CN102659655B - 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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- CN102659655B CN102659655B CN201210132144.3A CN201210132144A CN102659655B CN 102659655 B CN102659655 B CN 102659655B CN 201210132144 A CN201210132144 A CN 201210132144A CN 102659655 B CN102659655 B CN 102659655B
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- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000654 additive Substances 0.000 title claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 122
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000012535 impurity Substances 0.000 claims abstract description 56
- 229960000583 acetic acid Drugs 0.000 claims abstract description 29
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 25
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 18
- 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 15
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001728 nano-filtration Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 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
- 239000012528 membrane Substances 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000003809 water extraction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 17
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 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
- 239000000243 solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 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
- 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
- 238000012360 testing method Methods 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
- 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
- 239000000126 substance Substances 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
- 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
- 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 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 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
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- -1 poly(vinylidene fluoride) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003908 quality control 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
- 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
- 238000004061 bleaching Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion 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
- 239000003344 environmental pollutant 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant 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
- 238000012545 processing Methods 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 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
- 239000013589 supplement 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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, easily decompose, and under the conditions such as alkalescence, reducing substances and metal 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, the multiple germ such as kill bacteria, gemma fungi, yeast fast, thereby can be used as the sterilizing agent of transmissible disease, tap water, food etc.At SARS epidemic period, during 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.Meanwhile, 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, industrial goods Peracetic Acid requires the mass concentration > 15% of Peracetic Acid.But meet at present the industry product Peracetic Acid of this concentration requirement in storage and use procedure, the situation that decomposition of peracetic acid even explodes very easily occurs.According to the investigation ，46Jia Peracetic Acid manufacturing enterprise of 2004 such as Wen Dongsheng of Shaanxi health monitoring institutions, the product of 60 batches, qualified 39 batches, qualification rate is only 65%.Different storage times, qualification rate is that 90.9%, 11 day qualification rate is 27.27% in three days, surpasses 20 days, all defective.According to just in July, 2003 investigation of the national Register of chemicals Li Yun of registration center, 1 to 12 May in 2003, there is more than 30 of Peracetic Acid accident in addition, dead 5 people, people more than 70 is poisoning or burn.In November, 2003, the blast of Yunnan Peracetic Acid storage tank, 5 people are dead, and 4 buildings are burnt.Visible, the unstable of Peracetic Acid has caused very adverse influence to economy and the security in its use procedure.Therefore, need to improve its stability and strengthen economy and the security in its storage and use procedure.
Domestic a lot of scholar, as Hao Wenhui, Ma Chunyu, Wang Lihua etc. have also noticed problems, has also carried out trying to explore of related fields, makes some progress.But on the whole, effect is little, do not form extensive high stable property Peracetic Acid Industrialized processing technique in batches.The production of our times main flow is to adopt to add the stability that stablizer improves Peracetic Acid.Yet, use the additives such as phosphorus not only to increase the foreign matter content in Peracetic Acid, make it can not be in sector applications such as biotechnological formulation, food, and the interpolation of the additive such as phosphorus, also can cause corrosion to equipment, reduce equipment life, cause other side reaction, by product, also can make the eutrophication such as water body, to environment simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of not containing additive and the extraordinary peracetic acid soln of stability.
The present invention also will provide a kind of preparation method of peracetic acid soln simultaneously, peracetic acid soln good stability prepared by the method, and purity is high, can be applied to the 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, 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 forms, in described peracetic acid soln, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml.
The another technical scheme that the present invention takes is: a kind of above-mentioned not containing the preparation method of the peracetic acid soln of additive, it makes concentration is high-purity hydrogen peroxide of 30wt%～70wt% and high-purity Glacial acetic acid of concentration >=99.9wt% insulated and stirred 20～40 hours in reactor, at 40 ℃～50 ℃ of temperature, then filter, fillingly obtain described peracetic acid soln, wherein:
Individual event impurity metal ion content≤1ppb in described high-purity hydrogen peroxide, unidirectional anionic impurity content≤1ppm, organic impurities content≤5ppm, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml;
Reducing substance content≤0.03wt% in described high-purity Glacial acetic acid, individual event metallic impurity ion content < 10ppb, organic impurities content≤5ppm, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml;
At the described reactor of use with before for filling pail pack, the distilled water that the high purity peroxyacetic acid solution that employing concentration is 35wt～40wt% and specific conductivity are greater than 18.2M carries out clean to reactor and pail pack, described high purity peroxyacetic acid solution individual event impurity metal ion content≤5ppb for clean, individual event anionic impurity content≤1ppm, organic impurities content≤5ppm.
Preferably, high-purity hydrogen peroxide and high-purity Glacial acetic acid to add the mol ratio that weight ratio meets hydrogen peroxide and Glacial acetic acid be 1～2: 1, more preferably 1～1.5: 1.
Preferably, the concentration of described high-purity hydrogen peroxide is 40wt%～50wt%.Preferably, individual event impurity metal ion content≤50ppt in high-purity hydrogen peroxide.
High-purity hydrogen peroxide can be by the commercially available pure acquisition of common dioxygen water extraction or directly commercially available (concentration be below 40%).According to a concrete aspect, the purification of hydrogen peroxide can be taked following method: at 0 ℃～15 ℃ of temperature, taking nanofiltration membrane filtration or nanofiltration membrane to filter combines and removes organism with absorption with macroporous adsorbent resin, take Zeo-karb to remove metallic impurity ion, take anionite-exchange resin to remove anionic impurity.According to a further embodiment: the purification of hydrogen peroxide comprises the following step of carrying out successively:
1. prepare the hydrogen peroxide of prescribed concentration, be cooled to 0 ℃～15 ℃, with the speed of about 500L/H, pass through macroporous adsorbent resin, to reduce the organic residues such as anthraquinone.The selectable macroporous adsorbent resin trade mark has the HPD of Cangzhou Bao En Chemical Co., Ltd. series macroporous adsorbent resin, the YWD of Cangzhou Yuan Wei Chemical Co., Ltd. series macroporous adsorbent resin, the AB of TianXing, Bengbu resin company series macroporous adsorbent resin etc.
2. use nanofiltration membrane (material is poly(vinylidene fluoride) or tetrafluoroethylene, aperture 1～5 nanometer, porosity 70～80%, 100～150 microns of thickness, working pressure 1～1.5Mpa) to carry out nanofiltration to hydrogen peroxide, further reduce the organism such as anthraquinone in hydrogen peroxide;
3. by hydrogen peroxide with about 500L/H speed by Zeo-karb, styrene type cation exchange resin, optional trade mark China 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. hydrogen peroxide is passed through to 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 can be purified and be obtained by commercially available common ice acetic acid.Can adopt chemical subtraction, molecular sieve, ion-exchange, the compound purifying technique such as rectifying, is reduced to individual event metal concentration in Glacial acetic acid below 10ppb, and purity is greater than 99.9%.A concrete embodiment is as follows:
1. Glacial acetic acid is passed through to molecular sieve (3A type molecular sieve), further reduce the ratio of water in Glacial acetic acid;
2. according to Incoming Quality Control situation, 0.1%～0.01% ratio is added potassium permanganate in mass ratio, and preparation distillation stoste reduces the amount of the reducing substance such as formic acid, acetaldehyde in raw material, and reduzate quality is reduced to below 0.03% by 0.3%;
3. Glacial acetic acid is passed into rectifying tower, rectifying;
4. by Glacial acetic acid by strong cation-exchanging resin, styrene type cation exchange resin, optional trade mark China 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, is down to individual event impurity metal ion content below 10ppb.
In high-purity hydrogen peroxide and high-purity Glacial acetic acid, the large I of particle is controlled by filtering, and generally, after purification step completes, makes the filter element filtering through 0.1 μ m, and preferably takes circulating filtration method.
Preparation in accordance with the present invention, the clean step of described reactor and pail pack is as follows: first by specific conductivity, be greater than the distilled water cleaning of 18.2M, then the high purity peroxyacetic acid solution of filling described 35wt～40wt%, room temperature (for example 25 ℃) is stored 24～36 hours, drain peracetic acid soln, by specific conductivity, be greater than again the distilled water cleaning of 18.2M, standby.Clean is generally carried out 1～2 time.Reactor and pail pack are carried out to clean can be reduced to the leachable impurity of reactor and pail pack below 5ppb.
Used in the present invention can be first batch of peracetic acid soln producing according to the inventive method for the high purity peroxyacetic acid solution cleaning.
The further embodiment of method produced according to the present invention: described method also comprises the step of utilizing Peracetic Acid waste liquid that clean produces to prepare ultrapure peracetic acid soln, detailed process is: the Peracetic Acid waste liquid that clean is produced is at 40 ℃～50 ℃ of temperature, rectification under vacuum under pressure 0.05～0.15atm, it is 2wt%～40wt% that rectifying cut is diluted to Peracetic Acid concentration, is ultrapure peracetic acid soln.In this ultrapure peracetic acid soln, do not contain hydrogen peroxide and acetic acid.
Preferably, the rectifying tower that rectification under vacuum is used and pipeline etc. before use, were also processed according to the aforesaid reaction vessel clean method identical with pail pack.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 micro-Glacial acetic acid and hydrogen peroxide.This part raffinate can for example,, according to the peracetic acid soln product of test result and the existing low side purposes of reference (thimerosal), be supplemented Glacial acetic acid, hydrogen peroxide, stablizer etc. and be made into the sale of low side Peracetic Acid product to.
The present invention is also 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 forms.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.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Add the additives such as stablizer to improve the thinking of peracetic acid soln storage stability different from tradition utilization, the present invention is by having realized the stability of peracetic acid soln excellence to the control of impurity ion content in peracetic acid soln, thereby avoid the interpolation of any stabilizer element, the one,, peracetic acid soln product purity is higher, can be applied to the high-end fields such as medical treatment, food, biotechnological formulation, open up the Application Areas of Peracetic Acid; The 2nd, be applied in the synthetic field of reagent, can reduce side reaction, reduce by product, improve reaction yield; The 3rd,, because it is completely not phosphorous and part complex compound, inner complex additive, make product have more environment friendly.
The peracetic acid soln of preparing according to the preparation method of peracetic acid soln of the present invention, its purity is high, and foreign matter content is strictly controlled, good stability.In addition, take the method, can also be when obtaining fluoroacetic acid solution, obtain and can be applicable to the more ultrapure peracetic acid soln byproduct of high-end field and conventional low side peracetic acid soln product, the waste without any raw material, has reduced production cost.
The inventive method is equally applicable to the production technique of the similar superoxide such as peroxyformic acid, Perpropionic Acid, and can expect to obtain desirable effect.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the invention is not restricted to following examples.
Embodiment 1
It is the preparation method of high-purity hydrogen peroxide of 70% that the 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 hydrogen peroxide (70wt%), control 0～15 ℃ of temperature, then hydrogen peroxide is passed through to absorption with macroporous adsorbent resin post (AB of TianXing, Bengbu resin company series macroporous adsorbent resin), coutroi velocity 500L/H, in the plastic resin treatment life-span (2000 times of resin volumes of <), organic impurities content in hydrogen peroxide is reduced to below 20ppm.
2., will pass through cationic exchange coloum (styrene type cation exchange resin, trade mark China 732), coutroi velocity 500L/H through step hydrogen peroxide 1..Impurity metal ion content in hydrogen peroxide is reduced to below 100ppb.
3., will pass through anion-exchange column (the polystyrene weak basic ion exchange resin of macroporous structure, D351) coutroi velocity 500L/H through step hydrogen peroxide 2..Anionic impurity content in hydrogen peroxide is reduced to below 800ppb.
(2), the preparation of 70% high-purity UP grade hydrogen peroxide:
1. the EL grade hydrogen peroxide of, being prepared by step (1) is by cationic exchange coloum, coutroi velocity 400L/H.Impurity metal ion content in hydrogen peroxide is reduced to below 8ppb.
2., will pass through anion-exchange column through step hydrogen peroxide 1..Coutroi velocity 400L/H.Anionic impurity content in hydrogen peroxide is reduced to below 100ppb.
(3), the preparation of 70% high-purity UPS grade hydrogen peroxide:
1. the UP grade hydrogen peroxide of, being prepared by step (2) is by customization nanofiltration membrane (material is tetrafluoroethylene, aperture 1～5 nanometer, porosity 70～80%, 100～150 microns of thickness, working pressure 1～1.5Mpa), coutroi velocity 300L/H.Organic content in hydrogen peroxide is reduced to below 5ppm.
2., will be through hydrogen peroxide 1. of step by cationic exchange coloum, coutroi velocity 300L/H, is reduced to impurity metal ion content in hydrogen peroxide below 0.8ppb.
3., will pass through anion-exchange column through step hydrogen peroxide 2..Coutroi velocity 300L/H.Anionic impurity content in hydrogen peroxide is reduced to below 50ppb.
(4), the preparation of 70% high-purity UPSS grade hydrogen peroxide:
1., UPS grade hydrogen peroxide prepared by step (3) is by cationic exchange coloum, coutroi velocity 200L/H, is reduced to impurity metal ion content in hydrogen peroxide below 50ppt.
2., will be through hydrogen peroxide 1. of step by anion-exchange column, coutroi velocity 200L/H, is reduced to anionic impurity content in hydrogen peroxide below 30ppb.
(5) the filter core circulating filtration, by finished product with 0.1 micron, obtains high-purity hydrogen peroxide.Prepared high-purity hydrogen peroxide has been carried out to composition detection, and result is referring to table 1.
Table 1
Embodiment 2
The present embodiment provides the preparation method of high-purity Glacial acetic acid of a kind of mass concentration > 99.9%, specific as follows:
(1) Glacial acetic acid is passed through to molecular sieve (3A-EPG, 3A-PPG, particle diameter 3～5mm), moisture content in Glacial acetic acid is reduced to below 0.01wt%;
(2) according to Incoming Quality Control situation, 0.1%～0.01% ratio is added potassium permanganate in mass ratio, and preparation distillating material reduces the amount of the reducing substance such as formic acid, acetaldehyde in raw material, and reduzate quality is reduced to below 0.03% by 0.3%.
(3) Glacial acetic acid is passed into 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, are reduced to anion concentration below 200ppb, and the concentration of most of metallic impurity ion is reduced to below 5ppb.
(4) will, by strong cation-exchanging resin, the impurity metal ion content such as aluminium, calcium, zinc be reduced to below 5ppb.
(5) the filter core circulating filtration with 0.1 micron by finished product, obtains.Prepared high-purity Glacial acetic acid has been carried out to composition detection, and result is referring to table 2.
Table 2
Embodiment 3～7
The present embodiment provides preparation simultaneously not contain the peracetic acid soln of additive and the method for ultrapure peracetic acid soln, and it comprises the steps:
(1) reactor, pail pack and the rectifying tower that, will use production and pipeline etc. are implemented to clean, take pail pack as example, cleaning process is as follows: purify in room, be greater than the distilled water immersion pail pack 12h of 18.2M, then use 0.4Mpa pressure distilled water flushing, and drain by specific conductivity; Then by the filling 35% high purity peroxyacetic acid solution of pail pack, and 25 ℃ of storages are after 24 hours, and Peracetic Acid is drained, and be greater than the cleaning of 18.2M distilled water by specific conductivity, purified compressed air dries up standby, to cleaning distilled water, detects, and wherein various pollutant loads are lower than 5ppb.With 35% peracetic acid soln, be stored in the pail pack after cleaning, store 30 days for 25 ℃, various Leaching rule amounts are lower than 5ppb.
(2), successively high-purity Glacial acetic acid of high-purity hydrogen peroxide of 70% concentration of embodiment 1 preparation and embodiment 2 preparations is squeezed in reactor according to the ratio of table 3, by mixed solution circulating reaction 36h at 45 ℃, by 0.1 micron filter filter core circulating filtration of routine, filling with pail pack, obtain the peracetic acid soln product that does not contain additive.This product after testing, 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 table 3 over time.
(3), by cleaning the Peracetic Acid waste liquid producing in step (1), pass into rectification under vacuum tower, rectifying, cooling water flow 5 ± 1L/h, vapor pressure 0.01～0.05Mpa, feed rate 200 ± 50L/h, 45～50 ℃ of tower top temperatures, 0～5 ℃ of condenser and product temperature, the concentration that obtains Peracetic Acid rectifying liquid is approximately 45～50%, by this rectifying liquid, with ultrapure water dilution, is 35%, does ultrapure peracetic acid soln product and sells.After testing, in this product, do not contain hydrogen peroxide and acetic acid, the peracetic acid soln that the impurity ion content containing is also prepared lower than step (2).
(4) in the distillation residual liquid, after step (3) rectifying, Peracetic Acid content is approximately 3%～8%, in addition containing micro-Glacial acetic acid, hydrogen peroxide.Account for total feed 30～50%, according to test result, supplement Glacial acetic acid, hydrogen peroxide, stablizer, do normal conventional Peracetic Acid product and sell.
Table 3
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (8)
1. one kind containing the preparation method of the peracetic acid soln of additive, it is characterized in that: in weight content, described 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 forms, in described peracetic acid soln, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml, it is that high-purity hydrogen peroxide of 30wt% ~ 70wt% and high-purity Glacial acetic acid of concentration >=99.9wt% are in reactor that the method makes concentration, at 40 ℃～50 ℃ of temperature, insulated and stirred is 20～40 hours, then filter, peracetic acid soln described in filling obtaining, wherein:
Individual event impurity metal ion content≤1ppb in described high-purity hydrogen peroxide, unidirectional anionic impurity content≤1ppm, organic impurities content≤5ppm, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml;
Reducing substance content≤0.03wt% in described high-purity Glacial acetic acid, individual event metallic impurity ion content < 10ppb, organic impurities content≤5ppm, the concentration of the particle of particle diameter >=0.2 μ m is less than or equal to 100/ml;
At the described reactor of use with before for filling pail pack, the distilled water that the high purity peroxyacetic acid solution that employing concentration is 35wt ~ 40wt% and specific conductivity are greater than 18.2M carries out clean to reactor and pail pack, described high purity peroxyacetic acid solution individual event impurity metal ion content≤5ppb for clean, individual event anionic impurity content≤1ppm, organic impurities content≤5ppm.
2. the preparation method who does not contain the peracetic acid soln of additive according to claim 1, is characterized in that: the concentration of described high-purity hydrogen peroxide is 40wt% ~ 50wt%.
3. the preparation method who does not contain the peracetic acid soln of additive according to claim 1, is characterized in that: individual event impurity metal ion content≤50ppt in described high-purity hydrogen peroxide.
According to described in claim 1 or 3 not containing the preparation method of the peracetic acid soln of additive, it is characterized in that: described high-purity hydrogen peroxide is by pure the obtaining of common dioxygen water extraction, method of purification is: at 0 ℃ ~ 15 ℃ of temperature, taking nanofiltration membrane filtration or nanofiltration membrane to filter combines and removes organism with absorption with macroporous adsorbent resin, take Zeo-karb to remove metallic impurity ion, take anionite-exchange resin to remove anionic impurity.
5. according to claim 4 not containing the preparation method of the peracetic acid soln of additive, it is characterized in that: the purification of described hydrogen peroxide is carried out at 0 ℃ ~ 5 ℃ of temperature.
6. according to claim 1 not containing the preparation method of the peracetic acid soln of additive, it is characterized in that: described high-purity Glacial acetic acid is purified and obtained by common ice acetic acid, method of purification is: by adding potassium permanganate oxidation, remove reduzate wherein, by rectifying and Ion Exchange Resin Phase combination, remove impurity metal ion.
7. according to claim 1 not containing the preparation method of the peracetic acid soln of additive, it is characterized in that: the clean step of described reactor and pail pack is as follows: first by specific conductivity, be greater than the distilled water cleaning of 18.2M, then the high purity peroxyacetic acid solution of filling described 35wt ~ 40wt%, storage at room temperature 24 ~ 36 hours, drain peracetic acid soln, by specific conductivity, be greater than again the distilled water cleaning of 18.2M, standby.
According to described in claim 1 or 7 not containing the preparation method of the peracetic acid soln of additive, it is characterized in that: described method also comprises the step of utilizing Peracetic Acid waste liquid that clean produces to prepare ultrapure peracetic acid soln, its detailed process is for Peracetic Acid waste liquid that clean is produced is at 40 ℃ ~ 50 ℃ of temperature, rectification under vacuum under pressure 0.05 ~ 0.15atm, it is 2wt% ~ 40wt% that rectifying cut is diluted to Peracetic Acid concentration, obtains ultrapure peracetic acid soln.
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