CN102659655A - Peroxyacetic acid solution without additives and method for preparing same - Google Patents
Peroxyacetic acid solution without additives and method for preparing same Download PDFInfo
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- CN102659655A CN102659655A CN2012101321443A CN201210132144A CN102659655A CN 102659655 A CN102659655 A CN 102659655A CN 2012101321443 A CN2012101321443 A CN 2012101321443A CN 201210132144 A CN201210132144 A CN 201210132144A CN 102659655 A CN102659655 A CN 102659655A
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- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000654 additive Substances 0.000 title claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 59
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229960000583 acetic acid Drugs 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 25
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 8
- 150000002978 peroxides Chemical class 0.000 claims description 50
- 238000002360 preparation method Methods 0.000 claims description 28
- 230000000996 additive effect Effects 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 125000000129 anionic group Chemical group 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
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- 239000000047 product Substances 0.000 abstract description 17
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- 235000013305 food Nutrition 0.000 abstract description 5
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- 238000007086 side reaction Methods 0.000 abstract description 3
- 150000001450 anions Chemical class 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003124 biologic agent Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 108010054404 Adenylyl-sulfate kinase Proteins 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 102100039024 Sphingosine kinase 1 Human genes 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000726221 Gemma Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- -1 metals ion Chemical class 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 description 1
- 229940033663 thimerosal Drugs 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a peroxyacetic acid solution without additives and a method for preparing the same. The peroxyacetic acid solution consists of the following components: 2 to 40 percent of peroxyacetic acid, 10 to 35 percent of hydrogen peroxide, less than or equal to 5ppb of metal ion impurities, less than or equal to 1ppm of anion impurities, less than or equal to 5ppm of organic impurities and the balance of water, wherein less than or equal to 100 particles of which the size is more than or equal to 0.2 mu m exist in each milliliter of the peroxyacetic acid solution. The method comprises the following steps of putting high-purity hydrogen peroxide and high-purity glacial acetic acid in a reaction kettle, heating the mixture to between 40 and 50 DEG C, stirring the mixture for 20 to 40 hours, and then filtering and filling to obtain the finished product. The peroxyacetic acid solution obtained by the method has a high purity and can be applied to high-end fields such as medical treatment, food and biological agents, and the application field of the peroxyacetic acid is widened; when the peroxyacetic acid solution is applied to the field of reagent synthesis, side reaction and by-products are reduced, and the reaction yield is improved; and the peroxyacetic acid solution is environment-friendly.
Description
Technical field
The present invention relates to a kind of high stable peracetic acid soln that does not contain additive and preparation method thereof.
Background technology
Peracetic Acid is colourless irritating smell liquid, belongs to strong oxidizer, be prone to decompose, and under conditions such as alkalescence, reducing substances and metals ion, vigorous reaction, decomposition or even blast.Peracetic Acid is again good organo-peroxide; In the many-side field that has a wide range of applications; It has efficient quick sterilization effect, multiple germs such as kill bacteria, gemma fungi, yeast fast, thereby can be used as the sterilizing agent of transmissible disease, tap water, food etc.During SARS, during the Wenchuan earthquake epidemic prevention, Peracetic Acid has played significant role.Peracetic Acid also has good oxidation susceptibility, can be used as organic synthesis oxygenant, epoxidizing agent, polymerization starter etc.Simultaneously, Peracetic Acid also has been widely used in the fields such as desulfurization of bleaching, modification and the heavy oil of papermaking, textile industry.
At present, the industrial goods Peracetic Acid requires mass concentration＞15% of Peracetic Acid.But the situation that Peracetic Acid is decomposed even exploded very easily takes place in the industry article Peracetic Acid that satisfies this concentration requirement at present in storage and use.According to investigation in 2004 such as Wen Dongsheng of Shaanxi health monitoring institutions, 46 tame Peracetic Acid manufacturing enterprises, 60 batches product, qualified 39 batches, qualification rate is merely 65%.Different storage times, qualification rate is that 90.9%, 11 day qualification rate is 27.27% in three days, surpasses 20 days, and is then all defective.Register just in July, 2003 investigation of center Li Yun according to national chemical in addition, 1 to 12 May in 2003 more than 30 of Peracetic Acid accident takes place, dead 5 people, people more than 70 poisons or burns.In November, 2003, the blast of Yunnan Peracetic Acid storage tank, 5 people are dead, and 4 buildings are burnt.It is thus clear that the unstable of Peracetic Acid has caused very adverse influence for economy and the security in its use.Therefore, need to improve its stability and strengthen economy and security in its storage and the use.
Domestic a lot of scholar has also noticed this type of problem like Hao Wenhui, Ma Chunyu, Wang Lihua etc., has also carried out trying to explore of related fields, has obtained certain progress.But on the whole, effect is little, does not form extensive high stable property Peracetic Acid suitability for industrialized production technology in batches.The production of our times main flow is to adopt to add the stability that stablizer improves Peracetic Acid.Yet, use additive such as phosphorus not only to increase the foreign matter content in the Peracetic Acid, make it can not be in sector applications such as biotechnological formulation, food; And the interpolation of additive such as phosphorus, also can cause corrosion to equipment, reduce equipment life; Cause other side reaction; By product also can make eutrophication such as water body simultaneously, and environment is polluted.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, and a kind of additive and stable extraordinary peracetic acid soln of not containing is provided.
The present invention also will provide a kind of preparation method of peracetic acid soln simultaneously, the peracetic acid soln good stability of this method preparation, and purity is high, can be applied to high-end fields such as medical treatment, food, biotechnological formulation.
For solving the problems of the technologies described above; A kind of technical scheme that the present invention takes is: a kind of peracetic acid soln that does not contain additive, and in weight content, this peracetic acid soln is by Peracetic Acid 2%～40%; Hydrogen peroxide 10%～35%, individual event impurity metal ion content≤5ppb; Individual event anionic impurity content≤1ppm, organic impurities content≤5ppm and surplus are that water is formed, the particulate concentration of particle diameter in the said peracetic acid soln>=0.2 μ m is smaller or equal to 100/ml.
The another technical scheme that the present invention takes is: a kind of preparation method of the above-mentioned peracetic acid soln that does not contain additive; Its make concentration be high-purity Glacial acetic acid min. 99.5 of high-purity ydrogen peroxide 50 and concentration >=99.9wt% of 30wt%～70wt% in reaction kettle, 40 ℃～50 ℃ following insulated and stirred of temperature 20～40 hours; Filter then; Can obtains said peracetic acid soln, wherein:
Individual event impurity metal ion content≤1ppb in described high-purity ydrogen peroxide 50, unidirectional anionic impurity content≤1ppm, organic impurities content≤5ppm, the particulate concentration of particle diameter>=0.2 μ m is smaller or equal to 100/ml;
Reducing substance content≤0.03wt% in described high-purity Glacial acetic acid min. 99.5, individual event metallic impurity ion content＜10ppb, organic impurities content≤5ppm, the particulate concentration of particle diameter>=0.2 μ m is smaller or equal to 100/ml;
Before using said reaction kettle and being used for the pail pack of can; Adopting concentration is that high-purity peracetic acid soln and the specific conductivity of 35wt～40wt% carried out clean greater than the zero(ppm) water of 18.2M to reaction kettle and pail pack; The said high-purity peracetic acid soln individual event impurity metal ion content≤5ppb that is used for clean; Individual event anionic impurity content≤1ppm, organic impurities content≤5ppm.
Preferably, high-purity ydrogen peroxide 50 and high-purity Glacial acetic acid min. 99.5 to add the mol ratio that weight ratio satisfies hydrogen peroxide and Glacial acetic acid min. 99.5 be 1～2: 1, more preferably 1～1.5: 1.
Preferably, the concentration of said high-purity ydrogen peroxide 50 is 40wt%～50wt%.Preferably, individual event impurity metal ion content≤50ppt in high-purity ydrogen peroxide 50.
High-purity ydrogen peroxide 50 can be purified by commercially available common ydrogen peroxide 50 and obtained or directly be purchased acquisition (concentration is below 40%).According to a concrete aspect; The purification of ydrogen peroxide 50 can be taked following method: under 0 ℃～15 ℃ of temperature; Take nf membrane filtration or nf membrane filtration to combine and remove organism with absorption with macroporous adsorbent resin; Take Zeo-karb to remove the metallic impurity ion, take anionite-exchange resin to remove anionic impurity.According to a further embodiment: the purification of ydrogen peroxide 50 comprises the following step of carrying out successively:
1. prepare the ydrogen peroxide 50 of prescribed concentration, be cooled to 0 ℃～15 ℃, pass through macroporous adsorbent resin, with organic residues such as reduction anthraquinones with the speed of about 500L/H.The selectable macroporous adsorbent resin trade mark has Cangzhou precious grace chemical industry HPD of ltd series macroporous adsorbent resin, Cangzhou waffle worker YWD of ltd series far away macroporous adsorbent resin, the AB of TianXing, Bengbu resin company series macroporous adsorbent resin etc.
2. use nf membrane (material is PVDF or tetrafluoroethylene, aperture 1～5 nanometer, porosity 70～80%, 100～150 microns of thickness, applying pressure 1～1.5Mpa) carries out nanofiltration to ydrogen peroxide 50, further reduces organism such as anthraquinone in the ydrogen peroxide 50;
3. ydrogen peroxide 50 is passed through Zeo-karb with about 500L/H speed, styrene type cation exchange resin, the optional trade mark Chinese 732; Strong acid No. 1, No. 2, No. 3, No. 4; 010; The U.S.: AmberliteIR-120; Dowex-50, Germany: Lewatit-100, Japan: Diaion SK-1, France: AllassionCS; Duolite C-20, Russia: ky-3; SDB-3 etc.;
4. ydrogen peroxide 50 is passed through anionite-exchange resin with about 500L/H speed, the polystyrene weak basic ion exchange resin of macroporous structure, the optional trade mark is Chinese: D354, D351,710, D370; The U.S.: AmberliteIRA-93, Germany: Lewatit MP-60, Japan: Diaion WA-30, France: Duolite A305, Russia: AH-89 * 77II, Britain Zerolite MPH etc.
According to the present invention, high-purity Glacial acetic acid min. 99.5 can be purified by commercially available common ice acetic acid and obtained.Can adopt chemical subtraction, molecular sieve, IX, compound purifying technique such as rectifying is reduced to individual event metal concentration in the Glacial acetic acid min. 99.5 below the 10ppb, and purity is greater than 99.9%.A concrete embodiment is following:
1. Glacial acetic acid min. 99.5 is passed through molecular sieve (3A type molecular sieve), further reduce the ratio of water in the Glacial acetic acid min. 99.5;
2. according to the Incoming Quality Control situation, add potassium permanganate in mass ratio 0.1%～0.01% ratio, preparation distillation stoste, the amount of reducing substance such as formic acid, acetaldehyde is reduced to the reduzate quality below 0.03% by 0.3% in the reduction raw material;
3. Glacial acetic acid min. 99.5 is fed rectifying tower, rectifying;
4. Glacial acetic acid min. 99.5 is passed through strong cation-exchanging resin, styrene type cation exchange resin, the optional trade mark Chinese 732; Strong acid No. 1, No. 2, No. 3, No. 4; 010; The U.S.: Amberlite IR-120; Dowex-50, Germany: Lewatit-100, Japan: Diaion SK-1, France: AllassionCS; Duolite C-20, Russia: ky-3; SDB-3 reduces to individual event impurity metal ion content below the 10ppb.
The big I of particulate is controlled through filtering in high-purity ydrogen peroxide 50 and the high-purity Glacial acetic acid min. 99.5, generally after purification step is accomplished, the filter element filtering through 0.1 μ m is got final product, and preferably take the circulating filtration method.
Preparation in accordance with the present invention; The clean step of said reaction kettle and pail pack is following: at first clean with the zero(ppm) water of specific conductivity greater than 18.2M; High-purity peracetic acid soln of the said 35wt～40wt% of can then, room temperature (for example 25 ℃) storage 24～36 hours drains peracetic acid soln; Clean with the zero(ppm) water of specific conductivity again greater than 18.2M, subsequent use.Clean generally carries out getting final product for 1～2 time.Reaction kettle and pail pack are carried out clean can be reduced to the leachable impurity of reaction kettle and pail pack below the 5ppb.
The high-purity peracetic acid soln that is used to clean used in the present invention can be first batch of peracetic acid soln producing according to the inventive method.
The further embodiment of method produced according to the present invention: said method comprises that also the Peracetic Acid waste liquid that utilizes clean to produce prepares the step of ultrapure peracetic acid soln; Detailed process is: with Peracetic Acid waste liquid that clean produced under 40 ℃～50 ℃ of temperature; Rectification under vacuum under pressure 0.05～0.15atm; It is 2wt%～40wt% that the rectifying cut is diluted to Peracetic Acid concentration, is ultrapure peracetic acid soln.Do not contain ydrogen peroxide 50 and acetate in this ultrapure peracetic acid soln.
Preferably, rectifying tower that rectification under vacuum is used and pipeline etc. were also handled according to the aforesaid reaction vessel clean method identical with pail pack before use.So, can obtain individual event impurity metal ion content≤5ppb, the ultrapure peracetic acid soln of individual event anionic impurity content≤1ppm and organic impurities content≤5ppm.
Content through Peracetic Acid in the raffinate of above-mentioned rectification under vacuum is generally 3%～8%, in addition, also contains the Glacial acetic acid min. 99.5 and the ydrogen peroxide 50 of trace.This part raffinate can be replenished Glacial acetic acid min. 99.5, ydrogen peroxide 50, stablizer etc. and be made into the sale of low side Peracetic Acid product according to the peracetic acid soln product of test result and the existing low side purposes of reference (for example thimerosal).
The present invention also is particularly related to a kind of ultrapure peracetic acid soln; In weight content, this ultrapure peracetic acid soln is by Peracetic Acid 2%～40%, individual event impurity metal ion content≤5ppb; Individual event anionic impurity content≤1ppm, organic impurities content≤5ppm and surplus are that water is formed.This ultrapure peracetic acid soln provides the more high-end purposes of peracetic acid soln that does not contain additive than of the present invention, has further opened up the Application Areas of Peracetic Acid.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
Add additive such as stablizer to improve the thinking of peracetic acid soln storage stability different with the tradition utilization; The present invention has realized the excellent stability of peracetic acid soln through the control to impurity ion content in the peracetic acid soln; Thereby avoid the interpolation of any stabilizer element, the one,, the peracetic acid soln product purity is higher; Can be applied to high-end fields such as medical treatment, food, biotechnological formulation, open up the Application Areas of Peracetic Acid; The 2nd, it is applied in the synthetic field of reagent, can reduce side reaction, reduce by product, improve reaction yield; The 3rd, because its not phosphorous fully and part complex compound, inner complex additive make product have more environment friendly.
According to the peracetic acid soln of the preparation method of peracetic acid soln of the present invention preparation, its purity is high, the strict control of foreign matter content, good stability.In addition, take this method, can also when obtaining fluoroacetic acid solution, obtain can be applicable to the more ultrapure peracetic acid soln sub product and conventional low side peracetic acid soln product of high-end field, have no the waste of raw material, reduced production cost.
The inventive method is equally applicable to the production technique of similar superoxide such as peroxyformic acid, Perpropionic Acid, and can expect to obtain the ideal effect.
Embodiment
Below in conjunction with concrete embodiment, the present invention is done further detailed explanation, but the invention is not restricted to following examples.
Embodiment 1
It is the preparation method of high-purity ydrogen peroxide 50 of 70% that present embodiment provides a kind of mass concentration, and it comprises the steps:
(1), the preparation of 70% high-purity EL grade hydrogen peroxide
1., get commercially available common ydrogen peroxide 50 (70wt%); 0～15 ℃ of controlled temperature; Then ydrogen peroxide 50 is passed through absorption with macroporous adsorbent resin post (AB of TianXing, Bengbu resin company series macroporous adsorbent resin); Control flow velocity 500L/H in the plastic resin treatment life-span (＜2000 times of resin volumes), is reduced to organic impurities content in the ydrogen peroxide 50 below the 20ppm.
2., will pass through step ydrogen peroxide 50 1. through cationic exchange coloum (styrene type cation exchange resin, trade mark China 732), control flow velocity 500L/H.Impurity metal ion content in the ydrogen peroxide 50 is reduced to below the 100ppb.
3., will pass through step ydrogen peroxide 50 2. through anion-exchange column (the polystyrene weak basic ion exchange resin of macroporous structure, D351) control flow velocity 500L/H.Anionic impurity content in the ydrogen peroxide 50 is reduced to below the 800ppb.
(2), the preparation of 70% high-purity UP grade hydrogen peroxide:
1., the EL grade hydrogen peroxide with step (1) preparation passes through cationic exchange coloum, control flow velocity 400L/H.Impurity metal ion content in the ydrogen peroxide 50 is reduced to below the 8ppb.
2., will pass through step ydrogen peroxide 50 1. and pass through anion-exchange column.Control flow velocity 400L/H.Anionic impurity content in the ydrogen peroxide 50 is reduced to below the 100ppb.
(3), the preparation of 70% high-purity UPS grade hydrogen peroxide:
1., (material is a tetrafluoroethylene to the UP grade hydrogen peroxide that step (2) is prepared, aperture 1～5 nanometer, porosity 70～80%, 100～150 microns of thickness, applying pressure 1～1.5Mpa), control flow velocity 300L/H through the customization nf membrane.Organic content in the ydrogen peroxide 50 is reduced to below the 5ppm.
2., will pass through step ydrogen peroxide 50 1. through cationic exchange coloum, control flow velocity 300L/H is reduced to impurity metal ion content in the ydrogen peroxide 50 below the 0.8ppb.
3., will pass through step ydrogen peroxide 50 2. and pass through anion-exchange column.Control flow velocity 300L/H.Anionic impurity content in the ydrogen peroxide 50 is reduced to below the 50ppb.
(4), the preparation of 70% high-purity UPSS grade hydrogen peroxide:
1., with the UPS grade hydrogen peroxide of step (3) preparation through cationic exchange coloum, control flow velocity 200L/H is reduced to impurity metal ion content in the ydrogen peroxide 50 below the 50ppt.
2., will pass through step ydrogen peroxide 50 1. through anion-exchange column, control flow velocity 200L/H is reduced to anionic impurity content in the ydrogen peroxide 50 below the 30ppb.
(5), with the filter core circulating filtration of finished product with 0.1 micron, promptly get high-purity ydrogen peroxide 50.High-purity ydrogen peroxide 50 to prepared has carried out composition detection, and the result is referring to table 1.
Table 1
Embodiment 2
Present embodiment provides the preparation method of high-purity Glacial acetic acid min. 99.5 of a kind of mass concentration＞99.9%, and is specific as follows:
(1) (3A-EPG, 3A-PPG, particle diameter 3～5mm) are reduced to moisture content in the Glacial acetic acid min. 99.5 below the 0.01wt% through molecular sieve with Glacial acetic acid min. 99.5;
(2) according to the Incoming Quality Control situation, add potassium permanganate in mass ratio 0.1%～0.01% ratio, the preparation distillating material, the amount of reducing substance such as formic acid, acetaldehyde is reduced to the reduzate quality below 0.03% by 0.3% in the reduction raw material.
(3) Glacial acetic acid min. 99.5 is fed rectifying tower, rectifying, cooling water flow 5 ± 1L/H; Vapor pressure 0.10 ± 0.05Mpa, feed rate 200 ± 50L/H, 117.1 ± 0.1 ℃ of tower top temperatures; Anion concentration is reduced to below the 200ppb, most of metallic impurity ionic concentration is reduced to below the 5ppb.
(4) will impurity metal ion content such as aluminium, calcium, zinc be reduced to below the 5ppb through strong cation-exchanging resin.
(5) with the filter core circulating filtration of finished product, promptly get with 0.1 micron.High-purity Glacial acetic acid min. 99.5 to prepared has carried out composition detection, and the result is referring to table 2.
Table 2
Embodiment 3～7
Present embodiment provides preparation simultaneously not contain the method for the peracetic acid soln and the ultrapure peracetic acid soln of additive, and it comprises the steps:
(1), implements to clean to producing reaction kettle, pail pack and the rectifying tower that to use and pipeline etc.; With the pail pack is example; Cleaning process is following: purify in the room,, and drain greater than the distilled water immersion pail pack 12h of 18.2M, use 0.4Mpa pressure distilled water flushing then with specific conductivity; Then with pail pack can 35% high-purity peracetic acid soln, and 25 ℃ of storages after 24 hours drain Peracetic Acid; And clean greater than 18.2M zero(ppm) water with specific conductivity; Purified compressed air dries up subsequent use, detects cleaning zero(ppm) water, and wherein all contaminations content is lower than 5ppb.Be stored in the pail pack after the cleaning with 35% peracetic acid soln, 25 ℃ of storages 30 days, all contaminations stripping quantity is lower than 5ppb.
(2), successively high-purity ydrogen peroxide 50 of 70% concentration of embodiment 1 preparation and high-purity Glacial acetic acid min. 99.5 of embodiment 2 preparations are squeezed in the reaction kettle according to the ratio of table 3; With mixed solution at 45 ℃ of following circulating reaction 36h; 0.1 micron filter filter core circulating filtration through routine; Use the pail pack can, promptly get the peracetic acid soln product that does not contain additive.This product is through detecting individual event impurity metal ion content≤5ppb wherein, individual event anionic impurity content≤1ppm, organic impurities content≤5ppm.Stability to product is tested, and the content of Peracetic Acid and hydrogen peroxide is listed in the table 3 over time.
(3), feed rectification under vacuum tower, rectifying, cooling water flow 5 ± 1L/h with cleaning the Peracetic Acid waste liquid that is produced in the step (1); Vapor pressure 0.01～0.05Mpa, feed rate 200 ± 50L/h, 45～50 ℃ of tower top temperatures; 0～5 ℃ of condensing surface and product temperature; The concentration that obtains Peracetic Acid rectifying liquid is about 45～50%, and it is 35% that this rectifying liquid is used ultrapure water dilution, does ultrapure peracetic acid soln product and sells.Through detecting, do not contain ydrogen peroxide 50 and acetate in this product, the impurity ion content that contains also is lower than the peracetic acid soln of step (2) preparation.
(4), in the distillation residual liquid after step (3) rectifying, Peracetic Acid content is about 3%～8%, contains Glacial acetic acid min. 99.5, the ydrogen peroxide 50 of trace in addition.Account for total feed 30～50%,, replenish Glacial acetic acid min. 99.5, ydrogen peroxide 50, stablizer, do normal conventional Peracetic Acid product and sell according to test result.
Table 3
More than the present invention has been done detailed description; Its purpose is to let the personage that is familiar with this art can understand content of the present invention and implements; Can not limit protection scope of the present invention with this; All equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1. peracetic acid soln that does not contain additive; It is characterized in that: in weight content; Said peracetic acid soln is by Peracetic Acid 2%～40%, hydrogen peroxide 10%～35%, individual event impurity metal ion content≤5ppb, individual event anionic impurity content≤1ppm; Organic impurities content≤5ppm and surplus are that water is formed, and the particulate concentration of particle diameter in the said peracetic acid soln>=0.2 μ m is smaller or equal to 100/ml.
2. described preparation method who does not contain the peracetic acid soln of additive of claim 1; It is characterized in that: this method make concentration be high-purity Glacial acetic acid min. 99.5 of high-purity ydrogen peroxide 50 and concentration >=99.9wt% of 30wt% ~ 70wt% in reaction kettle, 40 ℃～50 ℃ following insulated and stirred of temperature 20～40 hours; Filter then; Can obtains described peracetic acid soln, wherein:
Individual event impurity metal ion content≤1ppb in described high-purity ydrogen peroxide 50, unidirectional anionic impurity content≤1ppm, organic impurities content≤5ppm, the particulate concentration of particle diameter>=0.2 μ m is smaller or equal to 100/ml;
Reducing substance content≤0.03wt% in described high-purity Glacial acetic acid min. 99.5, individual event metallic impurity ion content＜10ppb, organic impurities content≤5ppm, the particulate concentration of particle diameter>=0.2 μ m is smaller or equal to 100/ml;
Before using said reaction kettle and being used for the pail pack of can; Adopting concentration is that high-purity peracetic acid soln and the specific conductivity of 35wt ~ 40wt% carried out clean greater than the zero(ppm) water of 18.2M to reaction kettle and pail pack; The said high-purity peracetic acid soln individual event impurity metal ion content≤5ppb that is used for clean; Individual event anionic impurity content≤1ppm, organic impurities content≤5ppm.
3. the preparation method who does not contain the peracetic acid soln of additive according to claim 2 is characterized in that: the concentration of said high-purity ydrogen peroxide 50 is 40wt% ~ 50wt%.
4. the preparation method who does not contain the peracetic acid soln of additive according to claim 2 is characterized in that: individual event impurity metal ion content≤50ppt in described high-purity ydrogen peroxide 50.
5. according to claim 2 or the 4 described preparing methods that do not contain the peracetic acid soln of additive; It is characterized in that: said high-purity ydrogen peroxide 50 is purified by common ydrogen peroxide 50 and is obtained; Method of purification is: under 0 ℃ ~ 15 ℃ of temperature; Take nf membrane filtration or nf membrane filtration to combine and remove organism, take Zeo-karb to remove the metallic impurity ion, take anionite-exchange resin to remove anionic impurity with absorption with macroporous adsorbent resin.
6. the preparation method who does not contain the peracetic acid soln of additive according to claim 5 is characterized in that: the purification of said ydrogen peroxide 50 is carried out under 0 ℃ ~ 5 ℃ of temperature.
7. the preparation method who does not contain the peracetic acid soln of additive according to claim 2; It is characterized in that: said high-purity Glacial acetic acid min. 99.5 is purified by common ice acetic acid and is obtained; Method of purification is: remove reduzate wherein through adding the potassium permanganate oxidation, combine through rectifying and ion exchange resin and remove impurity metal ion.
8. the preparation method who does not contain the peracetic acid soln of additive according to claim 2; It is characterized in that: the clean step of said reaction kettle and pail pack is following: at first clean with the zero(ppm) water of specific conductivity greater than 18.2M; High-purity peracetic acid soln of the said 35wt ~ 40wt% of can then, storage at room temperature 24 ~ 36 hours drains peracetic acid soln; Clean with the zero(ppm) water of specific conductivity again greater than 18.2M, subsequent use.
9. according to claim 2 or the 8 described preparing methods that do not contain the peracetic acid soln of additive; It is characterized in that: said method comprises that also the Peracetic Acid waste liquid that utilizes clean to produce prepares the step of ultrapure peracetic acid soln; Its detailed process for Peracetic Acid waste liquid that clean produced under 40 ℃ ~ 50 ℃ of temperature; Rectification under vacuum under pressure 0.05 ~ 0.15atm, it is 2wt% ~ 40wt% that the rectifying cut is diluted to Peracetic Acid concentration, promptly gets ultrapure peracetic acid soln.
10. ultrapure peracetic acid soln; It is characterized in that: in weight content, said ultrapure peracetic acid soln is by Peracetic Acid 2%～40%, individual event impurity metal ion content≤5ppb; Individual event anionic impurity content≤1ppm, organic impurities content≤5ppm and surplus are that water is formed.
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| 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 |
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