EP4143130A1 - Wässerige chlordioxid-lösungen und verfahren zur herstellung derselben - Google Patents
Wässerige chlordioxid-lösungen und verfahren zur herstellung derselbenInfo
- Publication number
- EP4143130A1 EP4143130A1 EP21722186.0A EP21722186A EP4143130A1 EP 4143130 A1 EP4143130 A1 EP 4143130A1 EP 21722186 A EP21722186 A EP 21722186A EP 4143130 A1 EP4143130 A1 EP 4143130A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- chlorine dioxide
- solution
- aqueous
- chlorine
- sodium
- 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- Withdrawn
Links
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 446
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 224
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 222
- 238000000034 method Methods 0.000 title claims abstract description 110
- 230000000249 desinfective effect Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 139
- 230000008569 process Effects 0.000 claims description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000000460 chlorine Substances 0.000 claims description 29
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 26
- 229910052801 chlorine Inorganic materials 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 26
- 239000012159 carrier gas Substances 0.000 claims description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims description 24
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 20
- -1 alkaline earth metal salts Chemical class 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000007853 buffer solution Substances 0.000 claims description 11
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 11
- 229960002218 sodium chlorite Drugs 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 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 description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 241000700605 Viruses Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000008363 phosphate buffer Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 abstract description 6
- 229940099041 chlorine dioxide Drugs 0.000 abstract 11
- 238000004519 manufacturing process Methods 0.000 description 28
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 22
- 238000001816 cooling Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910001919 chlorite Inorganic materials 0.000 description 15
- 229910052619 chlorite group Inorganic materials 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 12
- 238000009835 boiling Methods 0.000 description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000645 desinfectant Substances 0.000 description 7
- 239000003651 drinking water Substances 0.000 description 7
- 235000020188 drinking water Nutrition 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 230000002452 interceptive effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229920006328 Styrofoam Polymers 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000008261 styrofoam Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- SBKUYFKOKNBHGB-UHFFFAOYSA-N Cl.O[Cl]=O Chemical compound Cl.O[Cl]=O SBKUYFKOKNBHGB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000009621 Solvay process Methods 0.000 description 2
- JJHVYBKFCASXME-UHFFFAOYSA-M [Cl+].[O-]Cl=O Chemical compound [Cl+].[O-]Cl=O JJHVYBKFCASXME-UHFFFAOYSA-M 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 229940127554 medical product Drugs 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 208000025721 COVID-19 Diseases 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 210000000003 hoof Anatomy 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000282 nail Anatomy 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/028—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/026—Preparation from chlorites or chlorates from chlorate ions in the presence of a peroxidic compound, e.g. hydrogen peroxide, ozone, peroxysulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Definitions
- the present invention relates to aqueous chlorine dioxide-containing solutions, in particular high-purity aqueous chlorine dioxide solutions which can be used, for example, in the field of human and veterinary medicine for disinfecting surfaces, devices and instruments, as well as a method for producing such aqueous chlorine dioxide solutions.
- the present invention provides a method for preparing an aqueous chlorine dioxide solution, in which a previously prepared aqueous chlorine dioxide solution is treated so that a high-purity aqueous chlorine dioxide solution is obtained.
- the method according to the invention can be applied to all previously prepared aqueous chlorine dioxide solutions, regardless of the method with which the previously prepared aqueous chlorine dioxide solution has been prepared.
- aqueous chlorine dioxide solutions can be produced far more simply and cost-effectively from previously produced aqueous chlorine dioxide solutions. It has surprisingly been found that the aqueous chlorine dioxide solutions obtainable with the process according to the invention have a high purity and a surprisingly high stability.
- Chlorine dioxide and aqueous chlorine dioxide solutions have long been known as very effective bleaching and disinfecting agents and are used on a large scale, for example, as bleaching agents for pulp bleaching (e.g. in paper production) and as disinfectants for disinfecting drinking water. Due to known problems in the production and storage of chlorine dioxide and aqueous solutions containing it (risk of explosion!), The technical production of chlorine dioxide usually takes place immediately before use from chlorate (CIO3) or chlorite (CIO 2 ), or the corresponding salts thereof, such as the corresponding alkali salts (e.g. sodium chlorate and sodium chlorite).
- chlorate CIO3
- chlorite CIO 2
- the corresponding salts thereof such as the corresponding alkali salts (e.g. sodium chlorate and sodium chlorite).
- Chlorates especially sodium chlorate, are used as an inexpensive starting material for the production of bleaches on an industrial scale, for example sulfur dioxide (Mathieson process) or hydrochloric acid or methanol (Solvay process) being used for chlorate reduction.
- chlorine dioxide is produced from more expensive chlorite, such as sodium chlorite, whereby for chlorite oxidation, for example, chlorine (chlorine- Chlorite process), a suitable acid (acid-chlorite process), such as hydrochloric acid (hydrochloric acid-chlorite process) or a suitable oxidizing agent, such as peroxodisulfate (peroxodisulfate-chlorite process) or electric current (chlorite electrolysis process ) be used.
- chlorite oxidation for example, chlorine (chlorine- Chlorite process), a suitable acid (acid-chlorite process), such as hydrochloric acid (hydrochloric acid-chlorite process) or a suitable oxidizing agent, such as peroxodisulfate (peroxodisulfate-chlorite process) or electric current (chlorite electrolysis process ) be used.
- aqueous chlorine dioxide solutions are also used in human and veterinary medicine as well as general hygiene, such as for the disinfection of surfaces, devices, instruments and the like in doctor's offices, hospitals, laboratories, vehicles, etc. Especially for such applications in the field of medicine, it is necessary that the aqueous chlorine dioxide solutions used are as free as possible of impurities and have sufficient storage stability, which enable appropriate storage and logistics. Due to the distribution channels via wholesalers and retailers as well as intermediate storage or stock keeping at the end consumer, storage stability of 18 to 24 months is a basic economic prerequisite.
- a product that can be realized from an economic point of view particularly requires long-term and stable storage in commercially available packaging without any special additional effort, such as the need for a continuous cold chain or the like.
- a high degree of purity of the chlorine dioxide solutions is required in order to avoid undesirable reactions with surfaces to be treated (e.g. corrosion, etc.) or with organic materials present on them (e.g. formation of toxic chlorinated organic compounds, etc.) .ä.), as well as to avoid the possible formation of harmful residues.
- the aim is to reduce potentially harmful impurities.
- toxic and environmentally harmful impurities should be avoided as completely as possible.
- the permissible limit value and thus also the permissible manufacturing method are significantly influenced by the (expected) residue of chlorates.
- the methods permitted for drinking water disinfection and the substances to be used in them are specified in detail.
- the environmental compatibility of chlorine dioxide products depends to a considerable extent on the chlorine they contain, since chlorine, for example, can also react with organic compounds to form toxic or otherwise environmentally harmful chlorinated organic compounds.
- GB 760,303 A describes a process for producing aqueous chlorine dioxide solutions, in which gaseous chlorine dioxide produced in a reaction zone is enriched in an inert gas flow and the gas flow is then passed into water in order to produce an aqueous chlorine dioxide solution.
- the disadvantage of this process is that undesired gases which are used or are created in the production of the gaseous chlorine dioxide, such as chlorine and / or sulfur dioxide, are also introduced into the chlorine dioxide solution produced and are enriched there.
- a chlorine dioxide solution produced by this process therefore contains undesired gases, in particular chlorine.
- US 2010/0209528 A1 describes a method for producing aqueous chlorine dioxide solutions in which dilute chlorine gas is passed through a bed of essentially solid sodium chlorite and then introduced into water in order to produce chlorine dioxide solutions which contain little sodium chloride.
- sodium chloride has a negative effect on the stability of aqueous chlorine dioxide solutions.
- the chlorites required for the process are relatively expensive and the chlorine dioxide solutions produced contain chlorine gas, which not only accelerates the decomposition of chlorine dioxide, but can also react with organic compounds to form toxic chlorinated organic compounds.
- the use of chlorine gas necessitates considerable safety precautions, which in (large-scale) practice necessitates expensive equipment.
- WO 2019/180049 A1 describes a method for producing aqueous chlorine dioxide solutions in which chlorine dioxide is produced from chlorites using a method known from drinking water disinfection and is introduced into water via an inert gas stream in order to produce an aqueous chlorine dioxide solution.
- suitable chlorine-free oxidizing agents such as, for example, peroxodisulfate
- this process can be used to produce aqueous chlorine dioxide solutions that contain little chlorine and salts.
- this requires relatively expensive chlorite as the starting product, as well as larger quantities of process chemicals and extremely complex equipment.
- the inventor of the present invention has found that storable aqueous chlorine dioxide solutions can be produced inexpensively on a large scale if existing chlorine dioxide solutions - regardless of their original production method - are treated in such a way that a highly pure aqueous chlorine dioxide solution is obtained.
- an aqueous chlorine dioxide solution is particularly stable and therefore storable if particularly impurities in the form of salts and reactive gases are reduced as far as possible in the process, so that the solution has a high degree of purity. It is believed that such impurities accelerate the decomposition of the dissolved chlorine dioxide.
- Aqueous chlorine dioxide solutions produced according to the present invention have a good shelf life of 18 to 24 months even without cooling.
- the present invention thus provides a fundamental solution to the problem of producing high-purity chlorine dioxide solutions by providing a general process for the purification of (already present) chlorine dioxide solutions which, regardless of the original production method, is an even further improved, purer one Final product supplies.
- the present invention takes the path of first removing the interfering gases by reaction (e.g. by reducing them to ionic compounds) or preventing their formation through intermittent decomposition of the chlorine dioxide or other impurities, regardless of the starting product, and then desalinating the intermediate product obtained.
- reaction e.g. by reducing them to ionic compounds
- this above offers considerable economic advantages.
- the present invention provides a method of making a purified aqueous solution of chlorine dioxide.
- the method according to the invention comprises the following steps:
- HCIO hypochlorous acid
- HCIO3 chloric acid
- SO2 sulfur dioxide
- the method according to the invention can be used according to the invention for treating (cleaning) aqueous chlorine dioxide solutions of any origin - regardless of the original production method of the first aqueous chlorine dioxide solution provided in step (1).
- chlorite-based processes or indirect processes
- Chlorite process via electrolysis can be used, but also the much cheaper chlorate-based processes.
- the large-scale plants already available in the paper industry can be used to produce the first aqueous chlorine dioxide solution provided in step (1).
- the first chlorine dioxide solution can be obtained by reacting a chlorate salt with sulfur dioxide (Mathieson method), by reacting a chlorate salt with hydrochloric acid or methanol (Solvay method), by reacting a chlorite Salt with an acid (acid-chlorite process or acid-hypochlorite-chlorite process), for example hydrochloric acid (hydrochloric acid-chlorite process), by reaction of a chlorite salt with chlorine (chlorine-chlorite process), by reaction from a chlorite salt with sodium peroxodisulfate (peroxodisulfate-chlorite process) or by electrochemical processes (e.g. chlorite electrolysis process or chlorite electrolysis process).
- the first chlorine dioxide solution is preferably produced from a chlorate salt, particularly preferably sodium chlorate.
- the first aqueous chlorine dioxide solution can be provided in step (1) either with a certain volume or continuously.
- the first chlorine dioxide solution provided in step (1) can be connected via a suitable siphon to a primary production device for chlorine dioxide, so that continuously post-produced chlorine dioxide solution is available as a source for the process according to the invention, which can then be carried out continuously.
- an aqueous chlorine dioxide solution (sometimes also referred to as an aqueous solution of chlorine dioxide) is a composition which is based on water as a solvent and which comprises chlorine dioxide in dissolved form.
- this first chlorine dioxide solution comprises not only chlorine dioxide but also unreacted starting materials, further reaction products (by-products) and / or decomposition products, such as dissolved ones Chlorite ions, hypochlorite ions, chlorate ions, chloride ions, peroxodisulfate ions, chlorine gas, sulfur dioxide, etc.
- the first aqueous chlorine dioxide solution which is provided in step (1) preferably comprises chlorine dioxide in a concentration of 2000 to 6500 ppm (unless stated further, the specification ppm refers to parts by weight), more preferably from 4000 to 5500 ppm, and particularly preferably from about 5000 ppm.
- step (2) of the method according to the invention proportions of undesired reactive gases from the chlorine dioxide solution are reduced, undesired gases are preferably removed from the chlorine dioxide solution, in particular the reactive gases chlorine (CL) and / or hypochlorous acid (HCIO) and / or Chloric acid (HCIO3) and / or sulfur dioxide (SO2), particularly preferably chlorine and / or sulfur dioxide, which were used in the production of the first chlorine dioxide solution provided in step (1) or can arise therein.
- a suitable chlorine dioxide-stable reactant is added to the first chlorine dioxide solution provided in step (1), with which such reactive gases can be reduced, preferably removed, from the solution.
- the expression "removal of undesired gases” is used to denote a chemical reaction by which a gas dissolved in the aqueous solution is chemically bound in such a way that it can no longer escape from the solution in gaseous form.
- a dissolved gas is chemically bound by reacting with the reagent to form corresponding dissolved ionic compounds.
- a gas can be oxidized or reduced, or converted into a larger (ionic) molecule through an addition reaction.
- adding the reagent to reduce the proportion of undesired gases, preferably to remove undesired gases, and the subsequent reaction with the dissolved gas, it is prevented that a gas can escape from the solution.
- the inventive reduction, preferably removal or chemical conversion of the interfering gases by reaction with the reagent in the aqueous solution has the advantage over other methods based, for example, on reactions in the gas phase, that a rapid reduction, preferably rapid and complete removal of the unwanted gases from the aqueous solution takes place under controlled reaction conditions.
- Hydrogen peroxide and carbonates, bicarbonates, chlorites and hydroxides are suitable as a reagent for reducing the proportion of undesired gases, preferably for removing undesired gases.
- sodium carbonate is very particularly preferably used as the reagent for removing undesired salts, preferably in the form of buffered sodium carbonate.
- the reagent added in step (2) for removing undesired gases can also contain two or more suitable reagents, preferably two or more of the reagents listed above.
- mixtures comprising sodium carbonate and sodium bicarbonate for example, mixtures comprising sodium carbonate and sodium chlorite, or mixtures comprising sodium carbonate and hydrogen peroxide are preferred.
- a mixture can be added in step (2) which comprises sodium carbonate and sodium bicarbonate in a suitable ratio.
- the reagent used in step (2) to reduce the proportion of unwanted gases, preferably to remove unwanted gases, is preferably added in a suitable (aqueous) solution, but can also be added in solid form (e.g. in salt form).
- aqueous solution the dosage is both easier and the reaction faster or less or no additional mixing is required.
- an aqueous solution can preferably be added which comprises one, two or more of the reagents listed above.
- Preferred examples are an aqueous solution comprising sodium carbonate, or an aqueous solution comprising a mixture of sodium carbonate and sodium chlorite, a mixture of sodium carbonate and hydrogen peroxide, or a mixture of sodium carbonate and sodium bicarbonate.
- the reagent is preferably added to reduce, preferably remove, undesired gases in amounts which are sufficient to reduce, preferably remove, all of the gases present in the first chlorine dioxide solution.
- the reagent is added in excess, preferably in a molar ratio of reagent to chlorine of 1.1: 1 to 5: 1, preferably 1.5: 1 to 2: 1.
- the reagent is added in a molar ratio of reagent to chlorine dioxide of 0.1: 1 to 2: 1, preferably in a molar ratio of 0.5: 1 to 1.5: 1, depending on the manufacturing process.
- Aqueous chlorine dioxide solutions that have been produced according to more recent processes or processes known as “cleaner” in the state of the art require a smaller amount of reagent than those from older processes or processes known as less “clean”.
- the pH of the first solution provided in step (1) is adjusted to a slightly acidic to neutral pH of 4.0 to 7.5 adjusted, particularly preferably to a neutral pH, preferably in the range from 6.5 to 7.5.
- the neutral pH value is more preferably a pH value in the range from 6.8 to 7.2 and the neutral pH value is particularly preferably approximately 7.0.
- the neutral pH is preferably stabilized by adding a buffer system. Suitable buffer systems and methods for establishing a neutral pH are known in the art. That is preferred Buffer system selected from a carbonate buffer system, a phosphate buffer system and a peroxodisulfate buffer system. When hydrogen peroxide and chlorites are added, the pH of the first solution is preferably not adjusted to a neutral value.
- step (1) By setting a neutral pH value for the first aqueous chlorine dioxide solution provided in step (1), the new formation of undesired gases, in particular chlorine gas, through any acid or base-mediated reactions (such as the decomposition of chlorine dioxide) is effectively prevented .
- the pH of the first solution provided in step (1) can be adjusted by adding the reagent to the Removal of unwanted gases in step 2) can be set to a neutral value.
- This special embodiment of the method according to the invention can be used in particular when the first chlorine dioxide solution provided in step (1) is an acidic solution (pH ⁇ 6.5). Since all known manufacturing processes for chlorine dioxide take place in the acidic range, an acidic solution will usually be present.
- step (3) of the process according to the invention the chlorine dioxide is then separated off from the chlorine dioxide solution which has been purified from undesired gases in step (2).
- the chlorine dioxide can be separated off from the chlorine dioxide solution which has been purified from undesired gases in step (2) using any method known in the art.
- the chlorine dioxide is preferably separated from the aqueous solution in step 3) in the gaseous state, for example by contacting a carrier gas stream (so-called "stripping" process) or by distilling under reduced pressure (so-called "sub-boiling” distillation) .
- the chlorine dioxide solution which has been purified from undesired gases in step (2) is mixed with a suitable one Carrier gas brought into contact.
- the carrier gas can, for example, be passed over the surface of the chlorine dioxide solution or blown through the chlorine dioxide solution using suitable nozzles in order to enrich the chlorine dioxide more quickly in the carrier gas.
- the carrier gas enriched with chlorine dioxide is then separated from the remaining aqueous solution using suitable lines, pumps, etc.
- the carrier gas used is preferably a carrier gas that is inert to chlorine dioxide, such as, for example, air, nitrogen, carbon dioxide, oxygen, a noble gas such as, for example, argon, and mixtures thereof.
- the carrier gas is preferably selected from nitrogen, carbon dioxide and argon.
- the preferred flow rate of carrier gas is related to the amount of chlorine dioxide solution.
- the carrier gas is preferably blown at a flow rate of 0.01 to 1% of the volume of the chlorine dioxide solution per minute over the surface of the chlorine dioxide solution cleaned of undesired gases in step (2) or at a flow rate of 0.1% to 10% of the volume of the chlorine dioxide solution per minute blown through the chlorine dioxide solution cleaned of undesired gases in step (2).
- the flow rate of an air stream is 1 to 100 liters per minute, preferably 5 to 10 liters per minute.
- the chlorine dioxide is separated from the chlorine dioxide solution which has been purified from undesired gases in step (2) by distillation under reduced pressure (so-called "sub-boiling" distillation).
- the process according to the invention enables sensible distillation by first removing all interfering gases from the chlorine dioxide-containing solution in step (2).
- the inventor of the present invention has found that a distillation of chlorine dioxide from an aqueous solution can be carried out safely if the distillation temperature is reduced to well below 45 ° C. by lowering the pressure. Under correspondingly reduced pressure conditions, chlorine dioxide can thus be separated from the chlorine dioxide solution, which has been purified from undesired gases in step (2), by distillation under reduced pressure, without product decomposition or explosion.
- the pressure is preferably reduced to such an extent that the distillation takes place at a temperature of 35.degree or less, more preferably at room temperature (for example a temperature of 20 to 25 ° C.) or a temperature of 20 ° C. or 25 ° C. (standard room temperature).
- room temperature for example a temperature of 20 to 25 ° C.
- 20 ° C. or 25 ° C. standard room temperature.
- a temperature-pressure combination is selected at which the water does not yet boil, for example more than 30 mbar at 20 ° C or more than 40 mbar at 25 ° C.
- a temperature-pressure combination is selected to increase process reliability at which the water also boils, for example 23 mbar at 20 ° C or 32 mbar at 25 ° C. More preferably, the boiling point of the water has not yet been reached, so that there is no significant bubble formation with even higher impurities caused by this, for example 24 mbar at 20 ° C. or 33 mbar at 25 ° C. Due to the (almost) boiling of the water, certain impurities are accepted, on the other hand, the water-chlorine dioxide mixture ensures that the chlorine dioxide concentration does not exceed 10% at any time and therefore that there is no theoretical risk of explosion at any time. Since in this embodiment a significantly larger amount of distillate arrives in the collecting container due to the distilled water, a greater temperature difference between the output container and the collecting container and / or cooling of the collecting container is desirable in this embodiment.
- distillation steps can take place one after the other, the distillation can be carried out via a cascade of several water containers or the distillation can be repeated one or more times.
- a distillation is carried out under reduced pressure in combination with a stream of carrier gas being blown through the chlorine dioxide solution which has been purified from undesired gases in step (2).
- additional (chemical) filters can preferably be used to increase the purity in the distillation stream between the containers, such as, in particular, solid NaCl0 2 as a chemical chlorine filter or chlorine dioxide-resistant particle filter as Salt filters, for example HEPA / ULPA filters made of PTFE.
- the chlorine dioxide separated off in step (3) is redissolved in water in step (4) to produce a purified second aqueous chlorine dioxide solution.
- the water in which the chlorine dioxide separated off in step (3) is dissolved is preferably pure water, for example distilled water or water completely desalinated by osmosis (deionized water).
- the pH of the water can be adjusted to a neutral value (preferably a pH of 6.5 to 7.5, more preferably from 6.8 to 7.2, and particularly preferably about 7.0) with a suitable buffer system (preferably a carbonate, phosphate or peroxodisulfate buffer system).
- a suitable buffer system preferably a carbonate, phosphate or peroxodisulfate buffer system.
- the second aqueous chlorine dioxide solution produced contains not only water and chlorine dioxide but also the respective buffer system.
- the second aqueous chlorine dioxide solution produced can also comprise one or more suitable, chlorine dioxide-stable surfactants.
- Suitable surfactants or surfactant combinations include, for example, quaternary ammonium compounds and / or non-ionic surfactants, preferably carboxylic acid esters and / or phosphate esters, such as, in particular, ethoxylated aliphatic phosphate esters or phosphate diesters and / or ethoxylated carboxylic acid esters, preferably aliphatic carboxylic acid esters and / or alkyl ethers Phosphates, as well as ethoxylated fatty alcohols, ethoxylated fatty amines, ethoxylated alkylphenols, and / or ethoxylated fatty acids.
- a chlorine dioxide solution according to the invention preferably contains a surfactant or a surfactant combination in a concentration of 10% by weight or less, more preferably in a concentration of 5% by weight or less, and particularly preferably in a concentration of 1% by weight. % Or less.
- the surfactant is contained in the aqueous collecting solution from the start, since it promotes the absorption of the chlorine dioxide gas or minimizes its renewed stripping by the gas flow from the collecting container to the vacuum pump or to the gas outlet.
- the water in which the chlorine dioxide separated off in step (3) is dissolved is cooled to a temperature of less than 20 ° C., preferably to a temperature of less than 10 ° C. and preferably kept there
- the carrier gas / chlorine dioxide mixture can preferably be injected into the (preferably cooled) water can be introduced and distributed in order to dissolve the chlorine dioxide more quickly in the water.
- Devices and methods suitable for this are known, for example, from GB 760,303 A and WO 2019/180049 A1.
- the chlorine dioxide can be passed directly into the (preferably cooled, e.g. to 10 ° C or less) water for condensation and thus dissolved therein.
- the distillation process represents a particularly preferred embodiment of the process according to the invention, since it offers the further advantage over the likewise possible carrier gas flow process, for example, that no gas flow has to be passed through the water.
- a flow through the manufactured product is always associated with the risk that the outflowing carrier gas flow in turn entrains chlorine dioxide from the product solution and thus leads to a reduced chlorine dioxide concentration in the product and the associated losses and costs.
- the chlorine dioxide separated off in step (3) (for example the sub-boiling distillate or the stripping chlorine dioxide carrier gas stream) is cooled to a temperature of less than 11 ° C., preferably to less than 0 ° C., and particularly preferably to -8 to -30 ° C.
- the temperature should preferably always be higher than the boiling or condensation temperature of chlorine (Cb) at the respective pressure (for example, at normal pressure always higher than -34.03 ° C., the boiling point of chlorine under normal pressure).
- the cooling is preferably carried out via suitable cooled surfaces, such as, for example, suitable cooling tubes, cooling spirals, cooling coils, and the like.
- Cooling can preferably take place, for example, with the aid of commercially available cooling devices, such as a circulating cooler or a cryostat device (such as model RC5 from IKA), which are operated as a cheap source of cold with a suitable cooling medium (e.g. ethanol in water 50% v / v) can be.
- a suitable cooling medium e.g. ethanol in water 50% v / v
- Such a cooling of the separated chlorine dioxide or chlorine dioxide-carrier gas mixture leads to condensation of the chlorine dioxide contained and, if applicable, of the water contained in the distillate or air stream, but not of any residual chlorine (Cb) content, which leads to further dechlorination of the product can be achieved by fractional condensation or sublimation.
- the pure chlorine dioxide condenses, while the water content (including any salts it may contain) freezes on the surface of the cooling device unit carrying the cooling medium (e.g. cooling coil in the Graham cooler) and in this way is withdrawn from the distillate.
- the temperature is likewise preferably above -34.03 ° C. in order to avoid temperatures being reached at which the residual chlorine possibly contained in the distillate or air stream also condenses.
- the frozen water content can after completion of the distillation or stripping Process or through periodic cleaning intervals with an increase in the temperature in the cooling circuit and removed from the system.
- the cooling process preferably takes place at a very low flow rate of the distillate or the stripping carrier gas stream (flow rate of 0.01 to 1% of the volume of the chlorine dioxide solution per minute) in order to achieve the most complete possible condensation of the chlorine dioxide.
- the chlorine dioxide separated off in step (3) e.g. the sub-boiling distillate or the stripping chlorine dioxide carrier gas stream
- the cooling unit or the cooling units preferably forms a gradient at the end of which the condensed chlorine dioxide can easily be separated off.
- the pure chlorine dioxide separated out in this way can either be converted directly into a suitable solvent, such as preferably pure (distilled or fully demineralized) water, or it can be processed further as a pure substance.
- a first aqueous chlorine dioxide solution is provided in a first step, which was prepared from chlorate, for example by reacting sodium chlorate with hydrochloric acid.
- the pH of this first aqueous chlorine dioxide solution is adjusted to a neutral value in the range from 6.5 to 7.5 and sodium carbonate is added in order to remove dissolved chlorine gas from the solution or to bind it chemically.
- the chlorine dioxide is distilled off under reduced pressure and dissolved in (pure) water to produce a purified second aqueous chlorine dioxide solution.
- the present invention provides a method for producing a high-purity aqueous chlorine dioxide solution, in which existing large-scale plants and methods can be used to produce an inexpensive first aqueous chlorine dioxide solution in large quantities, which is then purified by the method according to the invention that it is suitable, for example, for applications in the medical field.
- the costs can be reduced by 75 to 90% compared to other processes.
- the method according to the invention does not require the use of hazardous chemicals, such as chlorine gas or the like, which makes it easier to carry out and reduces costs compared to other methods.
- the inventive removal of the interfering gases by reaction in aqueous solution has the advantage over other methods based, for example, on reactions in the gas phase, that the undesired gases can be removed quickly and completely controllable reaction conditions takes place.
- the process according to the invention thus reliably produces chlorine-free chlorine dioxide solutions which are suitable, for example, for applications in the medical field.
- the separation of the chlorine dioxide from the aqueous solution previously purified from undesired gases, in particular chlorine and sulfur dioxide, which is particularly preferably carried out by distillation under reduced pressure, and the subsequent dissolution in (pure) water reliably leads to an aqueous chlorine dioxide solution, which does not contain unwanted salts.
- Chlorates for example, are undesirable because limit values for the use of chlorine dioxide are often determined by the chlorate content.
- the content of cations, such as sodium ions, and anions, such as chloride ions, is also advantageously low.
- the total content of impurities in the aqueous chlorine dioxide solution produced by the process according to the invention is preferably less than 1000 ppm, more preferably less than 500 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, and particularly preferably less than 10 ppm .
- an aqueous chlorine dioxide solution produced according to the invention has a chlorine dioxide concentration of at least 100 ppm.
- a chlorine dioxide solution can be used directly without a concentrate having to be prepared and diluted beforehand.
- the present invention also enables the manufacture of concentrates.
- Concentrates preferably have a chlorine dioxide concentration of at least 1500 ppm, more preferably of at least 2000 ppm.
- the total content of all impurities (gases and salts) is preferably less than 1000 ppm, more preferably less than 100 ppm, more preferably less than 10 ppm.
- both the chlorine content and the chlorate content and the sodium content and the calcium content are each less than 100, more preferably less than 1 ppm, and particularly preferably the total chlorine content is chlorate , Calcium, magnesium and sodium less than 100, preferably less than 10 ppm.
- the total content of chlorine, chlorate and sodium is preferably less than 100, preferably less than 5 ppm, more preferably less than 1 ppm.
- an aqueous chlorine dioxide solution produced according to the invention has a conductance of less than 25 pS / cm (microsiemens), particularly preferably less than 10 pS / cm, more preferably less than 2 pS / cm.
- the conductance of the aqueous chlorine dioxide solution can be measured, for example, using suitable laboratory equipment such as, for example, Seven Go Duo ph / lon / Cond meter SG 78-USP-K from Mettler Toledo.
- a chlorine dioxide solution prepared according to the invention preferably retains more than 90% of the original concentration of chlorine dioxide for at least 18 months when stored at room temperature (15 to 25 ° C.). In particular, a chlorine dioxide solution prepared according to the invention retains more than 95% of the original concentration of chlorine dioxide when stored at room temperature (15 to 25 ° C.) for at least 24 months.
- the inventively produced chlorine dioxide solutions are preferably packaged in suitable containers, for example in glass bottles with (poly) fluoroelastomers or PVC coated closures or caps, made of or containing (poly) fluoroelastomers, such as in particular PTFE, PEEK, Viton ®, or a PTFE-polymer mixture.
- suitable containers for example in glass bottles with (poly) fluoroelastomers or PVC coated closures or caps, made of or containing (poly) fluoroelastomers, such as in particular PTFE, PEEK, Viton ®, or a PTFE-polymer mixture.
- plastic bottles made from the polymers mentioned can also be used.
- Packaging preferably offers protection against light radiation and other external influences, such as rapid temperature fluctuations, shocks or the like.
- a packaging can be an opaque container (for example a dark glass bottle or the like).
- the chlorine dioxide solutions produced according to the invention are packaged in shipping units of 4 or 6 glass bottles in a suitably
- the present invention additionally also provides a disinfectant based on the chlorine dioxide solution prepared according to the invention.
- a disinfectant based on the chlorine dioxide solution prepared according to the invention.
- This is produced by adding at least one suitable, chlorine dioxide-stable surfactant to the chlorine dioxide solution prepared according to the invention, such as a quaternary ammonium compound and / or a non-ionic surfactant, preferably carboxylic acid esters and / or phosphate esters such as, in particular, ethoxylated aliphatic phosphate esters or Phosphate diesters and / or ethoxylated carboxylic acid esters, preferably aliphatic carboxylic acid esters and / or alkyl ether phosphates, as well as ethoxylated fatty alcohols, ethoxylated fatty amines, ethoxylated alkylphenols, and / or ethoxylated fatty acids.
- a surfactant or a surfactant combination is preferably added to the chlorine dioxide solution according to the invention in a concentration of 10% by weight or less, more preferably in a concentration of 5% by weight or less, and particularly preferably in a concentration of 1% by weight. -% Or less.
- the chlorine dioxide solutions produced by the process according to the invention are preferably used for surface disinfection and as medical products and in human and veterinary medicine. When used on surfaces, hardly any or only negligible residues are left behind. Finally, when used medicinally, it offers be it as a drug or as a medical product, there are significant advantages, as no impurities can influence the effect, which means that it can be defined much more clearly. This leads, among other things, to lower use quantities / concentrations or fewer side effects.
- a chlorine dioxide solution according to the invention can preferably be used, for example, to disinfect solid surfaces or water, in particular to remove bacteria, viruses, protozoa, molds and / or spores from these surfaces or the water.
- An application in the human or veterinary medical field can also relate to the treatment of skin, nails, hooves, claws, wounds, etc.
- a chlorine dioxide solution according to the invention can also be used for disinfecting food.
- pH-neutral chlorine dioxide solution according to the invention which contains one of the surfactants disclosed in a concentration of less than 500ppm, more preferably less than 150ppm, since this solution surprisingly proved to be particularly skin-friendly due to the low residues and the selected surfactant Has.
- the pH value of an aqueous chlorine dioxide solution (1.0 liter with a chlorine dioxide concentration of 5000 ppm and a pH value of 2.0) prepared by reacting sodium chlorate with hydrochloric acid according to the industrial process for bleaching agents is determined by adding an aqueous Solution of 5.0 wt .-% sodium carbonate and 2.0 wt .-% sodium hydrogen sulfate as a buffer adjusted to 7.0 in order to bind chlorine gas present in the solution. Then the chlorine dioxide is distilled off at room temperature (about 20 ° C) and a pressure of 40 mbar and dissolved directly in 1.0 liter of distilled water (deionized water), which is cooled to 10 ° C, up to a concentration of 2000 ppm .
- the aqueous chlorine dioxide solution produced in this way is packed in glass bottles with a stopper made of a PTFE-polymer mixture, and the bottles are again light-tight in a shock-absorbing styrofoam packaging.
- the chlorine dioxide solution After storage at room temperature for 18 months, the chlorine dioxide solution has a concentration of 1860 ppm (93% of the initial concentration) and after 24 months a concentration of 1820 ppm (91% of the initial concentration).
- a disinfectant solution containing chlorine dioxide chlorine dioxide is distilled off as in Example 1, but then at 10 ° C in 1.0 liter of distilled water that is mixed with a carbonate / phosphate buffer (sodium carbonate (soda) and phosphoric acid, each approx. 01 mol) is set to a pH of 7.0 and contains a surfactant (“Dehyton AB 30” from BASF) in a concentration of 2 g / l, up to a concentration of 2000 ppm in the solution.
- the aqueous disinfectant solution containing chlorine dioxide produced in this way is packed in glass bottles which are closed with a stopper made from a PTFE polymer, and the bottles are again light-tight in shock-absorbing styrofoam packaging.
- the disinfectant solution After storage at room temperature for 18 months, the disinfectant solution has a chlorine dioxide concentration of 1900 ppm (95% of the initial concentration) and a chlorine dioxide concentration of 1860 ppm after 24 months (93% of the initial concentration).
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Abstract
Description
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DE102020111417.6A DE102020111417A1 (de) | 2020-04-27 | 2020-04-27 | Wässerige Chlordioxid-Lösungen und Verfahren zur Herstellung derselben |
DE102020113390 | 2020-05-18 | ||
PCT/EP2021/060904 WO2021219587A1 (de) | 2020-04-27 | 2021-04-27 | Wässerige chlordioxid-lösungen und verfahren zur herstellung derselben |
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Country Status (5)
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US (1) | US20230183065A1 (de) |
EP (1) | EP4143130A1 (de) |
CN (1) | CN115461304A (de) |
CA (1) | CA3173825A1 (de) |
WO (1) | WO2021219587A1 (de) |
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GB460376A (en) * | 1935-07-26 | 1937-01-26 | Mathieson Alkali Works | Improvements in or relating to the production of chlorine dioxide |
GB760303A (en) | 1954-02-16 | 1956-10-31 | Cardox Corp | Improvements in or relating to apparatus for manufacture of chlorine dioxide hydrateand the like |
US5433938A (en) * | 1992-10-23 | 1995-07-18 | Vulcan Chemicals | Chlorine-destruct method |
DE19514612A1 (de) | 1995-04-25 | 1996-10-31 | Fritz Dr Kueke | Verfahren zur Herstellung einer wässrigen Chlordioxid-Lösung |
EP1957401A4 (de) | 2005-11-14 | 2013-09-04 | Cdg Environmental Llc | Lagerstabile wässrige lösungen aus chlorindioxid und verfahren zu ihrer herstellung und verwendung |
WO2010011989A1 (en) * | 2008-07-25 | 2010-01-28 | Siemens Water Technologies Corp. | Chlorine dioxide generation systems and methods |
TW201808792A (zh) * | 2016-09-14 | 2018-03-16 | 優尼克生技股份有限公司 | 二氧化氯純化方法 |
DE102018107018A1 (de) | 2018-03-23 | 2019-09-26 | Fritz Küke | Verfahren und Vorrichtung zum Herstellen einer Chlordioxid enthaltenden wässrigen Lösung |
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2021
- 2021-04-27 CA CA3173825A patent/CA3173825A1/en active Pending
- 2021-04-27 EP EP21722186.0A patent/EP4143130A1/de not_active Withdrawn
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US20230183065A1 (en) | 2023-06-15 |
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