CN1345385A - 稳定溴溶液、其制备方法及其用于生物污垢控制的应用 - Google Patents
稳定溴溶液、其制备方法及其用于生物污垢控制的应用 Download PDFInfo
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 25
- 229910052801 chlorine Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 230000003115 biocidal effect Effects 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003139 biocide Substances 0.000 claims description 8
- 239000008235 industrial water Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- -1 alkyl hydantoin Chemical compound 0.000 claims description 6
- 239000007844 bleaching agent Substances 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 4
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002332 oil field water Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910001616 alkaline earth metal bromide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229910001919 chlorite Inorganic materials 0.000 claims description 2
- 229910052619 chlorite group Inorganic materials 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 229940109239 creatinine Drugs 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229940091173 hydantoin Drugs 0.000 claims description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims description 2
- 238000011012 sanitization Methods 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical group 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 58
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 22
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 13
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 8
- 230000031709 bromination Effects 0.000 description 7
- 238000005893 bromination reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 6
- 238000000207 volumetry Methods 0.000 description 6
- 238000011021 bench scale process Methods 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZZDUJRFHYVLCJF-UHFFFAOYSA-N O[Br][Na] Chemical compound O[Br][Na] ZZDUJRFHYVLCJF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000006150 trypticase soy agar Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/24—Inter-halogen compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/10—Bromides
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- 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
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- 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
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3951—Bleaching agents combined with specific additives
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/3953—Inorganic bleaching agents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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Abstract
通过以下步骤制备稳定溴溶液:结合溴源和稳定剂形成混合物,向混合物中加入氧化剂,然后加入碱源将混合物的pH调到至少13。
Description
发明领域
本发明总体上涉及水处理，更具体地说，涉及稳定溴溶液、其制备方法及其用于生物污垢控制的应用。
发明背景
次氯酸钠被广泛地用于各种工业和再生水系统中以控制生物污垢。然而，次氯酸钠是不稳定的，并且必须以稳定的形式提供。在本领域中有几种已知的用于稳定次氯酸钠的方法(例如，参见美国专利第3,328,294号和第3,767,586号)。
在水处理的应用中，溴比氯优选，因为它在高pH和胺环境中具有更低的挥发性和更好的性能。然而，与次氯酸钠一样，次溴酸钠在典型的存储条件下是不稳定的，因此也必须以稳定的形式提供。美国专利第5,683,654号和5,795,487号以及其中公开的参考文献提供了多种用于稳定次溴酸钠的方法。该两个专利公开了间歇式方法，该方法利用次氯酸钠和溴化纳作为原料，随后添加稳定剂。WO 97/20909同样公开了一种方法，该方法包括次溴酸盐生成步骤后的溴稳定化步骤。然而，该技术的不利之处在于，不稳定的次溴酸盐是在单独的步骤中在高浓度和pH下形成。已知不稳定的次溴酸盐在这种条件下迅速降解，形成溴酸盐，溴酸盐是一种非杀生物的化合物，毒性非常大，并且怀疑是一种致癌物质。
另外，WO 97/43392公开了一种方法，该方法首先形成稳定的氯化合物，然后将氯化合物转化为稳定的溴化合物。但是，这种类型的方法具有局限性，因为只能使用释次氯酸盐化合物作为氧化源。
因此，由于稳定的溴溶液优于氯溶液，将来对稳定溴溶液的需求有望增加，所以，需要提供其它成本合理的制备稳定溴的方法，该方法可以使用较宽范围的氧化剂，并以较高的产率生产较高浓度的产品。
所以，需要提供一种制备稳定溴溶液的方法，该方法可以以间歇式或连续式操作进行，并可以以较高的产率生产较高浓度的产品。也需要开发一种制备稳定溴溶液的方法，该方法是灵活的并允许利用多种氧化剂。
发明概述
本发明的稳定溴溶液是这样制备的：混合溴源和稳定剂形成混合物，向上述混合物中加入氧化剂，然后加入碱源将混合物的pH调到至少13。
本发明方法具有经济上的吸引力，因为它可以以间歇式或连续式操作进行，并且以较高的产率生产较高浓度的稳定溴溶液。该制备方法也很灵活并允许利用多种氧化剂。本发明的详细描述
本发明涉及制备稳定溴溶液的方法。根据本发明，将溴源和稳定剂结合形成混合物，接着向混合物中加入氧化剂，然后加入碱源将混合物的pH调到至少13。
在本发明的实施中，可使用的溴源包括氢溴酸、氯化溴、元素溴和碱金属或碱土金属溴化物如溴化纳、溴化钾和溴化锂。
可用于本发明的稳定剂具有化学式R-NH-R1，其中，R和R1选自R2CO、R2SO2、R2CF2、R2CHF、H、OH和PO(OH)2，并且R2是烷基或芳基。适合的稳定剂包括糖精、尿素、硫脲、肌酸酐、氰尿酸、烷基乙内酰脲、一乙醇胺、二乙醇胺、有机氨磺酰、缩二脲、氨基磺酸、有机氨基磺酸盐和蜜胺。氨基磺酸是最优选的稳定剂。
可使用的氧化剂包括氯气、次氯酸、次氯酸盐、亚氯酸盐、氯酸盐、元素溴、氯化溴、过氧化氢、过硫酸盐、高锰酸钾和过乙酸。根据本发明，相信也可使用其它的过氧化合物。
碱源优选碱金属或碱土金属氢氧化物。适合的碱源包括氢氧化钠、氢氧化锂、氢氧化钾、氢氧化镁和氢氧化钙。
溴源和稳定剂之间的摩尔比优选在约0.2到5的范围内。溴源和氧化剂之间的摩尔比优选应在约0.5到2的范围内。
在本发明的方法中，将温度保持在低于80°F，优选在约40到70°F范围内。在加入氧化剂的过程中，混合物的pH应保持在约低于7。本发明可以以间歇式或连续式操作进行。
根据本发明制备的稳定溴溶液可以用于各种工业应用。这些应用包括但不局限于稳定溴溶液的应用：(1)作为漂白剂用于清洗脏衣服的方法中，其中，在含有洗涤剂和漂白剂的水介质中清洗脏衣服；(2)作为氧化剂用于制备纤维素材料的方法，在该方法中漂白纤维素纤维；(3)作为氧化剂和杀生物剂用于再生水系统中控制生物污垢，在该再生水系统中中，加入氧化和杀生物剂来控制生物污垢；(4)作为氧化剂和杀生物剂用于控制硬质表面生物污垢的方法中，其中，将氧化剂和杀生物剂涂敷于该表面以控制该表面上的生物污垢；(5)在控制发生在与产油的油田水接触的设备表面上的生物污垢的方法中的应用；和(6)在控制水系统中生物污垢的方法中的应用。
在另一实施方案中，本发明提供了在与工业水系统接触的设备表面上防止生物污垢的方法。该方法包括向水系统加入控制生物污垢有效量的稳定溴溶液，其中，该溶液是这样制备的：结合溴源和稳定剂形成混合物，向混合物中加入氧化剂，然后加入碱源将混合物的pH调到至少13。
可使用稳定溴溶液来防止生物污垢的工业水系统的类型包括但不局限于冷却水系统、甜水系统、气体洗涤器系统、空气洗涤器系统、蒸发浓缩器、巴氏灭菌器、生产卫生洗涤剂水流、防火水系统和热交换管道。
优选地，加入到工业水系统的稳定溴溶液的量，基于有效溴浓度，在约0.1ppm到约2000ppm范围内，优选在约0.5ppm到约500ppm范围内。可通过任何常规方法，例如，通过导管，间歇地或连续地将稳定溴溶液加入水系统。
在另一实施方案中，本发明提供了制备稳定溴溶液的方法，该方法包括以下步骤：选择溴源，然后将稳定剂和氧化剂加入到溴源中形成混合物，其中，将稳定剂和氧化剂交替地加入到混合物中，加入量为足以将混合物的pH保持在约0到6.9之间，更优选在约3到6.5之间，最优选在4到6之间。那些本领域的技术人员将认识到，可通过基于混合物pH值的自动反馈控制，或简单的手工操作，来确定稳定剂和氧化剂的加入量。在稳定剂和氧化剂的添加结束后，向混合物中加入碱源将混合物的pH调到至少13。优选的溴源和稳定剂之间的摩尔比在约0.2到5范围内。溴源和氧化剂之间的摩尔比优选在约0.5到2范围内。根据本发明的实施方案，所有可以使用的适合溴源、稳定剂、氧化剂和碱源，以及温度条件，都与上述的情况相同。
实施例
下面的实施例用于说明本发明和教导普通的技术人员怎样实施和应用本发明。这些实施例不以任何方式限制本发明或其保护范围。实施例1
工作台规模的实验是这样进行的：
a.在250ml的烧瓶中混合6.83g 45％的溴化纳溶液和3.30g固体氨基磺酸，然后将烧瓶浸渍在冰-水浴中；
b.缓慢地将47.5g 4.0％的次氯酸钠溶液加入到烧瓶中，同时摇晃冰-水浴中的烧瓶以保持足够低的温度，使不出现气泡；和
c.在冷却烧瓶的同时缓慢地将4.5g 50％的氢氧化钠溶液加入到烧瓶中。
得到的产物为琥珀色溶液，pH为13.5，通过碘化钾-硫代硫酸钠滴定法测得总的卤素浓度为6.89％溴(或3.06％有效氯)。产物的紫外线(UV)光谱是典型的稳定的溴的图谱。无DPD和全DPD比色测定也表明，产物大多数为氧化的溴化合物(～98％)。实施例2
在工作台规模下，使用工业级次氯酸钠，按照上述实施例1进行的相同操作，制备较高浓度的产品。
产品是这样制备的：
a.在200ml的烧瓶中混合20.5g 45％的溴化纳溶液和8.70g固体氨基磺酸，然后将烧瓶浸渍在冰-水浴中以保持低温；
b.缓慢地将44.0g 14.2％(有效氯的重量比w/w)的工业级次氯酸钠加入到混合物中，同时摇晃冰-水浴中的烧瓶；和
c.将12.2g 50％的氢氧化钠溶液加入到混合物中。
得到的产物为琥珀色溶液，pH为13.5，根据碘化钾-硫代硫酸钠滴定法测得含有15.91％溴(或7.07％有效氯)。它的1,000倍稀释液的UV光谱是典型的稳定溴的图谱。无DPD和全DPD比色测定也表明，产物为100％氧化的溴化合物。实施例3
也可利用联机的方式测试本发明的方法。在连续的装备中氧化并稳定溴。通过在两个单独的烧瓶中制备两种溶液(A和B)开始该操作。通过混合60.9g固体氨基磺酸和143.5g 45％(w/w)的溴化纳溶液制备溶液A。加入水使溶液A的总体积达到约375毫升。通过用水将313.4g14.2％(氯的重量比w/w)的次氯酸钠稀释到375毫升来制备溶液B。然后，用复式泵头压力泵以每分钟约19毫升的速率将溶液A和B泵出烧瓶。这两种溶液经由浸渍在冰-水浴中的T型管连接器混合。然后，混合的溶液通过浸渍在水浴中的内径为1/8英寸的40英尺PVC管，然后注入另一个装有84.5g 50％(w/w)氢氧化钠溶液的烧瓶中。
得到的产物总重量为927g，pH大于13.5，具有9.07％溴(或4.03％有效氯)(根据碘化钾-硫代硫酸钠滴定法测得)。它的500倍稀释液的UV光谱是典型的稳定溴的图谱。无DPD和全DPD比色测定的测量结果也表明，产物为93％氧化的溴化合物。实施例4
也可使用氯气作为氧化剂进行工作台规模的间歇式操作。通过在1升的三颈瓶中混合340g 45％的溴化纳溶液、100g软水和144.4g固体氨基磺酸来制备原始溶液(溶液C)。将烧瓶浸渍在冰-水浴中以便将溶液温度保持在10℃到25℃之间。用氢氧化钠溶液(50％w/w)将溶液C的pH调至4.0到约5.0。加入氢氧化钠之后，将溶液C冷却到约10℃。然后，以鼓泡方式将氯气以稳定的速率通入溶液C中。在向溶液C通入氯气的过程中，用浓氢氧化钠溶液将pH保持在4.0到约5.0，并且温度保持在约10℃到约25℃。通入氯气直到溶液含有约10.59％有效氯(根据碘化钾-硫代硫酸钠滴定法测得)。另外再加入氢氧化钠溶液将产物的pH升到约13.5。通过过滤将任何反应过程中形成的混合的盐除去。
得到的产物为琥珀色溶液，pH为约13.5，根据碘化钾-硫代硫酸钠滴定法测得含有约21.85％溴(或9.71％有效氯)。产物的UV光谱是典型的稳定的溴的图谱。无DPD和全DPD比色测定的测量结果也表明，产物几乎为氧化的溴化合物(～97％)。实施例5
另一个工作台规模的实验是这样进行的：在500ml的烧瓶中混合75.0g 45％的溴化纳溶液和10g水，然后将烧瓶浸渍在冰-水浴中。将大约1g的氨基磺酸加入到500ml的烧瓶中，将溶液的pH降低到小于1，然后将24.0％(有效氯的重量百分比)的次氯酸钠溶液(Hypure-N，购自Olin Corporation of Cheshire，CT)缓慢地滴入烧瓶中，同时用磁搅拌棒混合溶液。当pH升至约6时，再加入一小部分的氨基磺酸，将pH降到2和3之间。通过次氯酸钠溶液和氨基磺酸的交替加入，将溶液的pH控制在2到6之间。加入的氨基磺酸的总量是35.0g，次氯酸钠溶液的总量是101.6 g。整个操作在溶液温度为约57到68°F范围内进行。然后，将31.75g 50％的氢氧化钠溶液缓慢地加入到烧瓶中，同时将溶液温度保持在68°F以下。
得到的产物为琥珀色溶液，pH为13.3，通过碘化钾-硫代硫酸钠滴定法测得总的卤素浓度为20.75％溴(或9.22％有效氯)。产物的UV光谱是典型的稳定的溴的图谱。实施例6
将一种次氯酸钠溶液(CLOROX)和两种稳定的次溴酸钠溶液(一种溶液是STABREXTM，购自Nalco Chemical Company of Naperville，IL；另一种溶液如以上实施例4所述的方法制备)都稀释，然后加入到冷水中，以得到1ppm的总的卤素残留量(以氯计)。合成的冷水含有10ppm的NH4Cl和大约106细胞/ml的混合冷水细菌。在0、0.5、1、2、5、10、20、30、45和60分钟时取出等分的处理过的样品，加入到含卤素中和剂(0.05％Na2S2O3)的磷酸盐缓冲稀释空白液中，然后在胰蛋白酶大豆琼脂板上计数。两种稳定的次溴酸钠溶液在NH4Cl存在下都具有比次氯酸钠更有效的杀生物力(参见下面的表1)。另外，在实施例4中制得的稳定的次溴酸钠溶液的效力与Nalco的STABREXTM产品的效力相同。表1
| 时间(分钟) | Log10活细菌细胞数/ml | |||
| 对照 | 不稳定的次氯酸钠(CLOROX) | Nalco的STABREXTM产品 | 稳定的次溴酸钠(由实施例4获得) | |
| 0 | 6.07 | 6.07 | 6.07 | 6.07 |
| 0.5 | - | 6.05 | 6.06 | 6.07 |
| 1 | - | 6.03 | 4.78 | 4.59 |
| 2 | - | 6.07 | 2.48 | 2.48 |
| 5 | 6.02 | 6.12 | ＜1 | ＜1 |
| 10 | 6.09 | 6.03 | ＜1 | ＜1 |
| 20 | 6.07 | 5.52 | ＜1 | ＜1 |
| 30 | 6.04 | 5.08 | ＜1 | ＜1 |
| 45 | 6.09 | 3.87 | ＜1 | ＜1 |
| 60 | 6.17 | 2.00 | ＜1 | ＜1 |
尽管以上结合优选的或举例说明的实施方案描述了本发明，但这些实施方案不是穷尽的，也不限制本发明的。更确切地说，本发明预期覆盖包括于所附权利要求限定的精神和保护范围之内的所有的改变、修改和等同物。
Claims (30)
1.一种制备稳定溴溶液的方法，该方法包括以下步骤：
a.结合溴源和稳定剂形成混合物；
b.向混合物中加入氧化剂；和
c.向混合物中加入碱源将混合物的pH调到至少13。
2.如权利要求1所述的方法，其中所述溴源选自氢溴酸、氯化溴、元素溴、碱金属溴化物和碱土金属溴化物。
3.如权利要求1所述的方法，其中所述稳定剂具有化学式R-NH-R1，其中，R和R1选自R2CO、R2SO2、R2CF2、R2CHF、H、OH和PO(OH)2，R2是烷基或芳基。
4.如权利要求1所述的方法，其中所述稳定剂选自糖精、尿素、硫脲、肌酸酐、氰尿酸、烷基乙内酰脲、一乙醇胺、二乙醇胺、有机氨磺酰、缩二脲、氨基磺酸、有机氨基磺酸盐和蜜胺。
5.如权利要求1所述的方法，其中所述稳定剂是氨基磺酸。
6.如权利要求1所述的方法，其中所述氧化剂选自氯气、次氯酸、次氯酸盐、亚氯酸盐、氯酸盐、元素溴、氯化溴、过氧化氢、过硫酸盐、高锰酸钾和过乙酸。
6.如权利要求1所述的方法，其中所述碱源选自碱金属氢氧化物和碱土金属氢氧化物。
8.如权利要求1所述的方法，其中所述碱源选自氢氧化钠、氢氧化锂、氢氧化钾、氢氧化镁和氢氧化钙。
9.如权利要求1所述的方法，其中所述溴源和所述稳定剂之间的摩尔比在约0.2到5范围内。
10.如权利要求1所述的方法，其中所述溴源和所述氧化剂之间的摩尔比在约0.5到2范围内。
11.如权利要求1所述的方法，其中步骤a、b、c的温度保持在低于80°F。
12.如权利要求1所述的方法，其中步骤a、b、c中的温度保持在约40到70°F。
13.如权利要求1所述的方法，其中在步骤b中，pH保持在低于约7。
14.由权利要求1所述方法制备的稳定溴溶液。
15.在清洗脏衣服的方法中，其中在含有洗涤剂和漂白剂的水介质中清洗所述脏衣服，改进之处包括使用权利要求14所述的稳定溴溶液作为漂白剂。
16.在制备纤维素材料的方法中，其中用氧化剂漂白纤维素纤维，改进之处包括使用权利要求14的稳定溴溶液作为氧化剂。
17.在控制再生水系统中生物污垢的方法中，其中加入氧化和杀生物剂来控制生物污垢，改进之处包括使用权利要求14所述的稳定溴溶液作为氧化和杀生物剂。
18.在硬质表面上控制生物污垢的方法中，其中将氧化剂和杀生物剂涂敷于该表面以控制该表面上的生物污垢，改进之处包括使用权利要求14所述的稳定溴溶液作为氧化剂和杀生物剂。
19.在控制发生在与产油的油田水接触的设备表面上的生物污垢的方法中，改进之处包括将控制生物污垢有效量的权利要求14所述的稳定溴溶液加入到产油的油田水中。
20.一种控制水系统中生物污垢的方法，包括将控制生物污垢有效量的权利要求14所述的稳定溴溶液加入到水系统中。
21.一种防止与工业水系统接触的设备表面的生物污垢的方法，包括将控制生物污垢有效量的稳定溴溶液加入到水系统中，所述溶液通过下列步骤制备：
a.结合溴源和稳定剂形成混合物；
b.向混合物中加入氧化剂；和
c.向混合物中加入碱源将混合物的pH调到至少13。
22.如权利要求21所述的方法，其中所述工业水系统选自冷却水系统、甜水系统、气体洗涤器系统、空气洗涤器系统、蒸发浓缩器、巴氏灭菌器、生产卫生洗涤剂水流、防火水系统和热交换管道。
23.如权利要求21所述的方法，其中以约0.1到约2000ppm有效溴的量将稳定溴溶液加入到工业水系统中。
24.如权利要求21所述的方法，其中以约0.5到约500ppm有效溴的量将稳定溴溶液加入到工业水系统中。
25.一种制备稳定溴溶液的方法，该方法包括以下步骤：
a.选择溴源；
b.将稳定剂和氧化剂加入到溴源中形成混合物，其中，将所述稳定剂和氧化剂交替地加入到混合物中，加入量为足以将混合物的pH保持在约0到6.9之间；和
c.向混合物中加入碱源将混合物的pH调到至少13。
26.如权利要求25所述的方法，其中步骤b的pH在约3到6.5之间。
27.如权利要求25所述的方法，其中步骤b的pH在约4到6之间。
28.如权利要求25所述的方法，其中所述溴源和所述稳定剂之间的摩尔比在约0.2到5范围内。
29.如权利要求25所述的方法，其中所述溴源和所述氧化剂之间的摩尔比在约0.5到2范围内。
30.由权利要求25的方法制备的稳定溴溶液。
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- 2000-02-11 WO PCT/US2000/003481 patent/WO2000058532A1/en active IP Right Grant
- 2000-02-11 DK DK00913427.1T patent/DK1171649T3/da active
- 2000-02-11 AT AT00913427T patent/ATE555062T1/de active
- 2000-02-11 AU AU34877/00A patent/AU766029B2/en not_active Expired
- 2000-02-11 ES ES00913427T patent/ES2386130T3/es not_active Expired - Lifetime
- 2000-02-11 EP EP00913427A patent/EP1171649B1/en not_active Expired - Lifetime
- 2000-02-11 PT PT00913427T patent/PT1171649E/pt unknown
- 2000-02-11 JP JP2000608809A patent/JP4148649B2/ja not_active Expired - Lifetime
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| CN103734189A (zh) * | 2013-11-04 | 2014-04-23 | 乌鲁木齐市科发展精细化工有限公司 | 一种活性溴液体氧化性杀菌灭藻剂及其制备方法 |
| CN107108277A (zh) * | 2014-12-25 | 2017-08-29 | 奥加诺株式会社 | 分离膜的黏质抑制方法 |
| CN107108277B (zh) * | 2014-12-25 | 2020-12-15 | 奥加诺株式会社 | 分离膜的黏质抑制方法 |
| CN107531523A (zh) * | 2015-04-30 | 2018-01-02 | 奥加诺株式会社 | 含氨性氮废水的处理方法和氨性氮分解剂 |
| CN107531523B (zh) * | 2015-04-30 | 2020-12-18 | 奥加诺株式会社 | 含氨性氮废水的处理方法和氨性氮分解剂 |
| CN108495822A (zh) * | 2016-02-18 | 2018-09-04 | 奥加诺株式会社 | 使用有反浸透膜的水处理系统及水处理方法 |
| CN108013072A (zh) * | 2016-11-02 | 2018-05-11 | 定州市荣鼎水环境生化技术有限公司 | 高效杀菌消毒剂及其制备方法 |
| CN108013072B (zh) * | 2016-11-02 | 2021-04-27 | 定州市荣鼎水环境生化技术有限公司 | 高效杀菌消毒剂及其制备方法 |
| CN112074188A (zh) * | 2018-05-04 | 2020-12-11 | 埃科莱布美国股份有限公司 | 非氯化氧化性杀生物剂化学物质、其生产方法、应用及其进料方法 |
Also Published As
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| JP4148649B2 (ja) | 2008-09-10 |
| NZ514203A (en) | 2003-02-28 |
| WO2000058532A1 (en) | 2000-10-05 |
| PT1171649E (pt) | 2012-07-04 |
| DK1171649T3 (da) | 2012-07-23 |
| ATE555062T1 (de) | 2012-05-15 |
| CA2363850C (en) | 2007-10-23 |
| NO20014626L (no) | 2001-09-24 |
| EP1171649A1 (en) | 2002-01-16 |
| NO20014626D0 (no) | 2001-09-24 |
| AU3487700A (en) | 2000-10-16 |
| BR0008816A (pt) | 2002-01-15 |
| BR0008816B1 (pt) | 2010-11-03 |
| ZA200106895B (en) | 2002-08-21 |
| TWI233951B (en) | 2005-06-11 |
| JP2002540297A (ja) | 2002-11-26 |
| EP1171649A4 (en) | 2004-05-06 |
| US6270722B1 (en) | 2001-08-07 |
| EP1171649B1 (en) | 2012-04-25 |
| CA2363850A1 (en) | 2000-10-05 |
| AR023231A1 (es) | 2002-09-04 |
| AU766029B2 (en) | 2003-10-09 |
| ES2386130T3 (es) | 2012-08-09 |
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