CN101268045B - 过氧酸的制备方法 - Google Patents
过氧酸的制备方法 Download PDFInfo
- Publication number
- CN101268045B CN101268045B CN2006800335742A CN200680033574A CN101268045B CN 101268045 B CN101268045 B CN 101268045B CN 2006800335742 A CN2006800335742 A CN 2006800335742A CN 200680033574 A CN200680033574 A CN 200680033574A CN 101268045 B CN101268045 B CN 101268045B
- Authority
- CN
- China
- Prior art keywords
- acid
- solution
- peroxy
- carboxylic acid
- carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000004965 peroxy acids Chemical class 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 100
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 88
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 235000019253 formic acid Nutrition 0.000 claims abstract description 50
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 42
- 244000005700 microbiome Species 0.000 claims abstract description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 94
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 150000002978 peroxides Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000000813 microbial effect Effects 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000004659 sterilization and disinfection Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- 239000003206 sterilizing agent Substances 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000001954 sterilising effect Effects 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- -1 peroxy maleic acid Chemical compound 0.000 claims description 4
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 4
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 4
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 3
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000645 desinfectant Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000123 paper Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000249 desinfective effect Effects 0.000 description 4
- 230000003641 microbiacidal effect Effects 0.000 description 4
- 229940124561 microbicide Drugs 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 235000013365 dairy product Nutrition 0.000 description 3
- 239000002855 microbicide agent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000050 nutritive effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000004076 pulp bleaching Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 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 description 1
- CNJLMVZFWLNOEP-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[4.1.0]heptan-5-one Chemical compound O=C1C(C)CCC2C(C)(C)C12 CNJLMVZFWLNOEP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000959949 Deinococcus geothermalis Species 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 241000508289 Meiothermus silvanus Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000748282 Pseudoxanthomonas taiwanensis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 231100000817 safety factor Toxicity 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/26—Peracetic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/30—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids a >C=O group being bound to a carbon atom of a six-membered aromatic ring
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
- D21H21/04—Slime-control agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Inorganic Chemistry (AREA)
Abstract
本发明涉及包括含过甲酸的第一过氧酸和第二过氧酸的溶液的制备方法,所述方法包括形成包括含甲酸、第二羧酸和过氧化氢的第一羧酸的羧酸溶液,其中甲酸的用量为第二羧酸用量的0.5-20wt%,并允许各组分反应,形成含过甲酸和所述第二过氧酸的溶液,其中过氧酸的用量为至少5wt%。本发明还涉及含过甲酸和所述第二过氧酸的可储存溶液。该溶液可用作控制微生物的消毒剂。
Description
发明领域
本发明涉及含有过甲酸的相对浓的可储存过氧酸溶液的制备方法。本发明还涉及相对浓的可储存过氧酸溶液和这种溶液的用途。
发明背景
过氧化氢被称为具有某种抑菌性能的中等有效的消毒剂。它应用于污水等的消毒剂。使用过氧化氢与金属离子的反应性(Fenton反应)是过氧化氢在消毒中最有效的用途。UV辐照是在消毒中活化过氧化氢的另一可采用的方式。Fenton反应和UV辐射二者产生反应介质用羟基自由基。然而,过氧化氢的消毒能力对于微生物来说是不足的。
对于常见细菌来说,过乙酸(PAA)被称为提供细菌生长快速下降的有效消毒剂。它应用于日用工业的设备消毒。而且,PAA用于纸浆和纸工业以控制工艺过程水内微生物的生长。另外,在脱木质素和过氧化物漂白步骤之后,过酸应用于牛皮纸浆的后漂白。
常规地借助过酸和过氧化氢之间的平衡反应(该反应导致平衡溶液),制备过酸:
乙酸+过氧化氢<----->过乙酸+水
仅仅当通过强无机酸,例如硫酸催化时才发生这一反应。
过酸的平衡溶液例如在工艺过程水的应用、温室、日用工业等中用作消毒剂。
采用甲酸和过氧化氢时发生类似的平衡反应,从而导致含有过甲酸(PFA)的溶液。证明PFA溶液是比过酸溶液更加有效的消毒剂。由于PFA的不稳定性和高反应性,因此PFA溶液不稳定。因此,必须就地制备PFA溶液。对于在温室、工业和机构(I&I)清洁与控制微生物生长的应用中,在工艺过程水中,例如在纸浆和纸(P&P)工业中,应当期望与PFA相当的稳定消毒剂。
在WO94/20424中,过甲酸成功地在horticulture中应用于控制微生物生长。供应到营养液或废水内的过甲酸的稀溶液防止在到达植物的管道内海藻生长,从而防止它们堵塞。申请人深入研究表明PAA的平衡混合物不可应用于这种应用中,这是因为它们对微生物的反应性较低。此外,证明在不存在过氧化氢的情况下,甲酸的消毒能力与过氧酸相比,可以忽略不计。
已知过氧酸的稳定性随着分子量增加而增加。另一方面,过氧酸的消毒能力连同反应性一起随着分子量的下降而增加。在过氧酸当中,过甲酸(PFA)被称为最强力的消毒剂。数种研究表明在微生物生长中过甲酸的影响。早期的参考文献之一是J.Hyg.Epidem.Microbiol.Immunol.(1968)12,115。
WO94/20424公开了通过使摩尔比为1∶10到10∶1,优选1∶1到1∶5的甲酸与过氧化氢反应,制备过甲酸溶液。可使用PFA溶液防止有害微生物并与之战斗。典型地使用用量为1-1000ppm的PFA。
EP231632A公开了过甲酸作为卫生洗涤剂的工业用途。通过由含有10-50wt%过氧化氢的水溶液和含有5-100wt%甲酸的溶液为原料,并在催化剂存在下使之反应,就地制备过甲酸溶液,其中过氧化氢与甲酸的重量比范围为1∶6到1∶1.5。
对于温室消毒目的来说,通过混合例如35%的过氧化氢与15%的甲酸溶液,制备PFA溶液。然后用营养液稀释所得溶液并供应到植物上。由于下述事实:过甲酸溶液在较高的浓度下爆炸,因此可安全地处理仅仅低浓度的过甲酸溶液。根据最近的专利文献,过甲酸和过乙酸的稀溶液的混合物是已知的。
US6211237B1公开了包括小量的过甲酸和过乙酸的稀释的消毒剂,这些过酸的总量典型地小于4wt%。该试剂的主要组分是过氧化氢,其用量典型地为约50wt%。该试剂可例如用于游泳池水的消毒。就地制备PFA和PAA与过氧化氢的稀溶液。本领域的技术人员还已知过氧酸溶液,甚至过甲酸的平衡溶液,在低浓度下,最多2wt%下相对稳定数天。
US2004/0035537公开了用含有过乙酸和过甲酸的溶液漂白纸浆的方法。同样在该申请中,通过使乙酸和甲酸与过氧化氢在大于50wt%的浓度下接触,从而就地制备过乙酸的稀溶液。乙酸+过乙酸与甲酸+过甲酸之比以体积计优选为9-1。在所得溶液内过酸的用量非常低,典型地小于2wt%。
US6284793B1公开了处理镇重海水(ballast sea water)的杀微生物剂。该杀微生物剂为含过乙酸、过甲酸、乙酸、甲酸、过氧化氢和水以及任选地无机酸催化剂和活性氧稳定剂的溶液形式。可通过添加甲酸到典型地含有1-15wt%过乙酸的过乙酸的平衡溶液中,从而获得这一溶液。根据这一文献,与过乙酸相比,过甲酸更加有效,而且对分解更加敏感,因此仅仅就在使用之前,将甲酸加入到含有过乙酸的溶液中。当结合使用过乙酸和甲酸的平衡溶液时,将甲酸直接加入到过乙酸中或者同时加入到镇重水中,其中基于过乙酸和乙酸之和,甲酸的使用量为10-1000wt%。在操作例中,基于过乙酸和乙酸之和,以约800wt%的用量将甲酸加入到平衡过乙酸中。
最常见地借助过氧化氢与合适的羧酸的平衡反应,制备过乙酸。在过乙酸和分子量较高的羧酸的情况下,要求酸催化,以便在合适的时间段内达到平衡。无机酸,例如硫酸、盐酸等在这一反应中常常用作酸催化剂。根据该文献,在甲酸的情况下,不需要额外的酸催化剂(Jones,C.W.,“Applications of hydrogen peroxide andderivatives”,Royal Society of Chemistry;Clean TechnologyMonographs,1999,pp.61-77)。
发明描述
根据本发明,令人惊奇地发现,在通过以范围为0.5∶1到8∶1的摩尔比(mol乙酸/mol过氧化氢)混合乙酸和过氧化氢制备的平衡溶液中,乙酸可被用量为最多20wt%的甲酸替代,且仍提供可储存的溶液。在常见的过氧化物稳定剂存在下,这种过氧酸浓溶液足够稳定地储存数周。根据本发明,发现可在没有损失所得过氧酸溶液的稳定性情况下,引入显著量的甲酸。
因此,在本发明的一个方面中,提供包括第一过氧酸和第二过氧酸的溶液的制备方法,所述第一过氧酸含甲酸,所述方法包括形成包括含甲酸的第一羧酸、第二羧酸和过氧化氢的羧酸溶液,其中甲酸的用量为第二羧酸用量的0.5-20wt%,并让各组分反应,形成含过甲酸和所述第二过氧酸的溶液,其中过氧酸的用量为至少5wt%。
可通过预混第一和第二羧酸,然后添加过氧化氢溶液,从而制备过氧酸溶液。或者,可通过混合第二羧酸,例如乙酸溶液,和过氧化氢溶液,然后添加第一羧酸,即甲酸到平衡混合物中,从而制备过氧酸溶液。在1-2小时内或者在较长的时间段内确立反应平衡,所述时间段主要取决于反应混合物的温度。反应温度可以是在0℃-80℃范围内。优选地,反应温度应当为0℃至50℃。最优选反应温度应当为0℃至25℃,以便获得过氧酸溶液的最好稳定性。
在形成过氧酸溶液中采用的羧酸溶液的浓度可从30%变化到100wt%。一般地,为了达到过氧酸较高的最终浓度,较高的浓度是有利的。
形成过氧酸溶液所使用的过氧化氢溶液的浓度可以介于10%至80wt%。将过氧化氢以过氧化氢水溶液形式引入到溶液内,所述过氧化氢水溶液优选浓度为10%-55%,更优选30%-55wt%。一般地,为了达到较高的过氧酸的最终浓度,较高浓度的过氧化氢是有利的。然而,在制备过氧酸的浓溶液中必须考虑安全因素。例如在“Concentrated Hydrogen Peroxide:Summary of Research Data andSafety Limitations”(Shell Chemical Corp.,Bull.SC 59-44)中公开了涉及制备过氧化氢和有机物质的混合物中安全方面的原理。
反应时间主要取决于所使用的羧酸。Mosovsky等人在CollectCzech.Chem.Commun.Vol.61,1996,pp.1457-1463中和O.D.Shapilov与Ua.L.Kostyukovskii在Kinetika Katalizvol.15,no:4,1974p.1065中公开了形成过甲酸的动力学。形成过甲酸的动力学在文献中也是众所周知的。然而,当采用羧酸的混合物时,形成过氧酸的动力学可能不同。
在所得溶液内过氧酸的用量优选5-20wt%,更优选10-20wt%。
甲酸的用量优选为第二羧酸用量的2-15wt%。
在羧酸溶液内羧酸与过氧化氢的摩尔比范围优选为0.5∶1到8∶1,更优选0.7∶1到2∶1。所述摩尔比范围也可以是2∶1到8∶1。
所得溶液优选为另外含甲酸、第二羧酸和过氧化氢的平衡溶液,
在该平衡溶液内甲酸与过甲酸的用量优选为2-20wt%。
所述第二羧酸优选是脂族C2-C18羧酸,其中包括乙酸、丙酸、苯二甲酸(phtalicacid)、草酸、苹果酸、马来酸和富马酸及其混合物,和所述第二过氧酸优选是脂族C2-C18过氧羧酸,其中包括过乙酸、过丙酸、过氧苯二甲酸、过氧草酸、过氧苹果酸、过氧马来酸和过氧富马酸及其混合物。特别优选乙酸和过乙酸。
可通过添加强酸来催化过氧酸的平衡混合物的形成。强酸可以是有机酸。优选地,低分子量的羧酸可用作反应催化剂。最优选甲酸可用作催化剂。
或者,可通过无机酸催化过氧酸的平衡混合物的形成。可用于催化形成过氧酸的无机酸包括硫酸、磷酸、盐酸、焦磷酸和聚磷酸及其混合物。例如硫酸催化剂的一个优点是它在一定程度上还形成过氧酸(Caron酸)。
酸催化剂的用量可以是溶液重量的0.1-20wt%,更优选溶液重量的1-10%,最优选溶液重量的1-5%。
另外,酸性形式的离子交换树脂可用作所述溶液的催化剂。
另外,常规的添加剂可引入到该溶液内。添加剂包括稳定剂,例如膦酸酯,例如1-羟基亚乙基-1,1-二膦酸(HEDPA)和吡啶羧酸,例如吡啶二羧酸,螯合剂和自由基清除剂。也可使用稳定剂的混合物。稳定剂的用量可以是0.01-1wt%,优选0.05-0.5wt%。
在本发明第二方面中,提供一种可储存的溶液,所述可储存的溶液包括含过甲酸的第一过氧酸、第二过氧酸、含甲酸的第一羧酸、第二羧酸和过氧化氢,其中甲酸和过甲酸的用量为第二羧酸和第二过氧酸总量的0.5-20wt%,和过氧酸为至少5wt%。
在本说明书中,“可储存”是指在室温下储存7天之后,在过氧酸溶液中活性氧(过氧酸+过氧化氢)的下降小于20mol%。这种下降优选小于15mol%,和更优选小于10mol%。
在溶液中过氧酸的用量优选为5-20wt%,更优选10-20wt%。
在溶液内过氧酸和羧酸对过氧化氢的摩尔比范围优选为0.5∶1到8∶1,更优选0.7∶1到2∶1。所述摩尔比也可在2∶1到8∶1范围内。
该溶液优选为平衡溶液。
在溶液内甲酸和过甲酸的用量优选为2-20wt%。
所述第二羧酸和所述第二过氧酸如上所定义。
优选地,该溶液另外包括以上所定义的稳定剂。
本发明还涉及以上所定义的溶液作为消毒剂用于控制微生物的用途。本发明的溶液可例如在工艺过程水应用、温室、日用工业、I& I清洁、P&P工业中用作消毒剂例如控制在造纸机等上的微生物生长。过氧酸溶液也可在纸浆漂白中用作漂白剂,其中它可例如用作残留木质素的后漂白剂。另外,在制备机械纸浆之前,过氧酸溶液是木片的有效浸渍剂。
与纯的过乙酸溶液相比,根据本发明的过甲酸和过乙酸的浓溶液在工艺过程水、温室营养液、污水的消毒等中控制微生物生长方面具有优异的有效性。
此外,这些PFA/PAA溶液可制备并储存数周且没有显著的分解。由于所述溶液的抗微生物的特征相当于过甲酸溶液,因此使用PFA/PAA溶液提供使用过甲酸溶液的安全替代品。
这是显著的优点,因为过甲酸溶液不稳定,因此它们必须在使用之前就地制备。与过甲酸溶液相比的另一优点是,改进的安全因子。在安全性方面,PFA/PAA溶液与纯PAA溶液相当。
本发明的PFA/PAA溶液的良好稳定性是令人惊奇的,因为较高浓度的过甲酸溶液被视为不稳定。
与使用过甲酸相比,这些PAA和PFA的溶液在腐蚀性方面同样提供良好的替代。通过采用与过甲酸抗微生物特征相类似的PAA和PFA的混合物,设备的腐蚀危险显著降低。
如上所述,最多20wt%,优选最多15wt%的过乙酸或另一过氧酸可被过甲酸替代,同时仍提供可储存的溶液。可通过本发明获得下述优点:
第一,显著量的过甲酸制成溶液,这将增加过氧酸溶液的消毒能力。第二,制备并储存适合于温室应用等的过氧酸溶液,而当今PFA溶液必须由甲酸和过氧化氢的溶液来就地制备。第三,所得过氧酸溶液可在纸浆漂白中用作漂白剂,其中它可例如用作残留木质素的后漂白剂。另外,在制备机械纸浆之前,过氧酸混合物是木片的有效浸渍剂。
在本说明书中,百分数是指wt%,除非另有说明。在下述实施例中更加详细地解释本发明。
实施例1
制备0.6%、3.04%、4.99%、10.04%和15.01%的甲酸(FA)在乙酸(AA)内的溶液。以2∶1(AA/H2O2)的摩尔比混合该溶液与50.5%H2O2。作为稳定剂,膦酸酯(HEDPA,500mg/l)和吡啶二羧酸(DPA,300mg/l)加入到每一溶液中。在室温下搅拌所得溶液过夜。在黑暗处在室温下储存该溶液7天,并通过滴定测定过氧酸(此处以过乙酸的形式计算)和过氧化氢的浓度。在储存3天之后,添加0.48%的硫酸,进一步催化该反应。测定每一样品总的活性氧含量(过酸+过氧化物)。在下表1-3中示出了试验结果。稳定性%表示过酸(mol/kg)+H2O2(mol/kg)的分析量与最初添加的H2O2(mol/kg)之比。
表1(1天之后的结果)
在AA内的FA% | H2O2g/kg | H2O2mol/kg | 过酸g/kg | 过酸mol/kg | 活性(O)mol/kg | 稳定性% |
0.603.044.9910.0415.01 | 141.18129.06129.74117.09110.41 | 4.153.803.823.443.25 | 87.34101.29103.64113.88117.73 | 1.121.301.331.461.51 | 5.275.095.144.904.76 | 100.59%97.33%97.61%93.32%90.65% |
表2(储存3天之后的结果)
在AA内的FA% | H2O2g/kg | H2O2mol/kg | 过酸g/kg | 过酸mol/kg | 活性(O)mol/kg | 稳定性% |
0.603.044.9910.0415.01 | 122.27112.31111.3299.3489.29 | 3.603.303.272.922.63 | 123.16135.52131.05137.37136.67 | 1.581.741.681.761.75 | 5.185.044.954.684.38 | 99.36%96.16%94.64%89.46%84.67% |
表3(储存7天之后的结果)
在AA内的FA% | H2O2g/kg | H2O2mol/kg | 过酸g/kg | 过酸mol/kg | 活性(O)mol/kg | 稳定性% |
0.603.044.9910.0415.01 | 68.1868.6667.6664.3362.55 | 2.012.021.991.891.84 | 241.53233.59224.47204.29191.27 | 3.102.992.882.622.45 | 5.105.014.874.514.29 | 98.06%94.89%92.90%86.64%82.01% |
根据表1-3可看出当不同用量的乙酸被甲酸替代时过酸的含量和形成速度。活性氧(过酸+过氧化物)的下降表明当在起始溶液内甲酸含量增加时,总的过氧酸分解。然而,甚至当15%的乙酸被甲酸替代时,在储存7天之后超过80%的活性氧被保留。
实施例2
PFA-PAA混合物对在不锈钢表面上预生长的生物膜的影响
Kemira开发了一种新的试验拟快速有效测试抗生物膜剂。在专利申请WO 2005/045132中公开了该试验。在这一分析中,比较不同产物在失活/除去预生长生物膜方面的相对效率。在造纸机中的真实情况常常是,它不足以防止新的生物膜的形成,但抗生物膜剂应当还在预污染的表面上起作用。在该新的试验中预生长的生物膜短时间地暴露,和之后量化残留生物膜的存活率。
在不锈钢凸出物的表面上生产生物膜。这通过以下来实现:在与来自中性纸板机的澄清滤液混合的造纸工业中真实的主要生物膜形成剂(Deinococcus geothermalis、Pseudoxanthomonas taiwanensis和Meiothermus silvanus)的混合物内浸渍具有凸出物的钢板并在连续摇动下培养(2天,45℃)。
在室温下,将在凸出物上生长的生物膜暴露于不同的抗微生物剂下1.5小时。通过将不锈钢板转移到灭菌的R2肉汤内,并在45℃下培养21小时,从而测量残留生物膜的存活率。所形成的新生物膜表明起始处理过的生物膜的存活率。所测试的抗微生物剂是:PFA-PAA:过甲酸和过乙酸的混合物,它通过混合5.9g甲酸溶液(浓度75wt%)到44.6g乙酸溶液(浓度99wt%)中来制备,并在冷却下,将100g过氧化氢溶液(浓度50wt%)加入到羧酸混合物中。另外添加2.0g稳定剂和7.5g浓硫酸。过氧酸含量为9.3wt%和H2O2含量为28wt%。
ePAA:过乙酸的平衡溶液商品名Kemirox WT,它含有15wt%的纯过乙酸,15wt%的过氧化氢和24wt%的乙酸。
混合物的剂量以过酸之和为基础。所使用的剂量依次分别为0、2、3、4、5、6、7.5、10和15ppm的PAA或PAA与PFA的混合物。作为活性成分处理所有的杀微生物剂,并在去离子水内称重和在自来水内稀释。
试验结果表明PFA-PAA混合物是明显好于ePAA的杀微生物剂。采用3ppm观察到明显的影响和采用5ppm完全失活。当采用普通的ePAA溶液时,没有观察到明显的影响,直到采用10ppm的浓PAA。甚至15ppm浓度的ePAA没有导致微生物完全失活。基于活性PAA含量,PFA-PAA混合物比ePAA有效3-4倍多。作为产品,PFA-PAA在生物膜失活方面是ePAA效率的大约2倍。
Claims (25)
1.制备包括第一过氧酸和第二过氧酸的溶液的方法,所述第一过氧酸含甲酸,所述方法包括形成包括含甲酸的第一羧酸、第二羧酸和过氧化氢的羧酸溶液,其中甲酸的用量为第二羧酸用量的0.5-20wt%,和其中在羧酸溶液内羧酸与过氧化氢的摩尔比范围为0.5∶1到8∶1,并让各组分反应,形成含过甲酸和所述第二过氧酸的溶液,其中过氧酸的含量为至少5wt%。
2.权利要求1的方法,其中在所得溶液内过氧酸的含量为5-20wt%。
3.权利要求1或2的方法,其中在羧酸溶液内羧酸与过氧化氢的摩尔比范围为0.7∶1到2∶1。
4.权利要求1或2的方法,其中所得溶液是另外含甲酸,第二羧酸和过氧化氢的平衡溶液。
5.权利要求4的方法,其中在平衡溶液内甲酸和过甲酸的含量为2-20wt%。
6.权利要求1或2的方法,其中所述第二羧酸是乙酸、丙酸、苯二甲酸、草酸、苹果酸、马来酸或富马酸或这些酸的混合物,和所述第二过氧酸是过乙酸、过丙酸、过氧苯二甲酸、过氧草酸、过氧苹果酸、过氧马来酸或过氧富马酸或这些酸的混合物。
7.权利要求1或2的方法,其中将催化剂引入到该溶液内。
8.权利要求7的方法,其中催化剂包括无机酸。
9.权利要求7的方法,其中催化剂包括硫酸。
10.权利要求7的方法,其中催化剂包括有机酸。
11.权利要求7的方法,其中催化剂包括甲酸。
12.权利要求1或2的方法,其中将稳定剂引入到该溶液内。
13.权利要求10的方法,其中稳定剂包括膦酸酯或吡啶羧酸或其混合物。
14.权利要求12的方法,其中稳定剂包括1-羟基亚乙基-1,1-二膦酸或吡啶二羧酸或其混合物。
15.一种可储存的溶液,它包括含过甲酸的第一过氧酸、第二过氧酸、含甲酸的第一羧酸、第二羧酸和过氧化氢,其中甲酸和过甲酸的含量为第二羧酸和第二过氧酸总量的0.5-20wt%,过氧酸和羧酸与过氧化氢的摩尔比范围为0.5∶1到8∶1,和过氧酸的含量为至少5wt%。
16.权利要求15的溶液,其中在该溶液内过氧酸的含量为5-20wt%。
17.权利要求15或16的溶液,其中过氧酸和羧酸对过氧化氢的摩尔比范围为0.7∶1到2∶1。
18.权利要求15或16的溶液,其中该溶液是平衡溶液。
19.权利要求15或16的溶液,其中在该溶液内甲酸和过甲酸的含量为2-20wt%。
20.权利要求15或16的溶液,其中所述第二羧酸是乙酸、丙酸、苯二甲酸、草酸、苹果酸、马来酸或富马酸或这些酸的混合物,和所述第二过氧酸是过乙酸、过丙酸、过氧苯二甲酸、过氧草酸、过氧苹果酸、过氧马来酸或过氧富马酸或这些酸的混合物。
21.权利要求15或16的溶液,它另外包括稳定剂。
22.权利要求21的溶液,其中稳定剂包括膦酸酯或吡啶羧酸或其混合物。
23.权利要求21的溶液,其中稳定剂包括1-羟基亚乙基-1,1-二膦酸,或吡啶二羧酸或其混合物。
24.权利要求15-23任何一项的溶液作为控制微生物的消毒剂的用途。
25.权利要求24的用途,其用于温室消毒或污水消毒或控制造纸机上的微生物生长。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20050913 | 2005-09-13 | ||
FI20050913A FI118735B (fi) | 2005-09-13 | 2005-09-13 | Menetelmä peroksihappojen valmistamiseksi |
PCT/FI2006/000303 WO2007031596A2 (en) | 2005-09-13 | 2006-09-13 | Process for the preparation of peroxy acids |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101268045A CN101268045A (zh) | 2008-09-17 |
CN101268045B true CN101268045B (zh) | 2011-04-13 |
Family
ID=35151372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006800335742A Active CN101268045B (zh) | 2005-09-13 | 2006-09-13 | 过氧酸的制备方法 |
Country Status (13)
Country | Link |
---|---|
US (1) | US8828910B2 (zh) |
EP (1) | EP1931628B1 (zh) |
JP (1) | JP2009507903A (zh) |
KR (1) | KR101325236B1 (zh) |
CN (1) | CN101268045B (zh) |
AT (1) | ATE489362T1 (zh) |
BR (1) | BRPI0615696A2 (zh) |
CA (1) | CA2627597C (zh) |
DE (1) | DE602006018491D1 (zh) |
ES (1) | ES2359261T3 (zh) |
FI (1) | FI118735B (zh) |
NO (1) | NO340754B1 (zh) |
WO (1) | WO2007031596A2 (zh) |
Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2463181B (en) | 2007-05-14 | 2013-03-27 | Univ New York State Res Found | Induction of a physiological dispersion response in bacterial cells in a biofilm |
US8871807B2 (en) | 2008-03-28 | 2014-10-28 | Ecolab Usa Inc. | Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids |
JP5584194B2 (ja) | 2008-03-28 | 2014-09-03 | エコラボ インコーポレイティド | スルホペルオキシカルボン酸、それらの製造方法並びに漂白剤および殺菌剤としての使用方法。 |
US8809392B2 (en) | 2008-03-28 | 2014-08-19 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US20110311645A1 (en) * | 2010-06-16 | 2011-12-22 | Diaz Raul O | Microbiological control in oil and gas operations |
WO2012037294A2 (en) | 2010-09-14 | 2012-03-22 | Pimi Agro Cleantech Ltd. (Israel) | Compositions and methods of treating edible matter and substrates therefor |
US8889900B2 (en) | 2010-12-29 | 2014-11-18 | Ecolab Usa Inc. | Sugar ester peracid on site generator and formulator |
US9321664B2 (en) | 2011-12-20 | 2016-04-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
PT2609990T (pt) * | 2011-12-30 | 2022-08-25 | Kemira Oyj | Método para prevenção de crescimento microbiano em membrana de filtração |
BR112014020748B1 (pt) | 2012-03-30 | 2021-02-23 | Ecolab Usa Inc. | método de tratamento de águas, método de tratamento de uma fonte de água e composição aquosa de tratamento de água com atividade antimicrobiana |
US8835140B2 (en) * | 2012-06-21 | 2014-09-16 | Ecolab Usa Inc. | Methods using peracids for controlling corn ethanol fermentation process infection and yield loss |
US20140256811A1 (en) | 2013-03-05 | 2014-09-11 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
JP6427334B2 (ja) * | 2014-04-22 | 2018-11-21 | 保土谷化学工業株式会社 | 非腐食性過酢酸製剤とその製造方法 |
FI126082B (en) | 2014-07-15 | 2016-06-15 | Kemira Oyj | Procedure to prevent sludge formation |
WO2016100700A1 (en) * | 2014-12-18 | 2016-06-23 | Ecolab Usa Inc. | Methods for forming peroxyformic acid and uses thereof |
US11040902B2 (en) | 2014-12-18 | 2021-06-22 | Ecolab Usa Inc. | Use of percarboxylic acids for scale prevention in treatment systems |
KR20170096032A (ko) | 2014-12-18 | 2017-08-23 | 에코랍 유에스에이 인코퍼레이티드 | 다가 알콜 폼에이트를 통한 퍼옥시폼산의 생성 |
FI127444B (en) * | 2015-05-27 | 2018-06-15 | Kemira Oyj | A method for reducing the viscosity of a pulp in the manufacture of soluble cellulose |
CN104973666B (zh) * | 2015-07-10 | 2017-07-04 | 江苏鸿佑环保有限公司 | 智能化污水无氯消毒杀菌系统 |
CN104961209A (zh) * | 2015-07-10 | 2015-10-07 | 江苏鸿佑环保有限公司 | 污水高效无氯消毒杀菌系统 |
CN104944539A (zh) * | 2015-07-10 | 2015-09-30 | 江苏鸿佑环保有限公司 | 自来水无氯消毒杀菌系统 |
CN104944540A (zh) * | 2015-07-10 | 2015-09-30 | 江苏鸿佑环保有限公司 | 智能化自来水无氯消毒杀菌系统 |
US9814796B2 (en) | 2015-07-31 | 2017-11-14 | Performance Packaging Of Nevada, Llc | Methods for sterilization and/or disinfection |
US10172351B2 (en) | 2015-09-04 | 2019-01-08 | Ecolab Usa Inc. | Performic acid on-site generator and formulator |
EP3904526A1 (en) | 2015-09-10 | 2021-11-03 | Ecolab USA Inc. | Self indicating antimicrobial chemistry |
BR112018007928A2 (pt) | 2015-11-12 | 2018-10-30 | Ecolab Usa Inc. | método para inibir corrosão, e, composição. |
WO2017106623A1 (en) | 2015-12-16 | 2017-06-22 | Ecolab Usa Inc. | Peroxyformic acid compositions for membrane filtration cleaning |
US9907305B2 (en) | 2016-03-22 | 2018-03-06 | Solvay Sa | Production of disinfecting solutions |
CA3020824C (en) | 2016-04-15 | 2021-06-15 | Ecolab Usa Inc. | Performic acid biofilm prevention for industrial co2 scrubbers |
EP3554238A4 (en) | 2016-12-15 | 2020-05-27 | Ecolab USA Inc. | PEROXYFORMIC ACID COMPOSITIONS FOR CLEANING FILTRATION MEMBRANES IN ENERGY SERVICES |
US11541105B2 (en) | 2018-06-01 | 2023-01-03 | The Research Foundation For The State University Of New York | Compositions and methods for disrupting biofilm formation and maintenance |
CN115400146A (zh) | 2018-06-15 | 2022-11-29 | 埃科莱布美国股份有限公司 | 用于乳头治疗的现场产生的过甲酸组合物 |
BR112021002549A2 (pt) * | 2018-08-22 | 2021-05-04 | Ecolab Usa Inc. | composição de ácido peroxicarboxílico estabilizada, e, método para reduzir uma população microbiana usando uma composição de ácido peroxicarboxílico estabilizada. |
CN109535055A (zh) * | 2019-01-10 | 2019-03-29 | 浙江工业大学 | 一种利用微波技术强化过氧酸制备的方法 |
US11713436B2 (en) | 2019-06-17 | 2023-08-01 | Ecolab Usa Inc. | Textile bleaching and disinfecting using the mixture of hydrophilic and hydrophobic peroxycarboxylic acid composition |
BR112022000569A2 (pt) * | 2019-07-12 | 2022-06-07 | Arxada Llc | Composição antimicrobiana e método de uso da mesma |
EP3797592A1 (en) * | 2019-09-25 | 2021-03-31 | Sani-Marc Inc. | Peracetic compositions, methods and kits for removing biofilms from an enclosed surface |
KR20230033843A (ko) | 2021-09-02 | 2023-03-09 | 정도성 | 포름산을 이용한 과산화카르복시산의 현장 제조방법 |
CN115784393A (zh) * | 2022-11-30 | 2023-03-14 | 广东省科学院生物与医学工程研究所 | 过甲酸溶液在制备消毒剂中的应用 |
CN115893610A (zh) * | 2022-11-30 | 2023-04-04 | 广东省科学院生物与医学工程研究所 | 一种新型环保净水剂的制备方法及其应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6211237B1 (en) * | 1998-03-23 | 2001-04-03 | Degussa-Huls Ag | Aqueous disinfecting agent containing performic acid and peracetic acid process for production and process for use thereof |
US6284793B1 (en) * | 1998-12-04 | 2001-09-04 | Degussa-Huls Ag | Process for preventing contamination of the aquatic environment with organisms from ballast water |
WO2004035537A2 (en) * | 2002-10-16 | 2004-04-29 | Euro-Celtique S.A. | Antibodies that bind cell-associated ca 125/o772p and methods of use thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4304762A (en) * | 1978-09-27 | 1981-12-08 | Lever Brothers Company | Stabilization of hydrogen peroxide |
GB8531384D0 (en) | 1985-12-20 | 1986-02-05 | Unilever Plc | Sanitizing process |
US5200189A (en) * | 1991-07-23 | 1993-04-06 | Ecolab Inc. | Peroxyacid antimicrobial composition |
NL9300445A (nl) | 1993-03-12 | 1994-10-03 | Kemira Peroxides Bv | Werkwijze voor het ontsmetten van water zoals "drain water" in de tuinbouw, alsmede daarbij toe te passen inrichting. |
DE19812591A1 (de) * | 1998-03-23 | 1999-09-30 | Degussa | Verfahren zur Bekämpfung pflanzenpathogener Mikroorganismen in Wasserkreisläufen von Gewächshäusern |
DE19856198A1 (de) * | 1998-12-05 | 2000-06-08 | Degussa | Verfahren zur Schwimmbadwasseraufbereitung |
US6955766B2 (en) * | 1999-11-24 | 2005-10-18 | Degussa Ag | Method for reducing harmful organisms in currents of water |
FR2814180B1 (fr) * | 2000-09-18 | 2003-12-05 | Michel Delmas | Procede de blanchiment de pates a papier en milieu organique a hydratation controlee |
FI117056B (fi) | 2003-11-06 | 2006-05-31 | Kemira Oyj | Menetelmä biofilmiä muodostavien mikro-organismien esiintymisen monitoroimiseksi paperiteollisuudessa |
-
2005
- 2005-09-13 FI FI20050913A patent/FI118735B/fi active IP Right Grant
-
2006
- 2006-09-13 DE DE602006018491T patent/DE602006018491D1/de active Active
- 2006-09-13 JP JP2008530553A patent/JP2009507903A/ja not_active Withdrawn
- 2006-09-13 US US12/066,686 patent/US8828910B2/en active Active
- 2006-09-13 KR KR1020087006098A patent/KR101325236B1/ko active IP Right Grant
- 2006-09-13 AT AT06778512T patent/ATE489362T1/de not_active IP Right Cessation
- 2006-09-13 WO PCT/FI2006/000303 patent/WO2007031596A2/en active Application Filing
- 2006-09-13 EP EP06778512A patent/EP1931628B1/en active Active
- 2006-09-13 BR BRPI0615696-7A patent/BRPI0615696A2/pt not_active IP Right Cessation
- 2006-09-13 CN CN2006800335742A patent/CN101268045B/zh active Active
- 2006-09-13 ES ES06778512T patent/ES2359261T3/es active Active
- 2006-09-13 CA CA2627597A patent/CA2627597C/en active Active
-
2008
- 2008-02-26 NO NO20080974A patent/NO340754B1/no unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6211237B1 (en) * | 1998-03-23 | 2001-04-03 | Degussa-Huls Ag | Aqueous disinfecting agent containing performic acid and peracetic acid process for production and process for use thereof |
US6284793B1 (en) * | 1998-12-04 | 2001-09-04 | Degussa-Huls Ag | Process for preventing contamination of the aquatic environment with organisms from ballast water |
WO2004035537A2 (en) * | 2002-10-16 | 2004-04-29 | Euro-Celtique S.A. | Antibodies that bind cell-associated ca 125/o772p and methods of use thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2627597A1 (en) | 2007-03-22 |
US20090221704A1 (en) | 2009-09-03 |
FI118735B (fi) | 2008-02-29 |
BRPI0615696A2 (pt) | 2012-04-10 |
FI20050913A0 (fi) | 2005-09-13 |
CN101268045A (zh) | 2008-09-17 |
NO340754B1 (no) | 2017-06-12 |
EP1931628A2 (en) | 2008-06-18 |
WO2007031596A3 (en) | 2007-06-07 |
DE602006018491D1 (zh) | 2011-01-05 |
ATE489362T1 (de) | 2010-12-15 |
KR20080049738A (ko) | 2008-06-04 |
FI20050913A (fi) | 2007-03-14 |
NO20080974L (no) | 2008-05-29 |
KR101325236B1 (ko) | 2013-11-04 |
US8828910B2 (en) | 2014-09-09 |
EP1931628B1 (en) | 2010-11-24 |
ES2359261T3 (es) | 2011-05-19 |
JP2009507903A (ja) | 2009-02-26 |
CA2627597C (en) | 2013-10-22 |
WO2007031596A2 (en) | 2007-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101268045B (zh) | 过氧酸的制备方法 | |
CA2266523C (en) | Aqueous disinfecting agent containing performic acid and peracetic acid | |
US5616616A (en) | Room Temperature sterilant | |
US6423868B1 (en) | Process for the production of an aqueous monoester peroxycarboxylic acid solution, the solution obtainable by this process, and its use as disinfectant | |
US5589507A (en) | Method for sterilizing medical devices utilizing a room temperature sterilant | |
CA2156299C (en) | Inhibition of microbial growth in aqueous streams | |
US5635195A (en) | Premix for room temperature sterilant | |
KR101307064B1 (ko) | 미생물들의 성장을 억제하기 위한 상승작용 합성물 및 방법 | |
US6627594B1 (en) | Peroxy-carboxylic acid and aqueous compositions thereof | |
GB2207354A (en) | Compositions containing chlorine and/or hypochlorite together with an aliphatic peracid for use in disinfection | |
JP5332679B2 (ja) | 安定性に優れる過酢酸水溶液 | |
CA3236801A1 (en) | Improved formulations for oxidation, bleaching and microbial control | |
EP0602086B1 (en) | Preparation of peroxyacids | |
US20040074847A1 (en) | Stable N-bromo-2-pyrrolidone and methods to make the same | |
MXPA99002647A (es) | Agente desinfectante que contiene acido performico y acido paracetico, procedimiento para su preparacion y su uso | |
MXPA99005845A (en) | Percarboxylic acid solutions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |