CN112958079A - Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant - Google Patents
Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant Download PDFInfo
- Publication number
- CN112958079A CN112958079A CN202110186997.4A CN202110186997A CN112958079A CN 112958079 A CN112958079 A CN 112958079A CN 202110186997 A CN202110186997 A CN 202110186997A CN 112958079 A CN112958079 A CN 112958079A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- hydrogen peroxide
- mass
- disinfectant
- 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.)
- Pending
Links
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000000645 desinfectant Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 204
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 239000011591 potassium Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000004913 activation Effects 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910017107 AlOx Inorganic materials 0.000 claims abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- 229910002673 PdOx Inorganic materials 0.000 claims abstract description 3
- 229910002842 PtOx Inorganic materials 0.000 claims abstract description 3
- 229910019897 RuOx Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 143
- 239000012452 mother liquor Substances 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 239000003381 stabilizer Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000004659 sterilization and disinfection Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003570 air Substances 0.000 claims description 8
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229960003540 oxyquinoline Drugs 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- YOBWBLFILQYRFY-UHFFFAOYSA-N 2-hexadecylpyridine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCC1=CC=CC=[NH+]1 YOBWBLFILQYRFY-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 238000005551 mechanical alloying Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229960000583 acetic acid Drugs 0.000 description 41
- 239000000047 product Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 241000711573 Coronaviridae Species 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 241000315672 SARS coronavirus Species 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 4
- 241000700605 Viruses Species 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 244000063299 Bacillus subtilis Species 0.000 description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- DMOXNIKYXJYCFQ-UHFFFAOYSA-N (2-hydroxy-1-phosphonooxyethyl) dihydrogen phosphate Chemical compound OP(=O)(O)OC(CO)OP(O)(O)=O DMOXNIKYXJYCFQ-UHFFFAOYSA-N 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000711549 Hepacivirus C Species 0.000 description 2
- 241000725303 Human immunodeficiency virus Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- DQGRFSFYQIYMHB-UHFFFAOYSA-N acetaldehyde;ethaneperoxoic acid Chemical compound CC=O.CC(=O)OO DQGRFSFYQIYMHB-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006806 disease prevention Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- FIUXEBBRCRBWTE-UHFFFAOYSA-M hexadecyl(tripropyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CCC)(CCC)CCC FIUXEBBRCRBWTE-UHFFFAOYSA-M 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241000712461 unidentified influenza virus Species 0.000 description 2
- 206010002091 Anaesthesia Diseases 0.000 description 1
- 208000006400 Arbovirus Encephalitis Diseases 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 241000304886 Bacilli Species 0.000 description 1
- NGJQIQUNRRHCHB-UHFFFAOYSA-N CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.OC(=O)C(O)=O Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.OC(=O)C(O)=O NGJQIQUNRRHCHB-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010052369 Encephalitis lethargica Diseases 0.000 description 1
- 208000007212 Foot-and-Mouth Disease Diseases 0.000 description 1
- 241000710198 Foot-and-mouth disease virus Species 0.000 description 1
- 241000700721 Hepatitis B virus Species 0.000 description 1
- 244000309467 Human Coronavirus Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000127282 Middle East respiratory syndrome-related coronavirus Species 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 206010037742 Rabies Diseases 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 241000282898 Sus scrofa Species 0.000 description 1
- 230000037005 anaesthesia Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 210000002865 immune cell Anatomy 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 241001529453 unidentified herpesvirus Species 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 201000002498 viral encephalitis Diseases 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
Abstract
The invention provides a catalyst for preparing peroxyacetic acid disinfectant and a preparation method of the disinfectant, wherein the catalyst is prepared by the following steps of uniformly mixing a catalyst precursor and auxiliary materials under a certain condition, and carrying out heat treatment and activation to obtain the catalyst; the catalyst precursor is one or more than two of metal precursor salt, metal oxide and metal simple substance, and the metal precursor salt is one or more than two of potassium chloroaurate, potassium chloropalladate, potassium chloroplatinate, ruthenium trichloride, silver nitrate and sodium hexachlororhodate; the metal oxide is one or more than two of PtOx, PdOx, RuOx, RhOx, IrOx, AuOx, AgOx and AlOx; the metal simple substance is one or more than two of Pt, Pd, Ru, Rh, Ir, Au, Ag and Al. The invention widens the application of low-concentration hydrogen peroxide in synthesis of peroxyacetic acid, avoids the dependence of a high-concentration hydrogen peroxide production device, and can realize popularization and production.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering and pharmaceutical chemical engineering, and particularly relates to a catalyst for preparing peroxyacetic acid disinfectant and a preparation method of the disinfectant.
Background
Peroxyacetic acid (C) in the field of disinfectants for air, surfaces, vegetables, fruits, medical instruments and the like2H4O3PAA) can kill bacteria, fungi, bacilli, viruses. According to the detection report of foreign laboratories (Dr. Gerd Schreiner, Ines Bube Kurzfassung in
OBST 66(1999) Heft 4, S.183-188), can kill various virulent viruses, bacteria, spores, fungi and other pathogenic microorganisms rapidly and thoroughly, and has good prevention (killing) effect on various infectious diseases (pathogens). Including but not limited to: escherichia coli, herpes virus, Human Immunodeficiency Virus (HIV), influenza virus, human coronavirus (CoV), Hepatitis B Virus (HBV), Hepatitis C Virus (HCV), avian influenza virus, swine fever, foot and mouth disease, rabies, epidemic encephalitis B, Salmonella, etc. The disinfectant is also effective against coronavirus in early 2020, and has the advantages of broad spectrum, high efficiency, quick action and the like. The decomposition products of the peracetic acid disinfectant are acetic acid, water, carbon dioxide and other harmless substances, so that the disinfectant has the great advantage of being green and harmless. The disinfectant has been used for disinfection in the fortieth years, and the research, production, popularization and application of China are started in the seventies. The action time of the peroxyacetic acid disinfectant for the coronavirus is only 2min, the peroxyacetic acid disinfectant is the best choice specified by the United states CDC for application to epidemic situation elimination, and the peroxyacetic acid disinfectant still has a strong bactericidal effect in an environment of-20-60 ℃, and is an ideal high-efficiency, environment-friendly and non-toxic disinfectant at present.
Because the stability of the peroxyacetic acid is poor, the effective concentration of the peroxyacetic acid can be rapidly reduced by factors such as temperature, illumination, organic matters, alkali, various metal ions and the like. Since the last 70s, how to improve the stability of peracetic acid in peracetic acid disinfectants has been the focus of research. There are two types of peroxyacetic acid products currently on the market: one is binary type, its product is divided into A, B two components, when in use, A, B component is mixed according to a certain proportion and placed for 24 hours to 48 hours, and then diluted to the required concentration according to the using environment or the sterilization object. The concentration of the peroxyacetic acid after the AB agent is mixed is reduced more quickly and is interfered by storage temperature, environment or a container, and the reduction trend is accelerated along with the increase of the concentration of the peroxyacetic acid. The other is a primary type, and the primary type peroxyacetic acid overcomes some defects of the secondary type peroxyacetic acid, but the stability of the primary type peroxyacetic acid is always a great technical problem in the disinfection field.
The acetaldehyde production process can produce anhydrous peroxyacetic acid solution by an acetaldehyde air/oxygen oxidation method, and the method has the advantages of complex equipment, high investment and high requirement on safety coefficient; meanwhile, acetaldehyde monoperacetate produced in the production process is a temperature-sensitive explosive compound, so that the explosion risk is high; if an acidic catalyst is used to inhibit the formation of acetaldehyde monoperacetate, the heavy metal acidic catalyst needs to be removed at a later stage, otherwise the stability of the anhydrous peroxyacetic acid solution is affected.
The foreign industrial production of peroxyacetic acid mostly adopts hydrogen peroxide and glacial acetic acid as main raw materials. But the production process is complex, the manufacturing cost is high, and the safety and the stability can not meet the production and use requirements. The concentration of the peroxyacetic acid produced by 30 percent or 27.5 percent of hydrogen peroxide by mass fraction is 12-16 percent. In order to obtain a peroxyacetic acid solution with the concentration of 30-40% in the industry, 60-70% by weight of hydrogen peroxide needs to be used, and peroxyacetic acid is highly dependent on a high-concentration hydrogen peroxide producer, so that the industrial production popularization of peroxyacetic acid is severely limited. The transportation risk of high-concentration hydrogen peroxide is very high, and explosion is easy to occur. Therefore, the problems of limiting factors of high-concentration hydrogen peroxide, low concentration of peroxyacetic acid produced by low-concentration hydrogen peroxide, long reaction time, uncontrollable risk and the like are urgently needed to be solved in the industrial production of peroxyacetic acid.
The old product of the AB agent has high risk, and the concentrated solution of the AB agent with the peroxyacetic acid concentration of 15-21 percent is not beneficial to the storage of common users and is difficult to complete the safe dilution and use through simple operation.
The 75% alcohol is water solution with 75% ethanol content, and has great flammability and explosion hazard, and fire is easily caused by improper control in the process of large-scale use and spraying. In SARS prevention and disinfection technical guideline published by the national ministry of health in 2003, the spraying of 0.1-0.2% disinfectant solution of peroxyacetic acid is only recommended for air disinfection.
During the decomposition process of the peroxyacetic acid, only oxygen and acetic acid are generated, and the acetic acid is gradually oxidized to finally form water and carbon dioxide without any other byproducts. Compared with other 84 disinfectants which can release toxic chlorine gas when not used in a standard way, flammable ethanol, toxic formaldehyde and chloroform, ether with anesthesia, potassium permanganate which can generate manganese-containing heavy metal wastewater and the like, the peracetic acid has obvious environmental protection advantages.
Peroxyacetic acid is potent in killing, acting in a mechanism similar to that of immune cells. It reacts with proteins and DNA of viruses, bacteria, fungi by releasing peroxidized free radicals, and after reaction, kills these microorganisms. The effect is also quick and efficient, 40ppm of peroxyacetic acid can kill bacteria in water in short 1 minute, and the effect is far superior to that of chlorine-containing disinfectants.
According to the summary of the disease prevention and control center of people's liberation force in China that the resistance and disinfection of coronavirus to a large number of coronavirus and disinfection scheme, research shows that 0.35g/L peroxyacetic acid disinfectant can inactivate the infection activity of SARS-CoV virus within 2 min. The work of SARS resistance is summarized by Jiangsu province disease prevention and control center, and the report of important role of disinfection in prevention and control of SARS proposes that the virus stock solution of SARS-CoV can be completely inactivated in a short time (1-10 min) by 0.2g/L of peroxyacetic acid disinfectant. According to the diagnosis and treatment scheme for pneumonia infected by novel coronavirus (trial sixth edition) published by Weijian Commission of China, peracetic acid can effectively inactivate coronavirus such as SARS-CoV and MERS-CoV.
TABLE 1 Effect of peroxyacetic acid on the inactivation of SARS-CoV Virus in a sample
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for preparing a peroxyacetic acid disinfectant and a preparation method of a disinfectant, so as to widen the application of low-concentration hydrogen peroxide to peroxyacetic acid synthesis, avoid the dependence of a high-concentration hydrogen peroxide production device, and realize popularization and production. The method has simple process route, and realizes the preparation of the high-concentration peroxyacetic acid intermediate by the quick reaction of low-concentration hydrogen peroxide through adjusting the proportioning concentration of the raw materials by the rectifying tower; the special stabilizer is added to prevent the hydrogen peroxide from decomposing, so that the utilization rate of the hydrogen peroxide is improved; the catalyst is adopted to reduce the reaction activation energy, accelerate the reaction speed and promote the carboxylic acid group peroxidation; the limit of high-concentration hydrogen peroxide is avoided, and the reaction risk dump is reduced from the aspect of intrinsic safety; reaction conditions are controlled, and the time consumption of the traditional production is greatly shortened; the reaction process is designed to directly produce the sterilizing end product.
The catalyst is adopted to reduce the activation energy of the reaction, accelerate the reaction speed and promote the peroxidation of carboxylic acid groups.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a catalyst for preparing peroxyacetic acid disinfectant comprises the following steps of uniformly mixing a catalyst precursor and auxiliary materials under a certain condition, and carrying out heat treatment and activation to obtain the catalyst; the catalyst precursor is one or more than two of metal precursor salt, metal oxide and metal simple substance, and the metal precursor salt is one or more than two of potassium chloroaurate, potassium chloropalladate, potassium chloroplatinate, ruthenium trichloride, silver nitrate and sodium hexachlororhodate; the metal oxide is one or more than two of PtOx, PdOx, RuOx, RhOx, IrOx, AuOx, AgOx and AlOx; the metal simple substance is one or more than two of Pt, Pd, Ru, Rh, Ir, Au, Ag and Al.
Preferably, when the catalyst precursor contains a metal precursor salt, the auxiliary material is a surfactant or an aqueous solution of strong base; when the catalyst precursor does not comprise metal precursor salt, the auxiliary material is a surfactant or an aqueous solution of strong base or a mixture of the surfactant and the aqueous solution of strong base; the surfactant is one or more than two of hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl tertiary amine acetate, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and hexadecyl pyridine chloride; preferably, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, most preferably cetyltrimethylammonium bromide; the strong base is sodium hydroxide or potassium hydroxide.
Preferably, the certain condition is one or a combination of several of the following conditions,
a) when the catalyst precursor does not contain a metal simple substance, the heating temperature is 60-90 ℃ during stirring and feeding reaction, and preferably 70-80 ℃;
b) when the catalyst precursor contains a metal simple substance, arc melting and induction melting are carried out, and the melting temperature is controlled to be not higher than 300-3000 ℃, preferably 700-2800 ℃;
c) when the catalyst precursor contains a metal simple substance, mechanical alloying is carried out, and the alloying time is controlled to be 1 hour to 30 days, preferably 2 hours to 15 days.
Preferably, the heat treatment is carried out at the temperature of 400-800 ℃, preferably 500-700 ℃; the time is 0.1-24 h; the atmosphere for the heat treatment is air, nitrogen, argon or hydrogen.
Preferably, the activation process is one of the following,
a) when the catalyst precursor contains metal precursor salt, activating the catalyst by sodium borohydride, potassium borohydride, hydrazine hydrate or citric acid aqueous solution at the temperature of 20-100 ℃, preferably by sodium borohydride, potassium borohydride or hydrazine hydrate;
b) when the catalyst precursor does not contain metal precursor salt, the catalyst is activated by aqueous solution of sodium hydroxide, hydrochloric acid, nitric acid, sulfuric acid or ferric trichloride at 20-100 ℃, and the preferred is sodium hydroxide, hydrochloric acid or ferric trichloride.
The invention also provides a preparation method of the peroxyacetic acid disinfectant, which comprises the following steps,
1) mixing hydrogen peroxide, a stabilizer and acetic acid or allowing single components to enter a rectifying tower; the stabilizer is sulfuric acid compounded with other stabilizers, and the other stabilizers are one or more than two of pyrophosphoric acid, sodium pyrophosphate, hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, 8-hydroxyquinoline and pyridine-2, 6-dicarboxylic acid; the concentration of hydrogen peroxide is 5-50 wt%, the mass of acetic acid in the feed of the rectifying tower is 0.1-150% of hydrogen peroxide, the mass of stabilizer sulfuric acid is 1-5% of hydrogen peroxide, and the mass of other stabilizers is 0.001-3% of hydrogen peroxide.
2) The temperature of an evaporator of the rectifying tower is 35-100 ℃, the vacuum is maintained at 2000-5000 Pa, and the reflux ratio is (1-10): 1, the content of hydrogen peroxide in the effluent liquid at the tower top is 0.01-3 wt%;
3) mixing the mother liquor in the tower kettle, acetic acid and other stabilizers replenished for the second time, and feeding the mixture into a continuous flow microchannel reactor filled with a catalyst, wherein the mass of the acetic acid is 0.1-150% of the mother liquor, the dosage of the catalyst is 0.1-1% of the mass of the mother liquor, and the mass of the stabilizer is 0.001-0.1% of the mass of the mother liquor; the temperature of the reactor is 50-180 ℃, the pressure is 0.1-1.8 MPa, and the retention time is 1-280 s; the catalyst is the catalyst according to any one of claims 1 to 5;
4) the concentration of the peroxyacetic acid in the solution at the outlet of the reactor is 20-45 wt%, and preferably, the method further comprises the step of diluting the fraction of the rectifying tower, acetic acid and water and the high-concentration peroxyacetic acid on line to obtain the peroxyacetic acid disinfectant for disinfection. The proportion of each component can be adjusted according to different production requirements.
Preferably, in the step 1), the concentration of hydrogen peroxide is 20-50 wt%; the mass of acetic acid in the feed of the rectifying tower is 20-50% of hydrogen peroxide, preferably 25-35%; the mass of the stabilizer sulfuric acid is 1.5-4.6% of that of the hydrogen peroxide, preferably 2.5-3.5%; the mass of other stabilizers is 0.01-0.3% of the mass of hydrogen peroxide, preferably 0.05-0.25%.
Preferably, in the step 2), the temperature of the evaporator is 50-80 ℃, preferably 65-75 ℃; the vacuum is maintained at 2500-4000 Pa, preferably 3000-3500 Pa; the reflux ratio is (2-7): 1, preferably (3-4): 1; the content of hydrogen peroxide in the effluent liquid at the tower top is 0.1-1 wt%, preferably 0.5-0.8 wt%.
Preferably, in the step 3), the mass of the acetic acid is 50-140% of that of the mother liquor, and preferably, 75-100%; the amount of the catalyst is 0.5-1% of the mass of the mother liquor; the mass of other stabilizers is 0.01-0.05% of the mass of the mother liquor, preferably 0.03-0.04%; the temperature of the reactor is 80-170 ℃, preferably 100-140 ℃; the pressure is 0.25-1.6 MPa, preferably 0.7-1.3 MPa; the retention time is 5-200 s, preferably 30-70 s.
Preferably, in the step 4), the concentration of the peroxyacetic acid in the solution at the outlet of the reactor is 25-40 wt%, preferably 30-37 wt%.
Compared with the prior art, the catalyst for preparing the peroxyacetic acid disinfectant and the preparation method of the disinfectant have the following advantages:
(1) the process route is simple, and the low-concentration hydrogen peroxide rapidly reacts to prepare the high-concentration peroxyacetic acid intermediate and the terminal disinfectant product.
(2) The sulfuric acid stabilizer is compounded with other stabilizers, acetic acid is added into low-concentration hydrogen peroxide to reduce the hydrogen peroxide content in the mother solution, and the hydrogen peroxide stability is improved.
(3) The hydrogen peroxide with the concentration of 5-50% is suitable for the process, so that the application of low-concentration hydrogen peroxide in synthesis of peroxyacetic acid is widened, the dependence of high-concentration hydrogen peroxide production devices is avoided, and the national popularization and production can be realized. .
(4) The reaction time can be reduced to 1-280 s, the reaction residence time is greatly shortened, and the reaction risk is reduced.
(5) The continuous flow microchannel reactor holds 500-600 mL of liquid agent, meets the requirement of 2-4 ten thousand tons per year of disinfectant production, and is intrinsically safe to control.
(6) The high-concentration peroxyacetic acid at the outlet of the reactor is mixed and diluted with distillate at the top of the rectifying tower, acetic acid and pure water on line, the concentration of the product at the outlet is a disinfection product, the mass concentration of the product is not higher than 0.5 percent peroxyacetic acid, the product is medical grade disinfectant, the product does not belong to dangerous chemicals, and the product is non-inflammable, free of risks such as explosion and the like, and is intrinsically safe.
Drawings
Fig. 1 is a schematic diagram of a simple structure of a device used in a method for rapidly preparing a peroxyacetic acid disinfectant with low-concentration hydrogen peroxide according to an embodiment of the present invention;
1. a hydrogen peroxide pump A; 2. a rectifying tower; 3. a condenser; 4. a continuous flow reactor; 5. an acetic acid pump A; 6. a pure water pump; 7. an acetic acid pump B; 8. a hydrogen peroxide pump B; 9. and (5) a finished product groove.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
The core optimal reaction conditions in the steps of the invention are as follows: hydrogen peroxide, a stabilizer and acetic acid are mixed or single components enter a rectifying tower. Acetic acid is 0.1-150% of hydrogen peroxide by mass, 1-5 wt% of sulfuric acid and 0.001-3 wt% of compound stabilizer are added into the hydrogen peroxide, the hydrogen peroxide content is 5-50 wt%, 2) the evaporator temperature is 35-100 ℃, the vacuum is maintained at 2000-5000 Pa, and the reflux ratio is (1-10): 1, the content of hydrogen peroxide in the effluent liquid at the tower top is 0.01-3 wt%. Mixing the mother liquor in the tower kettle, acetic acid and a secondary replenishing stabilizer, and feeding the mixture into a continuous flow microchannel reactor filled with a catalyst, wherein the mass of the acetic acid is 0.1-150% of the mother liquor, the dosage of the catalyst is 0.1-1% of the mass of the mother liquor, and the mass of the stabilizer is 0.001-0.1% of the mass of the mother liquor. The temperature of the reactor is 50-180 ℃, the pressure is 0.1-1.8 MPa, and the retention time is 1-280 s;
and (3) peroxyacetic acid with the concentration of 20-45% at the outlet of the reactor, and diluting the fraction of the rectifying tower, acetic acid and water and the high-concentration peroxyacetic acid on line to obtain the peroxyacetic acid disinfectant applied to air disinfection.
The examples illustrate the intrinsic safety control and technical advancement features of the process by describing the peracetic acid concentrate production process and the on-line serial dilution process.
(1) Catalyst preparation Process
Example 1
5g of hexadecyltripropylammonium bromide is dissolved in 60mL of a mixed solution of 0.5mol/L NaOH and 2.4L of deionized water, the mixed solution is stirred for 15min at the temperature of 80 ℃, 0.1L of 3.7 wt% formaldehyde solution is added, and 0.1L of 0.05mol/L potassium chloropalladate aqueous solution is added. Stirring for 10min, slowly adding 50g ethanol dropwise, reacting for 1 hr, centrifuging, washing with deionized water for 4 times, washing with ethanol for 1 time, and drying at 60 deg.C for 24 hr. Heating to 600 ℃ at the heating rate of 1 ℃/min under the air atmosphere, carrying out heat preservation and calcination for 6h, and removing hexadecyl tripropyl ammonium bromide to obtain the final catalyst.
Example 2
The materials are mixed according to the mass ratio of 2:3 of ruthenium to aluminum metal, namely the atomic ratio of 15: 85.In order to prevent the electric arc from rushing the materials out of the crucible in the smelting process, the sectional area is 9mm2The bulk ruthenium metal of (2) and filiform aluminum metal with the length of 5mm and the inner diameter of 1mm as auxiliary materials. According to the principle that the high-melting-point metal which is easy to splash is arranged below the crucible, the ruthenium metal is firstly arranged at the bottom of the copper crucible and then covered by the aluminum metal. Vacuum pumping the electric arc furnace to 6 x 10-3Pa, filling inert gas as protective atmosphere and then smelting. After smelting, continuously turning over and cooling to form ingots, and repeatedly smelting each alloy sample for multiple times in order to ensure that the alloy is evenly smelted. Raising the temperature to 600 ℃ at a heating rate of 1 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 6 h. The activation process is as follows: an excess of NaOH (15 wt%) solution was prepared and the temperature was raised to 50 ℃. Adding the alloy powder in batches under the stirring condition, and adding the next batch of powder after bubbles disappear so as to prevent alkali liquor from splashing. Then the temperature is raised to 90 ℃, and the temperature is kept for 1 h. And after the activation is finished, quickly placing the beaker in an ice water bath for cooling, and then washing the beaker to be neutral by using deionized water to obtain the final catalyst.
Example 3
Powdered platinum metal and aluminum metal are used as alloy raw materials. The materials are mixed according to the mass ratio of 1:4 of the platinum to the aluminum, and after a certain amount of process control agent is added, the powder materials are uniformly mixed. And then adding the mixture into a ball milling tank, adding grinding balls with the mass 20 times that of the raw materials, sealing the tank and vacuumizing. Rotating at 500rpm, switching the rotation direction every 2h, and continuously grinding for a certain time. After long-time ball milling, the grain diameter of the discharged powder is generally less than 1 μm, the ball milling tank is placed in a vacuum glove box, the tank is opened and the sample is taken under the protection of nitrogen, and finally the ball milling tank is stored in a container with a valve. After the alloy powder is passivated by air diffused into the alloy powder, 400 meshes of powder are sieved for later use. Raising the temperature to 600 ℃ at a heating rate of 1 ℃/min under the nitrogen atmosphere, and carrying out heat preservation and calcination for 6 h. The activation process is as follows: an excess of HCl (15 wt%) solution was prepared and warmed to 50 ℃. Adding the alloy powder in batches under the stirring condition, and adding the next batch of powder after bubbles disappear so as to prevent alkali liquor from splashing. Then the temperature is raised to 90 ℃, and the temperature is kept for 1 h. And after the activation is finished, quickly placing the beaker in an ice water bath for cooling, and then washing the beaker to be neutral by using deionized water to obtain the final catalyst.
(2) Production process of concentrated peroxyacetic acid solution
Example 4
Sulfuric acid with the mass of 1 percent of hydrogen peroxide, sodium pyrophosphate with the mass of 0.001 percent of hydrogen peroxide and acetic acid with the mass of 10 percent of hydrogen peroxide are added into the hydrogen peroxide, the concentration of the hydrogen peroxide is 10 weight percent, the flow rate of a hydrogen peroxide feeding pump A is 20.7Kg/h, the hydrogen peroxide enters a rectifying tower, the temperature of an evaporator is 35 ℃, the pressure of the top of the tower is 2000Pa, the reflux ratio is controlled to be 10:1, the mass of a distillate is 18.2Kg/h, and the mass concentration of hydrogen peroxide in the distillate is 0.01 percent.
2.45Kg/h of mother liquor flowing out of the tower bottom enters a continuous flow microchannel reactor (corning G3), the flow rate of a feeding acetic acid pump A of the reactor is 3.44Kg/h, sodium pyrophosphate with the mass of 0.001 percent of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in the embodiment 3 is selected) is 0.1 percent of the mass of the mother liquor, the temperature of the reactor is 50 ℃, the retention time of the reactor is 280s under the pressure of 0.1MPa, the mass concentration of the peroxyacetic acid in the distillate of the reactor is 20 percent, and the material flow is 5.89 Kg/h.
Example 5
Sulfuric acid accounting for 5% of the weight of hydrogen peroxide, oxalic acid tetraacetic acid accounting for 3% of the weight of hydrogen peroxide and acetic acid accounting for 150% of the weight of hydrogen peroxide are added into the hydrogen peroxide, the concentration of the hydrogen peroxide is 50 wt%, the flow rate of a hydrogen peroxide feeding pump A is 5.0Kg/h, the hydrogen peroxide enters a flash tower, the temperature of an evaporator is 35 ℃, the pressure of the top of the tower is 5000Pa, the reflux ratio is controlled to be 1:1, the mass of a distillate is 1.0Kg/h, and the mass concentration of hydrogen peroxide in the distillate is 3%.
3.9Kg/h of mother liquor flowing out of the column bottom enters a continuous flow microchannel reactor (corning G3), the flow rate of a reactor feeding acetic acid pump A is 5.7Kg/h, ethylene diamine tetraacetic acid with the mass of 0.1% of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in the embodiment 2 is selected) is 1% of the mass of the mother liquor, the temperature of the reactor is 180 ℃, the retention time of the reactor is 1s under the pressure of 1.8MPa, the mass concentration of the peroxyacetic acid in a distillate of the reactor is 20%, and the material flow is 9.5 Kg/h.
Example 6
Sulfuric acid accounting for 5% of the weight of hydrogen peroxide, 8-hydroxyquinoline accounting for 3% of the weight of hydrogen peroxide and acetic acid accounting for 150% of the weight of hydrogen peroxide are added into the hydrogen peroxide, the concentration of the hydrogen peroxide is 50 wt%, the flow rate of a hydrogen peroxide feeding pump A is 5.0Kg/h, the hydrogen peroxide enters a flash tower, the temperature of an evaporator is 35 ℃, the pressure of the top of the tower is 5000Pa, the reflux ratio is controlled to be 1:1, the mass of a distillate is 1.0Kg/h, and the mass concentration of hydrogen peroxide in the distillate is 3%.
3.9Kg/h of mother liquor flowing out of the column bottom enters a continuous flow microchannel reactor (corning G3), the flow rate of a reactor feeding acetic acid pump A is 5.7Kg/h, 8-hydroxyquinoline with the mass of 0.1 percent of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in the embodiment 2 is selected) is 1 percent of the mass of the mother liquor, the temperature of the reactor is 180 ℃, the retention time of the reactor is 10s under the pressure of 1.8MPa, the mass concentration of the peroxyacetic acid in the distillate of the reactor is 25 percent, and the material flow is 9.5 Kg/h.
Example 7
Sulfuric acid accounting for 1.02 percent of the mass of hydrogen peroxide, pyridine-2, 6-dicarboxylic acid accounting for 1.2 percent of the mass of hydrogen peroxide and acetic acid accounting for 10 percent of the mass of hydrogen peroxide are added into hydrogen peroxide, the concentration of the hydrogen peroxide is 48 percent by weight, a hydrogen peroxide feeding pump A enters a flash tower at the flow rate of 4.8Kg/h, the temperature of an evaporator is 65 ℃, the pressure of the top of the tower is 3000Pa, the reflux ratio is controlled to be 2:1, the mass of distillate is 0.5Kg/h, and the mass concentration of the hydrogen peroxide in the distillate is 1.5 percent.
4.3Kg/h of mother liquor flowing out of the column bottom enters a continuous flow microchannel reactor (the liquid holdup is 500 ml, the inner diameter is 3 mm), the flow rate of a reactor feeding acetic acid pump A is 2.5Kg/h, pyridine-2, 6-dicarboxylic acid with the mass of 0.01 percent of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in the embodiment 3 is selected) is 1 percent of the mass of the mother liquor, the temperature of the reactor is 140 ℃, the pressure of the reactor is 1.1MPa, the retention time is 48s, the mass concentration of the peracetic acid in a reactor distillate is 32 percent, and the material flow is 6.7 Kg/h.
Example 8
Sulfuric acid accounting for 1.02 percent of the mass of hydrogen peroxide, hydroxyethylidene diphosphoric acid accounting for 1.3 percent of the mass of hydrogen peroxide and acetic acid accounting for 5 percent of the mass of hydrogen peroxide are added into hydrogen peroxide, the concentration of the hydrogen peroxide is 48 percent by weight, a hydrogen peroxide feeding pump A enters a flash tower at the flow rate of 11.3Kg/h, the temperature of an evaporator is 75 ℃, the pressure of the top of the tower is 3500Pa, the reflux ratio is controlled to be 3:1, the mass of distillate is 0.9Kg/h, and the mass concentration of hydrogen peroxide in the distillate is 0.3 percent.
10.3Kg/h of mother liquor flowing out of the column bottom enters a continuous flow microchannel reactor (the liquid holdup is 500 ml, the inner diameter is 3 mm), the flow rate of a reactor feeding acetic acid pump A is 14.1Kg/h, 0.01 percent of hydroxy ethylidene diphosphonic acid by mass of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in example 2 and example 3 is added according to the mass ratio of 1: 1) is 1 percent of the mass of the mother liquor, the temperature of the reactor is 100 ℃, the pressure of the reactor is 1.6MPa, the retention time is 90s, the mass concentration of peracetic acid in a distillate of the reactor is 29 percent, and the material flow is 24.3 Kg/h.
Example 9
Sulfuric acid with the mass of 3.5 percent of hydrogen peroxide, hydroxyethylidene diphosphoric acid with the mass of 1.0 percent of hydrogen peroxide and acetic acid with the mass of 1.2 percent of hydrogen peroxide are added into hydrogen peroxide, the concentration of the hydrogen peroxide is 46 percent by weight, the flow rate of a hydrogen peroxide feeding pump A is 16.3Kg/h, the hydrogen peroxide enters a flash tower, the temperature of an evaporator is 85 ℃, the pressure of the top of the tower is 3500Pa, the reflux ratio is controlled to be 5:1, the mass of distillate is 5.9Kg/h, and the mass concentration of the hydrogen peroxide in the distillate is 0.5 percent.
The mother liquor flowing out of the column bottom is 10.2Kg/h and enters a continuous flow microchannel reactor (the liquid holdup is 500 ml, the inner diameter is 3 mm), the flow rate of a reactor feeding acetic acid pump A is 5.1Kg/h, 0.01 percent of hydroxy ethylidene diphosphonic acid by mass of the mother liquor is added into acetic acid, the adding amount of a catalyst (the catalyst prepared in example 2 and example 3 is added according to the mass ratio of 1: 1) is 1 percent of the mass of the mother liquor, the temperature of the reactor is 120 ℃, the pressure of the reactor is 1.5MPa, the retention time is 60s, the mass concentration of peracetic acid in the distillate of the reactor is 40 percent, and the material flow is 25.2 Kg/h.
(3) Continuous dilution production process
Example 10
The continuous flow reactor produces a concentrated peroxyacetic acid solution (the content of the peroxyacetic acid is 27.3 percent, the content of hydrogen peroxide is 5.0 percent, and the content of the acetic acid is 39.1 percent), the flow rate of the concentrated solution is 24.3Kg/h, the flow rate of a continuous dilution hydrogen peroxide (50 weight percent) pump B is 42.4Kg/h, the flow rate of a pure water pump is 1110.2Kg/h, the overhead fraction is 1.3Kg/h (the content of the hydrogen peroxide is 0.01 percent), the flow rate of an acetic acid pump B is 30.3Kg/h, and 0.5 percent peroxyacetic acid disinfectant is produced (the content of the peroxyacetic acid is 0.48 to 0.53 percent, the content of the acetic acid is 2.8 to 3.3 percent, and the content of the hydrogen peroxide is 3.
Disinfection ability test (Disinfection technical Specification of Ministry of health (2002 edition) for testing)
1. Under the test conditions, the sterile PBS solution containing 0.3% of sodium thiosulfate can effectively neutralize the sterilization effect of the residual peroxyacetic acid disinfectant (the disinfectant in example 10) on staphylococcus aureus, and the neutralizer and the neutralized product have no obvious influence on the growth of the tested bacteria.
2. Under the test conditions, the peroxyacetic acid disinfectant (the disinfectant in example 10) acts for 1min, and the killing log value of the peroxyacetic acid disinfectant on staphylococcus aureus is greater than 3.00.
3. Under the test conditions, the peroxyacetic acid disinfectant (the disinfectant in example 10) acts for 2min, and the killing logarithm value of the peroxyacetic acid disinfectant on escherichia coli is greater than 3.00.
4. Under the test conditions, the peracetic acid disinfectant (the disinfectant in example 10) acts for 1min, and the killing log value of the disinfectant on pseudomonas aeruginosa is greater than 3.00.
5. Under the test conditions, the sterile PBS solution containing 0.3% of sodium thiosulfate can effectively neutralize the sterilization effect of the residual peroxyacetic acid disinfectant (the disinfectant in example 10) on the Candida albicans, and the neutralizer and the neutralized product have no obvious influence on the growth of the tested bacteria.
6. Under the test conditions, the peroxyacetic acid disinfectant (the disinfectant in example 10) acts for 3min, and the killing log value of candida albicans is more than or equal to 3.00.
7. Under the test conditions, a sterile PBS solution of 0.5 percent sodium thiosulfate can effectively neutralize the sterilization effect of residual peroxyacetic acid disinfectant (the disinfectant in example 10) on the black variety spores of the bacillus subtilis, and the neutralizing agent and a neutralized product have no obvious influence on the growth of the tested bacteria.
8. Under the test conditions, the peroxyacetic acid disinfectant (the disinfectant of example 10) acts for 10min, and the killing logarithm value of the bacillus subtilis var niger spores is larger than 3.00.
9. 30-part sample tests show that under the test conditions, the peroxyacetic acid disinfectant (the disinfectant in example 10) acts for 10min, and the killing log value of the artificially polluted bacillus subtilis var niger spores on the tooth surfaces of the hemostatic forceps is 3.24 (3.15-3.34).
10. The 30-part sample test shows that under the test condition, the peracetic acid disinfectant (the disinfectant in the example 10) acts for 2min, and the average killing log value of the peracetic acid disinfectant on natural bacteria on a wooden square table (the surface of a wooden table) is 1.08 (1.19-1.35).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A catalyst for preparing peroxyacetic acid disinfectant is characterized in that: the method comprises the following steps of uniformly mixing a catalyst precursor and auxiliary materials under a certain condition, and carrying out heat treatment and activation to obtain a catalyst; the catalyst precursor is one or more than two of metal precursor salt, metal oxide and metal simple substance, and the metal precursor salt is one or more than two of potassium chloroaurate, potassium chloropalladate, potassium chloroplatinate, ruthenium trichloride, silver nitrate and sodium hexachlororhodate; the metal oxide is one or more than two of PtOx, PdOx, RuOx, RhOx, IrOx, AuOx, AgOx and AlOx; the metal simple substance is one or more than two of Pt, Pd, Ru, Rh, Ir, Au, Ag and Al.
2. The catalyst for use in the production of peroxyacetic acid disinfectant of claim 1, wherein: when the catalyst precursor contains metal precursor salt, the auxiliary material is a surfactant or an aqueous solution of strong base; when the catalyst precursor does not comprise metal precursor salt, the auxiliary material is a surfactant or an aqueous solution of strong base or a mixture of the surfactant and the aqueous solution of strong base; the surfactant is one or more than two of hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl tertiary amine acetate, dodecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium chloride and hexadecyl pyridine chloride; preferably, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, most preferably cetyltrimethylammonium bromide; the strong base is sodium hydroxide or potassium hydroxide.
3. The catalyst for use in the production of peroxyacetic acid disinfectant of claim 1, wherein: the certain condition is one or a combination of several of the following conditions,
a) when the catalyst precursor does not contain a metal simple substance, the heating temperature is 60-90 ℃ during stirring and feeding reaction, and preferably 70-80 ℃;
b) when the catalyst precursor contains a metal simple substance, arc melting and induction melting are carried out, and the melting temperature is controlled to be not higher than 300-3000 ℃, preferably 700-2800 ℃;
c) when the catalyst precursor contains a metal simple substance, mechanical alloying is carried out, and the alloying time is controlled to be 1 hour to 30 days, preferably 2 hours to 15 days.
4. The catalyst for use in the production of peroxyacetic acid disinfectant of claim 1, wherein: the heat treatment is carried out at the temperature of 400-800 ℃, and preferably at the temperature of 500-700 ℃; the time is 0.1-24 h; the atmosphere for the heat treatment is air, nitrogen, argon or hydrogen.
5. The catalyst for use in the production of peroxyacetic acid disinfectant of claim 1, wherein: the activation process is one of the following processes,
a) when the catalyst precursor contains metal precursor salt, activating the catalyst by sodium borohydride, potassium borohydride, hydrazine hydrate or citric acid aqueous solution at the temperature of 20-100 ℃, preferably by sodium borohydride, potassium borohydride or hydrazine hydrate;
b) when the catalyst precursor does not contain metal precursor salt, the catalyst is activated by aqueous solution of sodium hydroxide, hydrochloric acid, nitric acid, sulfuric acid or ferric trichloride at 20-100 ℃, and the preferred is sodium hydroxide, hydrochloric acid or ferric trichloride.
6. A preparation method of a peroxyacetic acid disinfectant is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
1) mixing hydrogen peroxide, a stabilizer and acetic acid or allowing single components to enter a rectifying tower; the stabilizer is sulfuric acid compounded with other stabilizers, and the other stabilizers are one or more than two of pyrophosphoric acid, sodium pyrophosphate, hydroxyethylidene diphosphonic acid, ethylene diamine tetraacetic acid, 8-hydroxyquinoline and pyridine-2, 6-dicarboxylic acid; the concentration of hydrogen peroxide is 5-50 wt%, the mass of acetic acid in the feed of the rectifying tower is 0.1-150% of hydrogen peroxide, the mass of stabilizer sulfuric acid is 1-5% of hydrogen peroxide, and the mass of other stabilizers is 0.001-3% of hydrogen peroxide.
2) The temperature of an evaporator of the rectifying tower is 35-100 ℃, the vacuum is maintained at 2000-5000 Pa, and the reflux ratio is (1-10): 1, the content of hydrogen peroxide in the effluent liquid at the tower top is 0.01-3 wt%;
3) mixing the mother liquor in the tower kettle, acetic acid and other stabilizers replenished for the second time, and feeding the mixture into a continuous flow microchannel reactor filled with a catalyst, wherein the mass of the acetic acid is 0.1-150% of the mother liquor, the dosage of the catalyst is 0.1-1% of the mass of the mother liquor, and the mass of the stabilizer is 0.001-0.1% of the mass of the mother liquor; the temperature of the reactor is 50-180 ℃, the pressure is 0.1-1.8 MPa, and the retention time is 1-280 s; the catalyst is the catalyst according to any one of claims 1 to 5;
4) the concentration of the peroxyacetic acid in the solution at the outlet of the reactor is 20-45 wt%, and preferably, the method further comprises the step of diluting the fraction of the rectifying tower, acetic acid and water and the high-concentration peroxyacetic acid on line to obtain the peroxyacetic acid disinfectant for disinfection.
7. The method of claim 6, wherein: in the step 1), the concentration of hydrogen peroxide is 20-50 wt%; the mass of acetic acid in the feed of the rectifying tower is 20-50% of hydrogen peroxide, preferably 25-35%; the mass of the stabilizer sulfuric acid is 1.5-4.6% of that of the hydrogen peroxide, preferably 2.5-3.5%; the mass of other stabilizers is 0.01-0.3% of the mass of hydrogen peroxide, preferably 0.05-0.25%.
8. The method of claim 6, wherein: in the step 2), the temperature of an evaporator is 50-80 ℃, preferably 65-75 ℃; the vacuum is maintained at 2500-4000 Pa, preferably 3000-3500 Pa; the reflux ratio is (2-7): 1, preferably (3-4): 1; the content of hydrogen peroxide in the effluent liquid at the tower top is 0.1-1 wt%, preferably 0.5-0.8 wt%.
9. The method of claim 6, wherein: in the step 3), the mass of the acetic acid is 50-140% of that of the mother liquor, preferably 75-100%; the amount of the catalyst is 0.5-1% of the mass of the mother liquor; the mass of other stabilizers is 0.01-0.05% of the mass of the mother liquor, preferably 0.03-0.04%; the temperature of the reactor is 80-170 ℃, preferably 100-140 ℃; the pressure is 0.25-1.6 MPa, preferably 0.7-1.3 MPa; the retention time is 5-200 s, preferably 30-70 s.
10. The method of claim 6, wherein: in the step 4), the concentration of the peroxyacetic acid in the solution at the outlet of the reactor is 25-40 wt%, preferably 30-37 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110186997.4A CN112958079A (en) | 2021-02-09 | 2021-02-09 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110186997.4A CN112958079A (en) | 2021-02-09 | 2021-02-09 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112958079A true CN112958079A (en) | 2021-06-15 |
Family
ID=76284975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110186997.4A Pending CN112958079A (en) | 2021-02-09 | 2021-02-09 | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958079A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101929089A (en) * | 2009-06-22 | 2010-12-29 | 北京西桥阳光科技有限公司 | Wet catalytic oxidation clean pulping process and equipment for implementing same |
| CN102616751A (en) * | 2012-02-10 | 2012-08-01 | 黎明化工研究院 | Method for synchronously synthesizing hydrogen peroxide and peroxyacetic acid |
| CN102669094A (en) * | 2012-05-09 | 2012-09-19 | 广州粤丰动物保健有限公司 | Stable corrosion-resistant peroxyacetic acid disinfectant and production method thereof |
| CN103170636A (en) * | 2013-04-17 | 2013-06-26 | 新疆大学 | Method for preparing nano metal simple substance through solid-state chemical reaction |
| CN108849893A (en) * | 2018-07-27 | 2018-11-23 | 佛山市南海东方澳龙制药有限公司 | Peroxyacetic acid disinfectant and preparation method thereof |
| US20190039057A1 (en) * | 2017-08-03 | 2019-02-07 | Board Of Trustees Of The University Of Arkansas | Metal catalyst, method of c-n coupling using the same and applications of the same |
| CN109321753A (en) * | 2018-11-27 | 2019-02-12 | 贵研资源（易门）有限公司 | Fail palladium catalyst green reclaim method |
| CN111084194A (en) * | 2019-12-31 | 2020-05-01 | 山东特姆化工科技有限公司 | Peracetic acid disinfectant and preparation method thereof |
| CN111233728A (en) * | 2020-03-18 | 2020-06-05 | 中国天辰工程有限公司 | Method for rapidly preparing high-concentration peroxyacetic acid |
| CN111333559A (en) * | 2020-03-18 | 2020-06-26 | 中国天辰工程有限公司 | Method for rapidly preparing peroxyacetic acid by continuous flow |
-
2021
- 2021-02-09 CN CN202110186997.4A patent/CN112958079A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101929089A (en) * | 2009-06-22 | 2010-12-29 | 北京西桥阳光科技有限公司 | Wet catalytic oxidation clean pulping process and equipment for implementing same |
| CN102616751A (en) * | 2012-02-10 | 2012-08-01 | 黎明化工研究院 | Method for synchronously synthesizing hydrogen peroxide and peroxyacetic acid |
| CN102669094A (en) * | 2012-05-09 | 2012-09-19 | 广州粤丰动物保健有限公司 | Stable corrosion-resistant peroxyacetic acid disinfectant and production method thereof |
| CN103170636A (en) * | 2013-04-17 | 2013-06-26 | 新疆大学 | Method for preparing nano metal simple substance through solid-state chemical reaction |
| US20190039057A1 (en) * | 2017-08-03 | 2019-02-07 | Board Of Trustees Of The University Of Arkansas | Metal catalyst, method of c-n coupling using the same and applications of the same |
| CN108849893A (en) * | 2018-07-27 | 2018-11-23 | 佛山市南海东方澳龙制药有限公司 | Peroxyacetic acid disinfectant and preparation method thereof |
| CN109321753A (en) * | 2018-11-27 | 2019-02-12 | 贵研资源（易门）有限公司 | Fail palladium catalyst green reclaim method |
| CN111084194A (en) * | 2019-12-31 | 2020-05-01 | 山东特姆化工科技有限公司 | Peracetic acid disinfectant and preparation method thereof |
| CN111233728A (en) * | 2020-03-18 | 2020-06-05 | 中国天辰工程有限公司 | Method for rapidly preparing high-concentration peroxyacetic acid |
| CN111333559A (en) * | 2020-03-18 | 2020-06-26 | 中国天辰工程有限公司 | Method for rapidly preparing peroxyacetic acid by continuous flow |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101810874B (en) | Sustained-release chlorine dioxide gel, preparation method and application thereof | |
| US20030235623A1 (en) | Aqueous disinfecting compositions with rapid bactericidal effect | |
| CN102140073A (en) | Cocoyl dimethyl ammonium iodine oxide complex | |
| EP1382666A1 (en) | Aqueous disinfecting compositions with rapid bactericidal effect | |
| CN111280189A (en) | Disinfectant for food industry and preparation method thereof | |
| CN103374127A (en) | Polyether polyol and iodine complex | |
| CN111838174A (en) | Hydrogen peroxide disinfectant and preparation method thereof | |
| GB2222081A (en) | Sterilising pharmaceutical formulations | |
| CN112958079A (en) | Catalyst for preparing peroxyacetic acid disinfectant and preparation method of disinfectant | |
| CN100411518C (en) | Antiseptics for improving hydrogen peroxide sterilizing activity and preparing process thereof | |
| CN103636674A (en) | Peracetic acid disinfectant and preparation method thereof | |
| CN207544970U (en) | A kind of domestic ozone microbubble vegetables and fruits cleaning machine | |
| CN101480197B (en) | Stable type disinfecting liquid and method for producing the same | |
| CN108013072B (en) | High-efficiency sterilizing disinfectant and preparation method thereof | |
| EP1375634A1 (en) | Aqueous disinfecting compositions with rapid bactericidal effect | |
| CN108047113A (en) | A kind of synthesis technology of Peracetic acid | |
| CN112825856A (en) | Method for quickly preparing peroxyacetic acid disinfectant by using low-concentration hydrogen peroxide | |
| CN107983145A (en) | A kind of Indoor Air Formaldehyde purification agent prescription and preparation method thereof | |
| CN113519555A (en) | Water-based low-toxicity bactericide and production method thereof | |
| CN110150287B (en) | Application of rutin in preventing and treating bemisia tabaci | |
| CN113548804A (en) | Composite antibacterial glass particles, preparation method thereof and sterilization device | |
| CN1128257A (en) | Solid chemicals for preparing peroxyacetic acid and its preparation method | |
| CN106756600A (en) | A kind of stainless steel antibacterial cool-bag | |
| CN111053184A (en) | Method for producing high-concentration ozone water | |
| CN112430508B (en) | Disinfectant powder atomizing device cleaning agent, application and cleaning method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210615 |