CN111387205A - Long-acting chlorine dioxide slow-release composite material and preparation method thereof - Google Patents
Long-acting chlorine dioxide slow-release composite material and preparation method thereof Download PDFInfo
- Publication number
- CN111387205A CN111387205A CN202010311686.1A CN202010311686A CN111387205A CN 111387205 A CN111387205 A CN 111387205A CN 202010311686 A CN202010311686 A CN 202010311686A CN 111387205 A CN111387205 A CN 111387205A
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- CN
- China
- Prior art keywords
- chlorine dioxide
- slow
- release
- stirring
- composite material
- 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.)
- Withdrawn
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 88
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000003756 stirring Methods 0.000 claims abstract description 79
- 239000004005 microsphere Substances 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 40
- 239000004964 aerogel Substances 0.000 claims abstract description 39
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 10
- 239000000741 silica gel Substances 0.000 claims abstract description 10
- 238000007605 air drying Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000003921 oil Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011240 wet gel Substances 0.000 claims description 24
- 239000004965 Silica aerogel Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 229940014259 gelatin Drugs 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- 229920000136 polysorbate Polymers 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000011975 tartaric acid Substances 0.000 claims description 8
- 235000002906 tartaric acid Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002535 acidifier Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229960001631 carbomer Drugs 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000003349 gelling agent Substances 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 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 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
- 239000000783 alginic acid Substances 0.000 claims description 2
- 229920000615 alginic acid Polymers 0.000 claims description 2
- 229960001126 alginic acid Drugs 0.000 claims description 2
- 150000004781 alginic acids Chemical class 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 235000010410 calcium alginate Nutrition 0.000 claims description 2
- 239000000648 calcium alginate Substances 0.000 claims description 2
- 229960002681 calcium alginate Drugs 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 claims description 2
- 235000010418 carrageenan Nutrition 0.000 claims description 2
- 239000000679 carrageenan Substances 0.000 claims description 2
- 229920001525 carrageenan Polymers 0.000 claims description 2
- 229940113118 carrageenan Drugs 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 2
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 2
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- 235000010408 potassium alginate Nutrition 0.000 claims description 2
- 239000000737 potassium alginate Substances 0.000 claims description 2
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229940083542 sodium Drugs 0.000 claims description 2
- 235000015424 sodium Nutrition 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 229940032147 starch Drugs 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 14
- 238000001179 sorption measurement Methods 0.000 description 23
- 239000000126 substance Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000000645 desinfectant Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000003607 modifier Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000002156 adsorbate Substances 0.000 description 4
- 150000002978 peroxides Chemical group 0.000 description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 4
- 229960002218 sodium chlorite Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- USSBDBZGEDUBHE-UHFFFAOYSA-L magnesium;2-oxidooxycarbonylbenzoate Chemical compound [Mg+2].[O-]OC(=O)C1=CC=CC=C1C([O-])=O USSBDBZGEDUBHE-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 230000000674 effect on sodium Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- -1 sorbitan fatty acid ester Chemical class 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Classifications
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of a long-acting chlorine dioxide slow-release composite material, which comprises the following steps: the method comprises the following steps: adding the adsorbent carrier into the chlorine dioxide aqueous solution, and uniformly stirring and mixing; then adding a slow-release catalyst, stirring and mixing uniformly, and air-drying to obtain the slow-release catalyst; the adsorbent carrier is one of silica gel, silicon dioxide aerogel microspheres and carbon nano tube/silicon dioxide composite aerogel microspheres. Compared with the prior art, the invention adopts the silicon dioxide aerogel microspheres as the adsorbent carrier to be matched with the slow-release catalyst, can stably and effectively realize the slow release of the chlorine dioxide, avoids the condition of overhigh local chlorine dioxide concentration caused by uneven release, and realizes the long-acting stable sterilization and disinfection effect.
Description
Technical Field
The invention belongs to the field of chlorine dioxide slow-release materials, and particularly relates to a long-acting chlorine dioxide slow-release composite material and a preparation method thereof.
Background
In recent years, along with the enhancement of environmental awareness and improvement of living standard of residents in China, people pay more and more attention to the problem of air pollution, particularly the problem of indoor air disinfection and purification. The main methods for air disinfection and purification include physical disinfection, chemical disinfection, plant adsorption, odor masking, etc. The most widely used method is chemical disinfection, that is, the chemical reagent is used to disinfect and purify the environment. The most widely used of these is peroxide disinfectants. Peroxide disinfectant which is the product ofActive oxygen is a generic term for a class of disinfectants with strong oxidizing and sterilizing capabilities. Peroxide disinfectants are mainly classified into the following categories: (1) activated hydrogen peroxide (H)2O2) Disinfection system, i.e. hydrogen peroxide disinfection system activated with catalyst, increasing hydrogen peroxide (H)2O2) The sterilization and disinfection effect of the method is that the catalyst is mainly metal ions or transition metal ions, salt and the like, and the method improves the method of simply using hydrogen peroxide (H)2O2) The disinfection effect is not obvious, and the reaction is slow. (2) Organic peroxide disinfectant, whose representative preparation is peroxyacetic acid (CH)3CO3H) Percarbamide (CO (NH)2)2·H2O, Magnesium Monoperoxyphthalate (MMPP). The preparation has certain sterilization and disinfection performance, but the sterilization and disinfection product can generate excessive harmful substances, the environmental protection performance is poor, the product stability is not high, and the performance is still to be further improved. (3) Inorganic peroxide disinfection systems, inorganic salts of peroxy acids, are widely available, and among them, the ones that have been considered for sterilization and disinfection in recent years are: chlorine dioxide (ClO)2) (ii) a Persulfates such as: potassium hydrogen peroxymonosulfate complex salt (2 KHSO)5·KHSO4-K2SO4) Potassium persulfate (K)2S2O8) Sodium persulfate (Na)2S2O8) Etc.; percarbonates such as: sodium percarbonate (2 Na)2CO3·3H2O2) And so on. Comprehensive comparison of chlorine dioxide (ClO)2) The disinfectant has good sterilizing performance, convenient use and wide application range, and has low toxicity, environmental protection and no residue, thereby meeting the requirements of modern people on the disinfectant.
Chlorine dioxide is yellow green gas at normal temperature and normal pressure, and has a slight irritation in smell, and is easily dissolved in water, its solubility in water at 20 deg.C is five times that of chlorine gas and is 107.9 g/L. the hydrolysis degree of chlorine dioxide in water is far less than that of chlorine gas, and the chlorine dioxide in the chlorine dioxide solution is still in molecular state.
Chlorine dioxide (ClO)2) At present, the disinfectant is internationally recognized as a safe, nontoxic and high-activity disinfectant, deodorant and disinfectant without causing three-cause effects (carcinogenesis, teratogenesis and mutagenesis) and residue after action, and is known as A1 grade disinfectant by the World Health Organization (WHO). In order to meet the application requirements of people, different chlorine dioxide formulations are developed, and stable chlorine dioxide solution and immobilized chlorine dioxide are mainly used. At present, the stable chlorine dioxide solution is very inconvenient to transport and store, and the application range of the stable chlorine dioxide solution is greatly limited. The immobilized chlorine dioxide has the problems of unstable release, short release period and the like at present.
CN 108751385a discloses a solid chlorine dioxide slow release material and a preparation method thereof, which adopts silica aerogel micro powder as a carrier material to realize physical isolation of sodium chlorite and solid acid, so as to control reaction rate and realize slow release of chlorine dioxide. However, the microporous structure of the silica aerogel micro powder is mostly nano-scale pore diameter, the adsorption effect on solid powder such as sodium chlorite is limited, the physical isolation effect on sodium chlorite and solid acid is limited, and the slow release effect of the prepared solid chlorine dioxide slow release material is not stable enough.
Therefore, the development of a long-acting chlorine dioxide slow-release composite material with stable slow-release effect is urgently needed.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method of a long-acting chlorine dioxide composite material, which can effectively solve the problem of unstable slow release effect of the chlorine dioxide composite material.
According to the invention, silica gel is adopted to efficiently adsorb the chlorine dioxide aqueous solution, and the slow-release catalytic material containing a gel agent, an acidifier and a passivator is adopted to wrap the chlorine dioxide aqueous solution adsorbed by the silica gel, so that a good environment can be provided for the stable slow release of chlorine dioxide, and the problem of long-term slow release of chlorine dioxide is effectively solved.
The technical scheme of the invention is as follows: a long-acting chlorine dioxide slow-release composite material comprises the following steps that an adsorbent carrier is added into a chlorine dioxide aqueous solution, stirred and mixed uniformly, and chemical adsorption is carried out; then adding the slow-release catalyst, stirring and mixing uniformly, and air-drying to obtain the catalyst.
Specifically, the preparation method of the long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding the adsorbent carrier into the chlorine dioxide aqueous solution, stirring for 24-72 h, and carrying out chemical adsorption;
s2, adding a slow-release catalyst, and continuously stirring for 20-60 min;
s3, air-drying the mixture obtained in the step S2 at room temperature for 1-6 hours to obtain the product.
Preferably, the mass volume ratio of the adsorbent carrier, the chlorine dioxide aqueous solution and the slow-release catalyst is 1 (1-3) to 0.1-0.8 g/m L/g;
preferably, the mass fraction of the chlorine dioxide aqueous solution is 0.5-1.2%.
Preferably, the adsorbent carrier is one of silica gel, silica aerogel microspheres, and carbon nanotube/silica composite aerogel microspheres.
Silica gel is silica gel mSiO2·nH2And O is properly dehydrated to form porous substances with different particle sizes. Has an open porous structure, has a large specific surface area (surface area per unit mass), can adsorb a plurality of substances, and is a good drying agent, adsorbent and catalyst carrier.
The silicon dioxide aerogel as a novel nano porous material is mainly composed of a nano particle framework with a three-dimensional nano network structure, and compared with the traditional material, the silicon dioxide aerogel has relatively high specific surface area and holes, and the average particle size is about dozens of nanometers. Most importantly, the fine pore diameter of the aerogel penetrates through the whole material, so that the adsorption performance of the aerogel is good, and the adsorption efficiency of the aerogel is superior to that of common activated carbon fibers and silica gel. Due to the shape, the solid irregular bulk material cannot be well filled in the application of chlorine dioxide aqueous solution adsorption slow release, and the using effect is not good. Therefore, the silica aerogel microspheres prepared by the invention can adsorb a large amount of chlorine dioxide aqueous solution, and realize long-acting stable release of chlorine dioxide by combining with a slow-release catalyst.
Preferably, the preparation method of the silica aerogel microspheres comprises the following steps:
y1 uniformly mixing 4.5-6.0 m L silica sol and 1-3 m L of 5-8 wt% nitric acid aqueous solution, adding 6-9 m L ethanol solution, and uniformly stirring in a 15-40 ℃ constant-temperature water bath to obtain a water phase;
y2, dripping 0.03-0.05 g of span 80 and 0.003-0.005 g of Tween 85 into 45-60 m of L n-heptane under the condition of stirring to obtain an emulsifier, adding 2-3 m of L n-butanol into the emulsifier, and stirring uniformly to obtain an oil phase;
y3, dropwise adding the water phase prepared by Y1 and the oil phase prepared by Y2 into the oil phase at a speed of 2-6 m L/min under the condition of stirring according to the volume ratio of 1 (4-8), and uniformly stirring to form a relatively stable W/O emulsion;
y4, dropwise adding 8-25% by mass of an ammonia water solution into the W/O emulsion under the stirring condition to enable the pH value to be 7.0, stopping stirring when the bottom of the beaker is turbid, filtering, washing obtained filter residues for 1-3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microspheres to obtain the wet gel microspheres;
y5, adding the wet gel microspheres into 25-35 m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 4-7 h at 50-65 ℃, filtering, taking filter residues, adding the filter residues into 25-35 m of L mass percent of 5-15% of trimethylchlorosilane normal hexane solution, standing for 4-7 h at 50-65 ℃, filtering, and vacuum drying for 4-10 h at 25-40 ℃ to obtain the silica aerogel microspheres.
The silica aerogel microspheres have good adsorption capacity, and adsorb a large amount of chlorine dioxide aqueous solution, so that the structure of the silica aerogel microspheres is easy to collapse, the stability of the chlorine dioxide aqueous solution in the silica aerogel microspheres is further influenced, and the slow release effect of the chlorine dioxide slow release composite material is further influenced. Therefore, the carbon nano tube and silicon dioxide aerogel composite material are compounded, so that the structural stability of the silicon dioxide aerogel is effectively improved, and the stable adsorption and the stable slow release of the chlorine dioxide aqueous solution are realized.
Preferably, the preparation method of the carbon nanotube/silica composite aerogel microspheres comprises the following steps:
x1 adding the carbon nano tube into ethanol according to the mass ratio of (0.3-0.8) to 100, and carrying out ultrasonic treatment to obtain carbon nano tube ethanol dispersion liquid;
uniformly mixing 4.5-6.0 m L silica sol and 1-3 m L of 5-8 wt% nitric acid aqueous solution by using X2, adding 6-9 m L of carbon nanotube ethanol dispersion prepared in the step X1, and uniformly stirring at 15-40 ℃ to obtain a water phase;
x3, dripping 0.03-0.05 g of span 80 and 0.003-0.005 g of Tween 85 into 45-60 m of L n-heptane under the condition of stirring to obtain an emulsifier, adding 2-3 m of L n-butanol into the emulsifier, and stirring uniformly to obtain an oil phase;
the volume ratio of the water phase prepared by X2 to the oil phase prepared by X3 of X4 is 1 (4-8), the water phase is added into the oil phase drop by drop at the speed of 2-6 m L/min under the condition of stirring, and the mixture is uniformly stirred to form a relatively stable W/O emulsion;
x5, dropwise adding 8-25% by mass of an ammonia water solution into the W/O emulsion under the stirring condition to enable the pH value to be 7.0, stopping stirring when the bottom of a beaker is turbid, filtering, washing obtained filter residues for 1-3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microspheres to obtain the wet gel microspheres;
x6 adding 5g of wet gel microspheres into 25-35 m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 4-7 h at 50-65 ℃, filtering, calcining filter residues for 2-5 h at 250-350 ℃, cooling to room temperature, adding into 25-35 m of L hydrophilic modifier, standing for 4-7 h at 50-65 ℃, filtering, and drying in vacuum for 4-10 h at 25-40 ℃ to obtain the carbon nanotube/silicon dioxide composite aerogel microspheres, wherein the hydrophilic modifier is prepared by uniformly mixing 5-15 wt% of hexadecyl trimethyl ammonium bromide, 5-15 wt% of tetrabutylammonium fluoride and the balance of water.
Preferably, the slow-release catalyst is prepared by uniformly stirring and mixing 20-40 wt% of a gelling agent, 30-60 wt% of a passivating agent, 1-8 wt% of an acidifying agent and the balance of water.
Preferably, the gelling agent is one or a mixture of more than two of gelatin, carbomer, carrageenan, microcrystalline cellulose, hydroxypropyl methylcellulose, dextrin, sodium carboxymethyl starch, polyethylene glycol 4000, polyethylene glycol 6000, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, alginic acid, sodium alginate, calcium alginate, potassium alginate and carbomer.
Preferably, the passivating agent is one of sodium chloride, potassium chloride, calcium chloride and sodium stearate; the acidifier is one of oxalic acid, tartaric acid, stearic acid and ethylenediamine tetraacetic acid.
The invention also discloses a long-acting chlorine dioxide slow-release composite material which is prepared by adopting the method.
The invention has the beneficial effects that:
compared with the prior art, the invention adopts silica gel, silica aerogel microspheres, carbon nano tube/silica composite aerogel microspheres to match with the sustained-release catalyst to stably adsorb and wrap chlorine dioxide, realizes the stable and slow release of chlorine dioxide, and effectively solves the problems of poor adsorption effect and unstable sustained-release effect of the immobilized sodium chlorite similar technology.
The invention also improves the silicon dioxide aerogel microspheres through the carbon nano tubes, effectively solves the problems of unstable structure and easy collapse of the silicon dioxide aerogel microspheres after water absorption, improves the stability of the silicon dioxide aerogel microspheres after water absorption, and realizes long-acting stable chlorine dioxide slow release.
Detailed Description
The specific parameters of some substances in the embodiment of the invention are as follows:
carbon nanotube, type TNNF-6, external diameter 10-20nm, length 5-20nm, Chinese academy of sciences organic chemistry, Inc.
Silica sol, cat No. JN5-20/1, content 20 ± 1%, brand: deliki, Zhejiang Deliki micro-nano technology, Inc.
Span 80, also known as sorbitan fatty acid ester, CAS number: 1338-43-8.
Tween 85, CAS No.: 9005-70-3.
Cetyl trimethylammonium bromide, CTAB, CAS number: 57-09-0.
Tetrabutylammonium fluoride, CAS No.: 429-41-4.
Gelatin, CAS No.: 9000-70-8, cat number: 102, brand, xin fushend, jiangsu fushend bioengineering, ltd.
Trimethylchlorosilane, CAS number: 75-77-4.
Example 1
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of silica gel and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Experimental data prove that the long-acting chlorine dioxide slow-release composite material can kill 99.6 percent of influenza A virus H1N1 in 1 hour, 99.9 percent of white staphylococcus in 2 hours, 99.4 percent of air natural bacteria in 24 hours, and the average virus and bacteria killing rate is over 99.5 percent. (remark: 1 hour experimental method briefly: laying 125g of long-acting chlorine dioxide slow-release composite material on 1m3Carrying out an experiment in the test chamber; brief description of the 2 hour experimental procedure: in space 1m3In the test cabinet, namely under the condition of laboratory test, 125g of long-acting chlorine dioxide slow-release composite material is flatly paved in a cabin for 2 hours, a liquid impact type microorganism aerosol sampler is used for sampling at the flow rate of 11L/min, the volume of the sampling liquid is 20m L, the sampling time of the test group and the control group is 2min, and the result of the kill rate test eliminates the natural cause of death of microorganisms in the airThe 24-hour experimental method briefly comprises the steps of paving 125g of oxygen long-acting chlorine dioxide slow-release composite material in an experimental cabin for acting for 2 hours, sampling by using a sieve mesh impact type six-grade air microorganism sampler JW L-6 with the air draft of 28.3 liters/minute, wherein the sampling time is 5min, and the sampling space size is 1m3。)
Example 2
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of silicon dioxide composite aerogel microspheres and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The preparation method of the silicon dioxide composite aerogel microspheres comprises the following steps:
y1 transferring 5.5m L silica sol and 2m L of 6% nitric acid aqueous solution, mixing uniformly, slowly adding 8m L ethanol solution, and stirring uniformly in 30 ℃ constant temperature water bath to obtain a water phase;
y2 transferring 50m L n-heptane into a beaker, adding 0.04g span 80 and 0.004g tween 85 under the stirring condition, uniformly stirring at 1000rpm to obtain an emulsifier, adding 2.5m L n-butanol into the emulsifier, and mechanically stirring at 1000rpm for 30min to obtain a uniform oil phase;
y3 dropwise adding the water phase into the oil phase at a speed of 3m L/min by using the water phase prepared by Y1 and the oil phase prepared by Y2 according to a volume ratio of 1:6, and mechanically stirring at a rotating speed of 1000rpm for 30min to rapidly and uniformly disperse the water phase to form a relatively stable W/O emulsion;
y4, dropwise adding an ammonia water solution with the mass fraction of 10% into the W/O emulsion under the condition of 1000rpm to enable the pH value to be about 7, stopping stirring when a little turbidity appears at the bottom of a beaker, filtering, washing obtained filter residues for 3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y5, adding 5g of wet gel microspheres into 30m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 6 hours at 60 ℃, filtering, taking filter residues, adding the filter residues into 30m of L mass percent of 10% of trimethylchlorosilane normal hexane solution, standing for 6 hours at 60 ℃, filtering, and drying in vacuum for 6 hours at 30 ℃ to obtain the silicon dioxide aerogel microspheres.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Example 3
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of carbon nano tube/silicon dioxide composite aerogel microspheres and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The preparation method of the carbon nano tube/silicon dioxide composite aerogel microspheres comprises the following steps:
y1 adding carbon nano tubes into ethanol according to the mass ratio of 0.6:100, and carrying out ultrasonic treatment for 30min under the conditions of ultrasonic power of 300W and ultrasonic frequency of 30kHz to obtain carbon nano tube ethanol dispersion liquid;
y2 is prepared by mixing 5.5m L silica sol with 2m L of 6% nitric acid aqueous solution, adding 8m L of carbon nanotube ethanol dispersion prepared in step Y1, and stirring at 30 deg.C to obtain water phase;
y3 putting 50m L n-heptane in a beaker, adding 0.04g span 80 and 0.004g Tween 85 under the condition of stirring, and stirring uniformly at 1000rpm to obtain an emulsifier, adding 2.5m L n-butanol in the emulsifier, and mechanically stirring at 1000rpm for 30min to obtain a uniform oil phase;
y4 dropwise adding the water phase into the oil phase at a speed of 3m L/min by using the water phase prepared by Y2 and the oil phase prepared by Y3 according to a volume ratio of 1:6, and mechanically stirring at a rotating speed of 1000rpm for 30min to rapidly and uniformly disperse the water phase to form a relatively stable W/O emulsion;
y5, dropwise adding an ammonia water solution with the mass fraction of 10% into the W/O emulsion under the condition of 1000rpm to enable the pH value to be 7.0, stopping stirring when a little turbidity appears at the bottom of a beaker, filtering, washing obtained filter residues for 3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y6, adding 5g of wet gel microspheres into 30m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 6h at 60 ℃, filtering, taking filter residues, calcining for 3h at 300 ℃, cooling to room temperature, adding into 30m of L10 wt% of trimethylchlorosilane normal hexane solution, standing for 6h at 60 ℃, filtering, and vacuum drying for 6h at 30 ℃ to obtain the carbon nanotube/silicon dioxide composite aerogel microspheres.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Example 4
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of carbon nano tube/silicon dioxide composite aerogel microspheres and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The preparation method of the carbon nano tube/silicon dioxide composite aerogel microspheres comprises the following steps:
y1 adding carbon nano tubes into ethanol according to the mass ratio of 0.6:100, and carrying out ultrasonic treatment for 30min under the conditions of ultrasonic power of 300W and ultrasonic frequency of 30kHz to obtain carbon nano tube ethanol dispersion liquid;
y2 is prepared by mixing 5.5m L silica sol with 2m L of 6% nitric acid aqueous solution, adding 8m L of carbon nanotube ethanol dispersion prepared in step Y1, and stirring at 30 deg.C to obtain water phase;
y3 putting 50m L n-heptane in a beaker, adding 0.04g span 80 and 0.004g Tween 85 under the condition of stirring, and stirring uniformly at 1000rpm to obtain an emulsifier, adding 2.5m L n-butanol in the emulsifier, and mechanically stirring at 1000rpm for 30min to obtain a uniform oil phase;
y4 dropwise adding the water phase into the oil phase at a speed of 3m L/min by using the water phase prepared by Y2 and the oil phase prepared by Y3 according to a volume ratio of 1:6, and mechanically stirring at a rotating speed of 1000rpm for 30min to rapidly and uniformly disperse the water phase to form a relatively stable W/O emulsion;
y5, dropwise adding an ammonia water solution with the mass fraction of 10% into the W/O emulsion under the condition of 1000rpm to enable the pH value to be 7.0, stopping stirring when a little turbidity appears at the bottom of a beaker, filtering, washing obtained filter residues for 3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y6, adding 5g of wet gel microspheres into 30m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 6h at 60 ℃, filtering, calcining filter residues for 3h at 300 ℃, cooling to room temperature, adding into 30m of L of hydrophilic modifier, standing for 6h at 60 ℃, filtering, and vacuum drying for 6h at 30 ℃ to obtain the carbon nanotube/silicon dioxide composite aerogel microspheres, wherein the hydrophilic modifier is 20 wt% of hexadecyl trimethyl ammonium bromide aqueous solution.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Example 5
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of carbon nano tube/silicon dioxide composite aerogel microspheres and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The preparation method of the carbon nano tube/silicon dioxide composite aerogel microspheres comprises the following steps:
y1 adding carbon nano tubes into ethanol according to the mass ratio of 0.6:100, and carrying out ultrasonic treatment for 30min under the conditions of ultrasonic power of 300W and ultrasonic frequency of 30kHz to obtain carbon nano tube ethanol dispersion liquid;
y2 is prepared by mixing 5.5m L silica sol with 2m L of 6% nitric acid aqueous solution, adding 8m L of carbon nanotube ethanol dispersion prepared in step Y1, and stirring at 30 deg.C to obtain water phase;
y3 putting 50m L n-heptane in a beaker, adding 0.04g span 80 and 0.004g Tween 85 under the condition of stirring, and stirring uniformly at 1000rpm to obtain an emulsifier, adding 2.5m L n-butanol in the emulsifier, and mechanically stirring at 1000rpm for 30min to obtain a uniform oil phase;
y4 dropwise adding the water phase into the oil phase at a speed of 3m L/min by using the water phase prepared by Y2 and the oil phase prepared by Y3 according to a volume ratio of 1:6, and mechanically stirring at a rotating speed of 1000rpm for 30min to rapidly and uniformly disperse the water phase to form a relatively stable W/O emulsion;
y5, dropwise adding an ammonia water solution with the mass fraction of 10% into the W/O emulsion under the condition of 1000rpm to enable the pH value to be 7.0, stopping stirring when a little turbidity appears at the bottom of a beaker, filtering, washing obtained filter residues for 3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y6, adding 5g of wet gel microspheres into 30m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 6h at 60 ℃, filtering, calcining filter residues for 3h at 300 ℃, cooling to room temperature, adding into 30m of L of hydrophilic modifier, standing for 6h at 60 ℃, filtering, and vacuum drying for 6h at 30 ℃ to obtain the carbon nanotube/silicon dioxide composite aerogel microspheres, wherein the hydrophilic modifier is 20 wt% of tetrabutylammonium fluoride aqueous solution.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Example 6
A preparation method of a long-acting chlorine dioxide slow-release composite material comprises the following steps:
s1, adding 1Kg of carbon nano tube/silicon dioxide composite aerogel microspheres and 2L mass percent of 0.8 wt% of chlorine dioxide aqueous solution into a stainless steel container, stirring for 48 hours at 15 ℃, at the rotating speed of 200rpm and under the sealed condition, and carrying out chemical adsorption;
s2 adding 0.5Kg of slow-release catalyst into a stainless steel container, and continuously stirring for 30min at 15 ℃ and at the rotating speed of 200rpm under the sealed condition;
s3, drying the mixture obtained in the step S2 in an air dryer for 1 hour to obtain the product.
The preparation method of the carbon nano tube/silicon dioxide composite aerogel microspheres comprises the following steps:
y1 adding carbon nano tubes into ethanol according to the mass ratio of 0.6:100, and carrying out ultrasonic treatment for 30min under the conditions of ultrasonic power of 300W and ultrasonic frequency of 30kHz to obtain carbon nano tube ethanol dispersion liquid;
y2 is prepared by mixing 5.5m L silica sol with 2m L of 6% nitric acid aqueous solution, adding 8m L of carbon nanotube ethanol dispersion prepared in step Y1, and stirring at 30 deg.C to obtain water phase;
y3 putting 50m L n-heptane in a beaker, adding 0.04g span 80 and 0.004g Tween 85 under the condition of stirring, and stirring uniformly at 1000rpm to obtain an emulsifier, adding 2.5m L n-butanol in the emulsifier, and mechanically stirring at 1000rpm for 30min to obtain a uniform oil phase;
y4 dropwise adding the water phase into the oil phase at a speed of 3m L/min by using the water phase prepared by Y2 and the oil phase prepared by Y3 according to a volume ratio of 1:6, and mechanically stirring at a rotating speed of 1000rpm for 30min to rapidly and uniformly disperse the water phase to form a relatively stable W/O emulsion;
y5, dropwise adding an ammonia water solution with the mass fraction of 10% into the W/O emulsion under the condition of 1000rpm to enable the pH value to be 7.0, stopping stirring when a little turbidity appears at the bottom of a beaker, filtering, washing obtained filter residues for 3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y6, adding 5g of wet gel microspheres into 30m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 6h at 60 ℃, filtering, calcining filter residues for 3h at 300 ℃, cooling to room temperature, adding into 30m of L of hydrophilic modifier, standing for 6h at 60 ℃, filtering, and drying in vacuum for 6h at 30 ℃ to obtain the carbon nanotube/silicon dioxide composite aerogel microspheres, wherein the hydrophilic modifier is 10 wt% of hexadecyl trimethyl ammonium bromide, 10 wt% of tetrabutyl ammonium fluoride and the balance of water, and uniformly mixing.
The slow-release catalyst is prepared by uniformly stirring and mixing 160g of gelatin, 250g of sodium chloride, 20g of tartaric acid and 70g of water.
Test example 1
Chlorine dioxide release rate detection method
A40 g sample was contained in a controlled release bottle (total area of release holes 1.2 cm)2) The chlorine dioxide is put into a 5L glass dryer with an air inlet hole and an air outlet hole, an air sampler is used for collecting air in the glass dryer at the flow rate of 200m L/min, the air is absorbed by a pirox solution, and the release rate of the chlorine dioxide is calculated by a fluorescence spectrometry test.
Chlorine dioxide Release Rate test results of Table 1
As can be seen from table 1, the chlorine dioxide slow release effect of the long-acting chlorine dioxide slow release composite material prepared by using the carbon nanotube/silica composite aerogel microspheres is obviously better than that of the long-acting chlorine dioxide slow release composite material prepared by using the silica aerogel microspheres. The reason for this may be: the silica aerogel adsorbs a large amount of chlorine dioxide aqueous solution, so that the structure is easy to collapse, and the stability of the chlorine dioxide aqueous solution in the silica aerogel microspheres is further influenced; the adoption of the carbon nano tube/silicon dioxide aerogel can effectively improve the structural stability of the silicon dioxide aerogel and improve the chlorine dioxide slow-release compound
The slow release stability of the composite material.
Test example 2
Specific surface area test
The prepared silica aerogel microspheres and carbon nanotube/silica composite aerogel microspheres were analyzed for nitrogen adsorption-desorption curve, specific surface area, pore size distribution, etc. by nitrogen adsorption-desorption using an AUTOSORB-IQ type chemisorption instrument manufactured by ita corporation, usa. The method comprises the following basic steps: liquid nitrogen gas is used as an adsorbate, and an adsorption and desorption test is carried out on the adsorbate at 77K. Before measurement, a sample is subjected to vacuum degassing at a set temperature value (120 ℃) for at least 6 hours, points are taken within a range of relative pressure (P/Po) of 0.0001-0.9990 when the sample is tested, and the specific surface area of the sample to be measured is calculated by adopting a BET method; calculating the total pore volume of the test sample according to the adsorption amount corresponding to the maximum value of the relative pressure; and calculating the pore size distribution of the test sample and the corresponding pore volume Vt by a density function theory, namely a DFT method. Wherein the BET adsorption isotherm equation is as follows:
in the formula: v, gas adsorption capacity; vmSaturated adsorption capacity of the monolayer; p, adsorbate pressure; p0The adsorbate saturation vapor pressure; c, constant.
The adsorption quantity V of the monolayer can be obtainedmThereby calculating the specific surface area S of the sampleBET. Order to
Plotting Y against X, making a straight line, Y ═ AX + B, and substituting formula 4 and formula 5 into the straight line, 1/(oblique)Rate + intercept) ═ VmAnd substituting:
in the formula: vmSaturated adsorption amount of monolayer (m L), W, adsorbent mass (g), SBETSpecific surface area, (m)2/g)。
Table 2: specific surface area test results
| Specific surface area (m)2/g) | |
| Example 2 | 279 |
| Example 3 | 320 |
As can be seen from Table 2, the specific surface area of the carbon nanotube/silica composite aerogel microspheres prepared by the method of the present invention is significantly larger than the specific surface area of the silica aerogel microspheres.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the long-acting chlorine dioxide slow-release composite material is characterized by comprising the following steps of: adding the adsorbent carrier into the chlorine dioxide aqueous solution, and uniformly stirring and mixing; then adding the slow-release catalyst, stirring and mixing uniformly, and air-drying to obtain the catalyst.
2. The method for preparing a long-acting chlorine dioxide slow-release composite material according to claim 1, comprising the steps of:
s1, adding the adsorbent carrier into the chlorine dioxide aqueous solution, and stirring for 24-72 h;
s2, adding a slow-release catalyst, and continuously stirring for 20-60 min;
s3, air-drying the mixture obtained in the step S2 at room temperature for 1-6 hours to obtain the product.
3. The preparation method of the long-acting chlorine dioxide slow-release composite material as claimed in claim 1 or 2, wherein the mass volume ratio of the adsorbent carrier, the chlorine dioxide aqueous solution and the slow-release catalyst is 1 (1-3) to (0.1-0.8) g/m L/g.
4. A method for preparing a long-acting chlorine dioxide slow-release composite material as claimed in claim 1 or 2, characterized in that: the mass fraction of the chlorine dioxide aqueous solution is 0.5-1.2%.
5. A method for preparing a long-acting chlorine dioxide slow-release composite material as claimed in claim 1 or 2, characterized in that: the adsorbent carrier is one of silica gel, silicon dioxide aerogel microspheres and carbon nano tube/silicon dioxide composite aerogel microspheres.
6. The preparation method of the long-acting chlorine dioxide slow-release composite material according to claim 5, wherein the preparation method of the silica aerogel microspheres comprises the following steps:
y1 uniformly mixing 4.5-6.0 m L silica sol and 1-3 m L of 5-8 wt% nitric acid aqueous solution, adding 6-9 m L ethanol solution, and uniformly stirring in a 15-40 ℃ constant-temperature water bath to obtain a water phase;
y2, dripping 0.03-0.05 g of span 80 and 0.003-0.005 g of Tween 85 into 45-60 m of L n-heptane under the condition of stirring to obtain an emulsifier, adding 2-3 m of L n-butanol into the emulsifier, and stirring uniformly to obtain an oil phase;
y3 dropwise adding the water phase prepared by Y1 and the oil phase prepared by Y2 into the oil phase at a speed of 2-6 m L/min under the condition of stirring according to the volume ratio of 1 (4-8), and uniformly stirring to form a relatively stable W/O emulsion;
y4, dropwise adding 8-25% by mass of an ammonia water solution into the W/O emulsion under the stirring condition to enable the pH value to be 7, stopping stirring when a little turbidity appears at the bottom of the beaker, filtering, washing obtained filter residues for 1-3 times by using acetone, and removing an oil phase, ammonia water and the like on the surface of the wet gel microsphere to obtain the wet gel microsphere;
y5, adding 5g of wet gel microspheres into 25-35 m of L ethyl orthosilicate/ethanol solution (V/V is 1:3), standing for 4-7 h at 50-65 ℃, filtering, taking filter residues, adding the filter residues into 25-35 m of L n-hexane solution with the mass fraction of 5-15% of trimethylchlorosilane, standing for 4-7 h at 50-65 ℃, filtering, and vacuum-drying for 4-10 h at 25-40 ℃ to obtain the silica aerogel microspheres.
7. A method for preparing a long-acting chlorine dioxide slow-release composite material as claimed in claim 1 or 2, characterized in that: the slow-release catalyst is prepared by uniformly stirring and mixing 20-40 wt% of a gelling agent, 30-60 wt% of a passivating agent, 1-8 wt% of an acidifying agent and the balance of water.
8. A method of preparing a long-acting chlorine dioxide slow release composite material as claimed in claim 7, wherein: the gel is one or more of gelatin, carbomer, carrageenan, microcrystalline cellulose, hydroxypropyl methylcellulose, dextrin, sodium carboxymethyl starch, polyethylene glycol 4000, polyethylene glycol 6000, sodium carboxymethyl cellulose, calcium carboxymethyl cellulose, alginic acid, sodium alginate, calcium alginate, potassium alginate and carbomer.
9. A method of preparing a long-acting chlorine dioxide slow release composite material as claimed in claim 7, wherein: the passivating agent is one of sodium chloride, potassium chloride, calcium chloride and sodium stearate; the acidifier is one of oxalic acid, tartaric acid, stearic acid and ethylenediamine tetraacetic acid.
10. A long-acting chlorine dioxide slow-release composite material, which is prepared by the method of any one of claims 1 to 9.
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