobel N.V. | Method for producing peracetic acid |
| FI112363B (en) * | 2001-04-04 | 2003-11-28 | Kemira Chemicals Oy | Process for the preparation of peracetic acid |
| CN101724508A (en) * | 2009-10-30 | 2010-06-09 | 华南理工大学 | Method for preparing monoglyceride by utilizing circulating esterification reaction and molecular distillation of diester |
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