CN102428036A - 用卤化酰胺作为杀生物剂控制生物膜 - Google Patents
用卤化酰胺作为杀生物剂控制生物膜 Download PDFInfo
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
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- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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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
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
Abstract
Description
相关申请的交叉援引
本申请要求2009年5月18日递交的美国临时申请系列号61/179,161的权益,其通过援引以其全部内容在此加入。
发明领域
本发明涉及通过将水性或含湿体系用卤化酰胺杀生物剂处理而用于控制该体系中的生物膜的方法。
发明背景
生物膜生长在其中存在微生物,水分,养分和表面的组合的几乎任何环境。工业上,生物膜出现在水基工艺中,所述水基工艺包括水处理和分布。通过微生物生长而形成的生物膜通过设备和管线腐蚀,体系堵塞,产品失败和能量损失而在工业上造成巨大的经济损失。生物膜通过占据被包封在自发展聚合物基质内的结构化群体的微生物层的堆积而形成。在生物膜内的微生物被称作固着微生物,而游离漂浮的非生物膜微生物是浮游生物的。
通过在生物膜中生长,固着微生物更耐受抗菌处理。2,2-二溴-3-次氨基丙酰胺(″DBNPA″),例如,是一种能够非常有效地杀死浮游微生物的市售杀生物剂;但是,它在用于生物膜处理时不太有效,主要因为其快速水解,并因此与生物膜内的固着细菌接触时间短。
对生物膜-联合的微生物具有效力的杀生物剂不是必然有效地从污染表面上去除生物膜。生物膜残余物(如,外泌多糖和死细菌细胞)的物理存在仍导致金属表面不匀的氧可得性,使得腐蚀发生。因此,杀死生物膜中的微生物而不从表面上去除生物膜并不总是能解决腐蚀问题。
提供对浮游和固着细胞都具有高有效性和具有从污染表面上去除生物膜的高能力的杀生物剂,将是工业上的一个显著进步。
发明概述
本发明提供了一种用于控制水性或含湿体系中的固着微生物和生物膜的方法。所述方法包括将水性或含湿体系用有效量的式I化合物处理:
其中X是卤素;并且
R和R1分别是羟烷基和氰基基团(-C≡N),或
R和R1分别是氢和下式的酰氨基基团:
附图简述
图1是显示在杀生物剂处理之后对于不同时间间隔的活固着细菌减少的柱状图。
图2是显示杀生物剂在去除生物膜时的有效性的柱状图。
发明详述
如上所述,本发明涉及用于控制水性或含湿体系中的生物膜的方法。所述方法包括:将水性或水分体系用有效量的式(I)化合物处理。本发明人已经意外发现,式(I)化合物在控制固着细胞方面有效。另外,所述该化合物还在以下方面有效:去除水性或水分体系中的已形成的生物膜,如从在该体系中操作的设备表面上去除。
式(I)化合物具有以下化学结构:
其中X是卤素;并且R和R1分别是羟烷基和氰基基团(-C≡N),或R和R1分别是氢和下式的酰氨基基团:
优选地,式I化合物中的X是溴,氯,或碘,更优选它是溴。
优选的式(I)化合物是2,2-二溴-2-氰基-N-(3-羟丙基)乙酰胺。
进一步优选的式(I)化合物是2,2-二溴丙二酰胺。术语″2,2-二溴丙二酰胺″是指下式的化合物:
式(I)化合物可由本领域熟练技术人员使用熟知的文献技术制备。
除了其对生物膜总体有效之外,本发明化合物也意外地比其他杀生物剂更耐受在接近中性-至-碱性pH下的水解。例如,以下实施例说明,在pH 6.9,2,2-二溴丙二酰胺(DBMAL),本发明的一种示例性化合物,明显比DBNPA(一种对比杀生物剂)更稳定。在96小时内没有捡出DBMAL损失,而84%的DBNPA在该相同时间范围内在相同条件下损失。
因此,在一个进一步实施方案中,式(I)化合物用于一种用于控制水性或含湿体系中的固着微生物和生物膜的方法,其中水性或含湿组分的pH为5以上。在一些实施方案中,pH是6以上。在进一步的实施方案中,pH是7以上。在更进一步的实施方案中,pH是8以上。
可用本发明化合物处理的水性或含湿体系包括但不限于,纸浆和纸工厂,冷却塔操作,热交换器,金属加工流体,反渗透水处理,油气田注入,压裂和所产生的水,油气井和储器,脱气塔,油气操作和传输体系,油气分离体系和储存罐,油气管线,气体容器,抽水马桶,游泳池,家用排水道,家用表面,工艺设备,下水道体系,废水和处理体系,其他工业工艺水,锅炉体系,压舱水,和这些体系中的设备,导管(pipes),管道(tubes),和其他表面。优选的水性或湿体系是纸和纸浆工厂,冷却塔操作,反渗透水处理,油气田操作,分离,传输和储存体系,管线,气体容器,金属加工流体和膜-基过滤体系。
代表性膜-基过滤体系包括包含一种或多种半透膜的那些,包括但不限于:微过滤,超滤,纳米过滤,反渗透和离子-交换膜。可应用的体系包括:包含单一种类的膜(如微过滤)的那些和包含多种类型的膜(如超滤和反渗透)的那些。例如,膜-基过滤体系可包含上游微过滤或超滤膜和下游纳米过滤或反渗透膜。
可以将该主题杀生物化合物可在过滤之前加入到进料溶液中,(如加入含有所要处理的进料溶液的储存罐或池中)或在过滤过程中加入(如在过滤过程中被计量到到加压的进料溶液中)。另外,可以将主题杀生物化合物加入到接触膜的清洁或储存溶液中。就本说明书而言,接触体系的膜的任何水溶液(如原进料水,清洁溶液,膜储存溶液,等)被称作“进料溶液”。
当用于具有微或超滤和纳米过滤或反渗透膜两者的体系内时,该主题杀生物化合物向每种膜(如上游和下游膜两者)提供杀生物作用。
被一种或多种膜拒绝的那部分杀生物化合物可从浓缩物物流中回收并再循环用于随后的处理(如引导回到储存罐或在进来的进料内计量)。杀生物化合物的再循环可以是间歇或连续工艺的一部分。
在许多膜-基过滤体系中,进料溶液的pH是至少7,通常至少8,在一些实施方案中,至少9,并且在其他实施方案中,至少10。这些膜-基体系的实例描述于US 6,537,456和US 7,442,309中。另外,许多体系的膜通常用pH值为至少11并且在一些实施方案为至少12的进料溶液清洁或与其一起储存。不同于DBNPA(例如描述于WO 2008/091453),主题杀生物化合物在这些中性和碱性条件下保持有效。因此,主题杀生物化合物可被加入到与膜-基过滤体系一起使用的较宽范围的进料溶液(如pH调节的水性进料,水性清洁溶液,水性储存溶液)。
用于这些体系的膜的种类不特别受限并且包括平片,管状和中空纤维。一种优选种类的膜包括常用于纳米过滤和反渗透场合的薄-膜复合材料聚酰胺膜,例如通常描述于US 4,277,344;US 2007/0251883;和US2008/0185332。这些纳米过滤和/或反渗透膜通常作为平片提供成螺旋盘绕构型。微过滤和超滤膜的非限定性实例包括由包括聚砜,聚醚砜,聚酰胺,聚丙烯和聚偏二氟乙烯在内的各种材料制成的多孔膜。这些微和超滤膜通常作为中空纤维提供。
本领域普通技术人员无需过度实验就可以容易地确定式I化合物应该用于任何特定场合的有效量。例如,按重量计至少1ppm,另外至少5ppm,备选地至少10ppm,或至少50ppm的量一般是合适的。在一些实施方案中,该量是1000ppm以下,备选地500ppm以下或300ppm以下,或200ppm以下,或100ppm以下。在进一步的实施方案中,该量是约20至约30ppm。
式I化合物可与其他添加剂一起用于水性或含湿体系,所述添加剂例如但不限于,表面活性剂,离子/非离子聚合物和结垢和腐蚀抑制剂,氧清除剂,和/或其他的杀生物剂。
式I化合物可用于控制各种各样的微生物。在一个实施方案中,微生物是军团菌(Logionella)种的细菌,包括其数量通过经过阿米巴(amoeba)的传代而扩增的这些细菌。该军团菌(Logionella)实施方案的一种优选的杀生物剂是2,2-二溴丙二酰胺。
军团菌(Logionella)细菌已被认为是统称军团菌病的军团病和庞蒂亚克热的成因。军团菌病的许多发作已被归因于提供感染剂量的蒸发冷却体系。军团菌(Logionella)具有相对独特以下的存活能力:寄生并存在于阿米巴内,最终溶解其宿主细胞,从而以成熟的感染形式出现。该机理已被提出是军团菌(Logionella)成员在自然和人造水体系中扩增和其致病力增加的主要原因。非常需要一种可有效地控制军团菌(Logionella),包括通过经过阿米巴的传代而变得更致病的军团菌(Logionella)的形式的杀生物剂。如实施例所示,式I化合物如2,2-二溴丙二酰胺对于这种细菌控制是有效的。
本文所述的化合物意外地在控制固着/生物膜微生物方面比其他杀生物剂,包括商业化合物DBNPA有效,并因此代表了工业上的一个显著进步。
就本说明书而言,″微生物″是指细菌,藻类,或病毒。词语″控制″和″控制的″应该被宽泛地理解为,其含义包括但不限于,抑制固着微生物的生长或繁殖,杀死固着微生物,灭菌和/或防腐。″控制″和″控制的″还包括从其至少部分附着的表面上部分或完全去除固着微生物的生物膜。
″羟烷基″是指含有1至6个碳原子并且用羟基基团取代的烷基基团(即,直和支链脂族基团)。实例包括,但不限于,羟甲基,羟乙基,2-羟丙基,3-羟丙基等。
″卤素″是指氟,氯,溴,或碘。
除非另有所指,本文所用的比率,百分数,份数等以重量计。
以下实施例用于说明本发明,但无意于限定其范围。
实施例
以下组合物在实施例中评估:
2,2-二溴-3-次氨基丙酰胺(″DBNPA″)得自陶氏化学公司(DowChemical Company)。
2,2-二溴丙二酰胺(″DBMAL″)得自Johnson Mathey。
戊二醛得自陶氏化学公司。
CMIT/MIT(5-氯-2-甲基-4-异噻唑啉-3-酮和2-甲基-4-异噻唑啉-3-酮)得自陶氏化学公司。
二辛基二甲基氯化铵得自Lonza Inc。
实施例1
2,2-二溴-2-氰基-N-(3-羟丙基)乙酰胺(DBCHA)的制备
将0.1摩尔的3-氨基-1-丙醇(7.51克)加入到0.1摩尔氰基乙酸甲酯(10.1克)在甲醇(40克)中的溶液中。将混合物搅拌并且加热至60℃,历时30分钟。将甲醇溶剂从反应产物中真空汽提。无需任何必要的进一步纯化,将反应产物溶解在水中,并且与0.1摩尔的溴(16.0克)和0.03摩尔的溴酸钠(5.0克)反应。反应温度保持低于30℃。在溴和溴酸钠加入完成之后,将反应混合物搅拌30分钟,然后用稀氢氧化钠中和至pH 3至4。产率是0.09摩尔的2,2-二溴-2-氰基-N-(3-羟丙基)乙酰胺(28克)。
实施例2
对水解的稳定性:DBMAL和DBNPA的比较
在三种不同pH下制备DBMAL和DBNPA的稀溶液(低于0.5重量%)。pH通过使用标准缓冲剂溶液被设定并且保持在pH 6.9,8.0和9.0。然后保持这些溶液在或-1℃或30℃的恒定温度。定期地,等分试样用HPLC分析以确定剩余的DBMAL或DBNPA的水平。结果在表1中给出。
表1.
表1显示,即使在接近中性条件(pH=6.9)和30℃的温度,DBMAL明显比DBNPA(一种对比杀生物剂)更稳定。在96小时内没有捡出DBMAL损失,而84%的DBNPA在该相同时间范围内在相同条件下损失。
实施例3
对生物膜联合的细菌的效力
绿脓假单胞菌(P.aeruginosa)ATCC 10145的生物膜在Calgary生物膜设备(加拿大阿尔伯达的Innovotech)中生长42小时。将胰胨豆胨培养液(Trypticase Soy Broth)(TSB)作为培养基用于生物膜设备。在温育期之后,将松散联合的细胞从通过用无菌0.85%NaCl漂洗而从在浸没桩的表面上出现的生物膜上去除。生物膜随后用DBMAL(本发明杀生物剂),戊二醛(对比杀生物剂)或DBNPA(对比杀生物剂)处理。将稀盐溶液作为试验介质用于效力研究。盐溶液含有(克/升去离子水)CaCl2,0.2203g;MgSO4,0.1847g;和NaHCO3,0.2033g。溶液的最终pH被调节至8.5。
被测试的每一活性剂在盐溶液中的浓度分别是100ppm,50ppm,25ppm,12.5ppm,并且接触时间分别是4小时,24小时和48小时。在所有情况下,温育温度是37℃。无菌去离子水用作非杀生物剂处理的对照。在每一接触时间之后,桩用无菌0.85%NaCl洗涤,并且细菌通过超声处理从每个桩的表面上的生物膜上释放到无菌0.85%NaCl中(参见Ceri等,Journal of Clinical Microbiology 1999,37:1771-1776)。活细菌随后在TSB中使用连续稀释方法计数。将DBMAL与DBNPA和戊二醛比较的数据在图1中提供。
一般来说,DBMAL(本发明杀生物剂)比DBNPA(对比杀生物剂)对于固着细菌更有效。戊二醛在50ppm活性剂浓度下在48h处理之后仅具有低的有效性。在25ppm的活性剂浓度下,DBMAL是非常有效杀生物剂,并且其效力随着接触时间而增加。
实施例4
生物膜去除评估
将Calgary生物膜设备用来制备绿脓假单胞菌(P.aeruginosa)ATCC10145的生物膜。TSB用作培养基,并且生物膜在42小时内出现。表面上生长有生物膜的桩随后用无菌0.85%NaCl洗涤并随后用DBMAL(本发明杀生物剂)或DBNPA(对比杀生物剂)处理。被测试的活性剂在作为试验介质的无菌稀盐溶液中的浓度是25ppm,50ppm,100ppm。处理在37℃分别进行4小时和24小时。无菌去离子水用作未处理的对照。在处理之后,桩用无菌0.85%NaCl洗涤并随后测定在每个桩上的生物量/生物膜(参见步骤anovic等,Journal of Microbiological Methods,2000,40,175-179)。首先将生物膜用99%甲醇固定,并且在风干之后,将桩用2%(w/v)结晶紫染色并用自来水洗涤。桩随后被风干并将键接至生物膜上的结晶紫用33%冰乙酸提取。该提取溶液的光学密度(OD)在580nm测定。结果被描绘在图2中。
从数据可以看出,DBMAL(本发明杀生物剂)相比DBNPA(对比杀生物剂)具有总体更好的生物膜去除。对于这两种材料,生物膜去除的效力在较长时间的情况下提高(24h比4h)。
实施例5
阿米巴扩增的军团菌(Logionella)的控制
因为军团菌(Logionella)在自然和人造体系如冷却塔中通过经过阿米巴的传代而扩增,因此这些以阿米巴为生的军团菌(Logionella)的根除更加重要和相关。该实施例在评估合适的杀生物剂时使用以阿米巴为生的嗜肺军团菌嗜肺亚种(Legionella pneumophila)(AfLp)。
使军团菌(Logionella)在阿米巴(多噬棘阿米巴(Acanthamoebapolypohaga))内部从低感染复数(1个军团菌(Logionella)比100个阿米巴细胞)起始感染和生长。将这样的传代重复一次或多次以确立更致病的形式作为其占优势的生理机能,然后暴露于各种浓度的杀生物剂中。评估在暴露2和24小时之后进行。杀生物剂的合适中和在计数幸存者之前进行。下表6比较了各种杀生物剂对AfLp和游离的(free)正常生长的军团菌(Logionella)细胞的有效性。
表2
DDAC=二癸基二甲基氯化铵
数据显示,对所测试的每种杀生物剂,杀死AfLp所需的量大于杀死游离军团菌(Logionella)所需的量。但是,军团菌(Logionella)控制所需的DBMAL量明显低于对于包括DBNPA在内的其他被测试杀生物剂所需的那些量。这是一个意想不到且惊人的发现。提供6log杀死所需的DBMAL水平仅是在相应时间点下用于控制游离细胞所需的水平的约两倍。DBMAL相比其他的常用杀生物剂提供了一种在低剂量下控制更致病形式的AfLp的手段。
尽管本发明以上已根据其优选的实施方案进行描述,但可在本公开内容的主旨和范围内进行改进。该申请因此意味着覆盖使用本文所公开的一般原则对本发明进行的任何变化,使用,或改进。另外,本申请意味着覆盖在本发明所涉领域中已知或常规实践范围内并落入以下权利要求书的限制内的背离本公开内容的那些。
Claims (13)
2.根据权利要求1的方法,其中X是溴。
3.根据权利要求1-2的方法,其中式(I)化合物是:2,2-二溴-2-氰基-N-(3-羟丙基)乙酰胺;2,2-二溴丙二酰胺;或其混合物。
4.根据权利要求1-3的方法,其中所述水性或含湿体系的pH为5以上。
5.根据权利要求1-4的方法,其中所述水性或含湿体系是:纸浆和纸工厂,冷却塔操作,热交换器,金属加工流体,反渗透水处理,油气田注入,压裂和所产生的水,油气井和储器,脱气塔,油气操作和传输体系,油气分离体系和储存罐,油气管线,气体容器,抽水马桶,游泳池,家用排水道,家用表面,工艺设备,下水道体系,废水和处理体系,其他工业工艺水,锅炉体系,压舱水,和这些体系中的设备,导管,管道,和其他表面。
6.根据权利要求1-5的方法,其中所述微生物是细菌。
7.根据权利要求1-6中任何一项的方法,其中所述微生物是细菌。
8.根据权利要求1-7中任何一项的方法,其中所述微生物是军团菌(Logionella)属的种。
9.根据权利要求1-8中任何一项的方法,其中所述微生物是在活阿米巴内部繁殖的军团菌(Logionella)种。
10.根据权利要求1-9的方法,其中所述体系包括膜-基过滤体系,所述膜-基过滤体系包括至少一种半透膜,所述半透膜选自以下各项中的至少一项:微过滤,超滤,纳米过滤,反渗透和离子交换膜;其中所述方法包括:将式I化合物加入到进料溶液中,随后使所述进料溶液与所述半透膜接触。
11.根据权利要求1-10的方法,其中所述膜-基过滤体系至少包括:i)一种微过滤或超滤膜和ii)至少一种纳米过滤或反渗透膜。
12.根据权利要求1-11的方法,其中所述进料溶液的pH为至少9。
13.根据权利要求1-12的方法,其中所述进料溶液的pH为至少11。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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---|---|---|---|---|
US3647610A (en) * | 1970-07-31 | 1972-03-07 | Dow Chemical Co | Preservation of aqueous dispersions with bromocyanoacetamides |
US3870795A (en) * | 1973-02-28 | 1975-03-11 | Rohm & Haas | Stabilization of solutions of 3-isothiazolones employing certain metal nitrates and nitrites |
US3839583A (en) * | 1973-06-28 | 1974-10-01 | Betz Laboratories | Slime control compositions and their use |
US3929562A (en) * | 1975-03-03 | 1975-12-30 | Betz Laboratories | Synergistic compositions containing 2,2-dibromo-3-nitriloproprionamide and their use |
US4163798A (en) * | 1977-12-14 | 1979-08-07 | The Dow Chemical Company | Stabilized aqueous amide antimicrobial composition |
US4163797A (en) * | 1977-12-14 | 1979-08-07 | The Dow Chemical Company | Stabilized aqueous amide antimicrobial composition |
US4163795A (en) * | 1977-12-14 | 1979-08-07 | The Dow Chemical Company | Stabilized aqueous amide antimicrobial composition |
US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
US4241080A (en) * | 1979-05-29 | 1980-12-23 | The Dow Chemical Company | Stabilized aqueous antimicrobial composition |
US4939266A (en) * | 1982-06-01 | 1990-07-03 | Rohm And Haas Company | Nitrosamine-free 3-isothiazolone |
US4708808A (en) * | 1985-04-30 | 1987-11-24 | The Board Of Governors Of Wayne State University | Synergistic antimicrobial or biocidal mixtures |
US4661503A (en) * | 1986-06-16 | 1987-04-28 | Nalco Chemical Company | Synergistic biocide of dodecyl guanidine hydrochloride and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one |
CA1319606C (en) * | 1986-09-24 | 1993-06-29 | James Edward Gannon | Control of biofouling in aqueous systems by non-polymeric quaternary ammonium polyhalides |
US4732913A (en) * | 1987-02-25 | 1988-03-22 | Betz Laboratories, Inc. | Biocidal compositions and use thereof containing a synergistic mixture of 2-bromo-2-nitropropane-1,3-diol and 2,2-dibromo-3-nitrilopropionamide |
US4800082A (en) | 1987-03-23 | 1989-01-24 | The Dow Chemical Company | Sustained release microbiological control composition |
US4959157A (en) * | 1988-11-18 | 1990-09-25 | The Dow Chemical Company | Wastewater disinfection with a combination of biocides |
CA2129489C (en) * | 1993-08-05 | 2000-10-10 | Judy G. Lazonby | Method and composition for inhibiting growth of microorganisms including peracetic acid and a non-oxidizing biocide |
US5565109B1 (en) * | 1994-10-14 | 1999-11-23 | Lonza Ag | Hydantoin-enhanced halogen efficacy in pulp and paper applications |
GB2326113B (en) * | 1995-07-19 | 1999-06-16 | Baker Hughes Ltd | Biofouling reduction |
US5723486A (en) * | 1996-07-10 | 1998-03-03 | The Dow Chemical Company | 1,3 dithiolo(4,5)-1,3-dithiolo-2-thione derivatives, compositions and use as antimicrobial and marine antifouling agents |
US6537456B2 (en) * | 1996-08-12 | 2003-03-25 | Debasish Mukhopadhyay | Method and apparatus for high efficiency reverse osmosis operation |
JP2004534718A (ja) * | 2000-09-20 | 2004-11-18 | ロンザ ア−ゲ− | 消毒剤 |
US7156997B2 (en) * | 2001-10-05 | 2007-01-02 | Dow Global Technologies Inc. | Package assembly for piperazine-based membranes |
US7442309B2 (en) * | 2002-06-13 | 2008-10-28 | Hydranautics | Methods for reducing boron concentration in high salinity liquid |
US7008545B2 (en) * | 2002-08-22 | 2006-03-07 | Hercules Incorporated | Synergistic biocidal mixtures |
NZ540823A (en) * | 2002-12-20 | 2008-03-28 | Lonza Ag | Method for removal of biofilm |
US20040261196A1 (en) * | 2003-06-27 | 2004-12-30 | The Procter & Gamble Company | Fabric care compositions for lipophilic fluid systems incorporating an antimicrobial agent |
JP2005161254A (ja) * | 2003-12-04 | 2005-06-23 | Katayama Chem Works Co Ltd | 水系のスライム付着防止方法 |
JP2006089402A (ja) * | 2004-09-22 | 2006-04-06 | Nomura Micro Sci Co Ltd | 殺菌剤及び殺菌剤を用いた純水及び超純水の製造方法 |
US7935521B2 (en) * | 2005-03-17 | 2011-05-03 | Phigenics, Llc | Methods and compositions for rapidly detecting and quantifying viable Legionella |
EP1991055A4 (en) * | 2006-02-24 | 2012-08-29 | Bromine Compounds Ltd | FORMULATIONS CONTAINING A NONOXIDATIVE BIOZIDE AND A SOURCE OF ACTIVE HALOGEN AND THEIR USE IN THE TREATMENT OF WATER |
US20070251883A1 (en) * | 2006-04-28 | 2007-11-01 | Niu Q Jason | Reverse Osmosis Membrane with Branched Poly(Alkylene Oxide) Modified Antifouling Surface |
US20080142453A1 (en) * | 2006-12-13 | 2008-06-19 | Michael Joseph Unhoch | Biocidal composition and method for treating recirculating water systems |
JP4775268B2 (ja) * | 2007-01-10 | 2011-09-21 | 栗田工業株式会社 | 澱粉を用いる紙の製造方法 |
US7905361B2 (en) * | 2007-02-05 | 2011-03-15 | Dow Global Technologies Llc | Modified polyamide membrane |
EP2306822B1 (en) * | 2008-07-15 | 2016-10-26 | Dow Global Technologies LLC | Biocidal composition and method |
-
2010
- 2010-05-14 JP JP2012511914A patent/JP5795575B2/ja not_active Expired - Fee Related
- 2010-05-14 RU RU2011151599/04A patent/RU2559892C2/ru not_active IP Right Cessation
- 2010-05-14 US US12/780,481 patent/US20100314319A1/en not_active Abandoned
- 2010-05-14 WO PCT/US2010/034939 patent/WO2010135195A1/en active Application Filing
- 2010-05-14 CN CN2010800217831A patent/CN102428036A/zh active Pending
- 2010-05-14 EP EP10719522.4A patent/EP2432739B1/en not_active Not-in-force
- 2010-05-14 BR BRPI1007580-1A patent/BRPI1007580A2/pt not_active Application Discontinuation
- 2010-05-14 MX MX2011012352A patent/MX339299B/es active IP Right Grant
-
2015
- 2015-01-16 JP JP2015006712A patent/JP2015128766A/ja not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4232041A (en) * | 1979-06-20 | 1980-11-04 | The Dow Chemical Company | Aqueous antimicrobial composition having improved stability |
CN1362018A (zh) * | 2000-12-28 | 2002-08-07 | 罗姆和哈斯公司 | 卤代氰基乙酰胺抗微生物组合物 |
WO2008091453A1 (en) * | 2007-01-22 | 2008-07-31 | Dow Global Technologies Inc. | Method to control reverse osmosis membrane biofouling in drinking water production |
Non-Patent Citations (1)
Title |
---|
KIM等: "Literature review-efficacy of various disinfectants against Legionella in water systems", 《WATER RESEARCH》 * |
Also Published As
Publication number | Publication date |
---|---|
RU2011151599A (ru) | 2013-06-27 |
RU2559892C2 (ru) | 2015-08-20 |
JP5795575B2 (ja) | 2015-10-14 |
MX339299B (es) | 2016-05-19 |
US20100314319A1 (en) | 2010-12-16 |
EP2432739A1 (en) | 2012-03-28 |
WO2010135195A1 (en) | 2010-11-25 |
JP2012527352A (ja) | 2012-11-08 |
BRPI1007580A2 (pt) | 2020-08-18 |
EP2432739B1 (en) | 2017-03-01 |
MX2011012352A (es) | 2011-12-14 |
JP2015128766A (ja) | 2015-07-16 |
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