CN102794278A - 采用预处理清洗工业设备的方法 - Google Patents
采用预处理清洗工业设备的方法 Download PDFInfo
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- CN102794278A CN102794278A CN2012102780827A CN201210278082A CN102794278A CN 102794278 A CN102794278 A CN 102794278A CN 2012102780827 A CN2012102780827 A CN 2012102780827A CN 201210278082 A CN201210278082 A CN 201210278082A CN 102794278 A CN102794278 A CN 102794278A
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- Prior art keywords
- acid
- solution
- dirt
- preprocessing solution
- preprocessing
- Prior art date
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Classifications
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
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- C11D2111/20—
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Abstract
在常规CIP清洗工艺之前使用原位清洗过程和预处理溶液清洗设备如换热器、蒸发器、罐和其它工业设备的方法。预处理步骤改进污物的软化程度，和因此促进它的脱除。预处理溶液可以是强酸性溶液、强碱性溶液、或包含渗透剂。优选的强酸性溶液是酸过氧化物溶液。在一些实施方案中，预处理可不包括强碱或酸成分；更合适地渗透剂提供可接受的预处理水平。
Description
本申请为分案申请，其母案申请的申请日为2006年10月11日，申请号为200680037701.6，发明名称为“采用预处理清洗工业设备的方法”。
技术领域
本发明涉及通常使用CIP(原位清洗)工艺的工业设备如蒸发器、换热器和其它这类设备的清洗。
背景技术
在许多工业应用如食品和饮料的制造中，硬表面通常由污物如碳水化合物、蛋白质类、和硬污物、食品油污物和其它污物污染。这些污物可来自液体和固体食品两者的制造。碳水化合物污物如纤维素类、单糖类、二糖类、寡糖类、淀粉、树胶和其它复合材料当被干燥时，可形成坚韧、难以脱除的污物，特别是当与其它污物组分如蛋白质、脂肪、油和其它污染组分结合时。这些碳水化合物污物的脱除可能成为明显的问题。相似地，其它材料如蛋白质、脂肪和油也可形成难以脱除的污物和残渣。
食品和饮料污物当在加工期间被加热时是特别牢固的。在加工期间由于各种原因加热食品和饮料。例如，在奶品场，将乳制品在巴氏灭菌器(如HTST-高温短时间巴氏灭菌器或UHT-超高温巴氏灭菌器)上加热以使乳制品巴氏灭菌。同样许多食品和饮料产品由于蒸发而被浓缩或产生。
使用蒸发器浓缩的食品和饮料产品的具体例子包括乳制品如全脂奶和脱脂奶、炼乳、乳清和乳清衍生物、酪乳、蛋白质、乳糖溶液和乳酸；蛋白质溶液如大豆乳清、营养酵母和饲料酵母、和全蛋；果汁如橙汁和其它柑桔汁、苹果汁和其它苹果类汁、红莓汁、椰汁和热带水果汁；蔬菜汁如番茄汁、甜菜根汁、胡萝卜汁和草汁；淀粉产品如葡萄糖、右旋糖、果糖、异构化糖、麦芽糖、淀粉糠浆和糊精；糖类如液体糖、精制白糖、糖水和菊粉；提取物如咖啡和茶提取物、啤酒花浸膏、麦精、酵母提取物、胶质、及肉和骨头提取物；水解产物如乳清水解产物、汤调味品、奶水解产物和蛋白质水解产物；啤酒如无醇啤酒和麦芽汁；及婴儿食品、蛋白、豆油和发酵液。
蒸发器通常至少有两侧。一侧保持蒸汽或蒸气热源(典型地212-350°F)。另一侧保持要浓缩的工艺液体。在蒸发过程期间，将要浓缩的液体引入蒸发器。经过管子或板的热交换从工艺物流中蒸发出水，从而浓缩液体固体。可以使要浓缩的液体经过蒸发器几次直到它足够浓缩。
存在许多不同类型的蒸发器，其包括降膜蒸发器、强制循环蒸发的蒸发器、板式蒸发器、循环蒸发器、流化床蒸发器、降膜式短程蒸发器、升膜蒸发器、逆流-滴流蒸发器、搅拌器蒸发器和螺旋管蒸发器。除蒸发器以外，在蒸发装置中存在几种其它设备件，其包括预热器和加热器、分离器、冷凝器、脱气/真空系统、泵、清洗系统、蒸气洗涤器、蒸气再压缩系统和冷凝物精制系统。应当清洗所有的蒸发装置设备，但是实际的蒸发器典型地具有最困难的污染问题。
当食品或饮料产品接触任何表面时发生污染，其中一部分食品或饮料产品留在该表面上。当该表面是换热表面时，污物被热降解使得它更难除去。随着时间的过去，当更多的食品或饮料产品通过换热表面时，污物层的厚度增加。污物层作为热量和被加热的产品之间的绝热器，从而降低换热表面的效率和要求更多的能量以产生换热表面清洁时相同的效果。当换热表面是蒸发器时，在清洁换热表面和污染的换热表面之间的差异可意味着蒸发器装置能量成本的几百万美元的差异。随着能量成本明显增加，以及通过保护自然资源而加强的保护环境的认识，需要可清洗换热表面和产生有效传热的清洗过程。
原位清洗的清洗技术是适于从典型地用于从处理液体产品物流如饮料、奶、汁液等的罐、管线、泵和其它工艺设备的内部组件脱除污物的特殊清洗方案。原位清洗的清洗包括将清洗溶液通过系统而不分解任何系统组件。最小的原位清洗技术包括将清洗溶液通过设备和然后再继续正常处理。可以抛弃由更清洁残余物污染的任何产品。通常原位清洗方法包括施加清洗溶液的第一次漂洗、采用饮用水的第二次漂洗，随后再继续操作。该工艺也可包括任何其它接触步骤，其中可以将漂洗物、酸性或碱性功能流体、溶剂或其它清洗组分如热水、冷水等与设备在工艺期间的任何步骤接触。通常省去最终的饮用水漂洗以防止在清洗和/或消毒步骤之后设备被细菌污染。原位清洗处理要求完全或部分关闭被清洗的设备，它导致损失的生产时间。许多时侯由于需要大量的停车时间，设备不能充分清洗。需要使用原位清洗工艺清洗这种设备的改进方法，其使用较少的时间以充分脱除污物。
正是在此背景下完成了本发明。
发明内容
令人惊奇地已经发现食品和饮料污物和特别是烘烤的食品和饮料污物可以使用两步骤方法从表面脱除，其中将污物在预处理步骤中与预处理组合物接触，随后进行常规的原位清洗工艺。本发明涉及使用原位清洗过程清洗设备如换热器、蒸发器、罐和其它工业设备的方法。该方法适于有机污物脱除，或更特别地，适于食品或饮料污物脱除。此外，该方法涉及使用原位清洗方法从食品和饮料制造位置脱除碳水化合物和蛋白质类污物的清洗方法。
在一方面，本发明涉及包括采用强酸性溶液预处理污染的表面的方法。常规的原位清洗工艺在这个预处理步骤之后。优选的酸性溶液是酸过氧化物溶液。已经发现在酸性预处理步骤之后使用碱性洗涤剂的常规原位清洗工艺提供特别有效的结果。活性成分在酸性预处理溶液中的浓度对于一些应用为至少0.1%和通常为至少0.6%。
在另一方面，本发明涉及采用强碱性溶液预处理污染的表面的方法。常规的原位清洗工艺在这个预处理步骤之后。已经发现在强碱性预处理步骤之后使用酸性洗涤剂的常规原位清洗工艺提供特别有效的结果。
酸性或碱性的任一种预处理可包括渗透剂。渗透剂的加入改进污物的软化程度，和因此促进污物的脱除。渗透剂在预处理溶液中的浓度为至少0.01和通常为至少0.15%。约1%的浓度是可接受的。
在另一方面，本发明涉及包括采用渗透剂预处理污染的表面而不存在明显量的酸或碱的方法。常规的原位清洗工艺在这个渗透剂预处理步骤之后。在此渗透剂在预处理溶液(没有酸或碱度)的浓度为至少0.01%和通常为至少0.15%。在一个特定的实施方案中，渗透剂预处理溶液包含大约0.9%溶剂；作为渗透剂的溶剂的其它水平是合适的。
在一个特定的实施方案中，本发明是使用CIP工艺从工业设备清洗污物的方法。该方法包括施加预处理溶液到污物，该溶液包含至少0.25wt%活性成分，及活性成分包括任意的碱源、酸源、渗透剂、氧化剂和助洗剂。该方法也包括在预处理溶液之后通过设备再循环第一CIP溶液，该CIP溶液包含稀洗涤剂，和然后漂洗设备。预处理溶液可含有0.25-1.5wt%酸和/或0.01-1wt%氧化剂如过氧化物。渗透剂如二醇醚可以存在的量为0.4-10wt%。
在另一个特定的实施方案中，该方法包括采用预处理溶液预处理污物，该预处理溶液包含至少0.5wt%活性成分，活性成分包括任意的碱源、酸源、渗透剂、氧化剂、表面活性剂和助洗剂，采用稀洗涤剂溶液除去至少一部分渗透的污物，和漂洗设备。在一些实施方案中，预处理溶液包含碱源和稀洗涤剂包含酸。在其它实施方案中，预处理溶液包含酸源和稀洗涤剂是碱。
本发明包括使用两种不同的CIP溶液。
考虑到如下的详细描述，这些和其它实施方案对本领域技术人员和其它人员是显然的。但是应当理解这个概述和详细描述仅说明一些例子，和不希望限制要求保护的本发明。
附图说明
图1是包括要清洗的设备、CIP工艺设备和预处理设备的工业方法的简图。
具体实施方式
本发明涉及使用与原位清洗过程结合的预处理步骤清洗工业设备。与常规原位清洗溶液和工艺结合使用预处理步骤比单独的常规工艺提供增加的污物脱除。另外，随后为水漂洗的预处理步骤的使用提供不可预料的污物脱除量。使用预处理步骤允许使用传统上不相容的化学品和在比常规清洗过程中应用的更高的浓度下。
在此使用的"重量百分比"、"wt%"、"按重量百分比"、"重量%"及其变体表示物质的浓度为物质重量除以组合物总重量和乘以100。理解在此使用的"百分比"、"%"等与"重量百分比"、"wt%"等同义。
在此使用的术语"约"表示数量的变化，该数量的变化例如可通过如下方式出现：通过用于制备浓缩物的典型测量和液体处理过程或实际的施用溶液；通过这些过程中的无意识错误；通过用于制备组合物或进行方法的成分的制造、来源或纯度的差异等。术语"约"也涵盖对于来自特定初始混合物的组合物，由于不同平衡条件而不同的量。不管是否由术语"约"修饰，权利要求包括数量的等同物。
应当注意到在此说明书和所附权利要求中使用的单数形式"a,""an"和"the"包括复数指示物，除非内容清楚地另外指示。因此例如，包含"化合物"的组合物包括具有两种或多种化合物。也应当注意到术语"或"通常以包括"和/或"的意义使用，除非内容清楚地另外指示。
本发明的方法适用于通常使用原位清洗(即CIP)清洗过程清洗的设备。这些设备的例子包括蒸发器、换热器(包括管管换热器、直接蒸汽注入换热器和板框式换热器)、加热盘管(包括蒸汽、火焰或传热流体加热的盘管)、再结晶器、盘式结晶器、喷雾干燥器、转鼓干燥器和罐。这种方法可通常用于任何应用，这些应用中需要除去在污物上结块或在污物上烧焦的如蛋白或碳水化合物；应用包括食品和饮料工业(特别是奶场)、酿造、油加工、工业农艺和乙醇处理。
CIP处理通常是公知的。该方法包括施加稀溶液(典型地约0.5-3%)到要清洗的表面上。溶液流过表面(3-6英尺/秒)，缓慢地除去污物。将新溶液再施加到表面或将相同的溶液再循环和再施加到表面。
除去污物(包括有机污物、无机污物或两种组分的混合物)的典型CIP工艺包括至少三个步骤：碱性溶液洗涤、酸溶液洗涤和然后新鲜水漂洗。碱性溶液软化污物和除去有机碱溶性污物。随后的酸溶液除去由碱清洗步骤留下的矿物污物。碱和酸溶液的强度及清洗步骤的持续时间典型地取决于污物的持久性。水漂洗除去任何残余的溶液和污物，及在将设备返回在线操作之前清洗表面。本发明提供在CIP工艺之前的预处理步骤，其渗透污物。渗透材料软化污物，用作催化剂或另外当常规CIP溶液接触污物时提高常规CIP溶液的活性。因此预处理促进污物脱除。
现在参考图1，工艺设备的简图用附图标记10说明。工艺10包括罐20，其是要清洗的设备。进料管线25供应各种清洗溶液到罐20和排料管线27从罐20除去溶液。通过适当管子、阀门、泵等操作性连接的是用于CIP工艺的设备，其用附图标记30表示。CIP工艺30包括用于保持稀CIP化学品的罐35。来自罐20的排料管线27用于从罐20将溶液再循环回到CIP工艺30和罐35。工艺10也包括用于预处理工艺的设备，其用附图标记40表示。预处理设备40包括第一罐42和第二罐44。当使用两个罐时，通常一个罐如罐42包含碱性预处理物和另一个罐如罐44包含酸性预处理物。适当的管子、阀门、泵等用于操作性地连接罐42、44与进料管线25进入罐20。工艺10的这种设置允许预处理应用到罐20而不使用大量的另外设备如管路。以下描述涉及清洗罐20的方法的另外详细情况。
预处理溶液
如上所述，在常规CIP化学处理应用之前将预处理溶液或预处理步骤应用到污物。选择预处理溶液的化学品以促进在要清洗的表面上污物的脱除。预处理溶液预涂覆和渗透入污物，从而软化污物。可以根据要清洗的污物选择使用的具体化学品。使用的化学品可以与CIP化学品相容。在一些实施方案中，需要预处理与CIP化学品不相容；在这种情况下，预处理与CIP化学品反应。已经发现使用不相容化学品进一步增加污物-脱除效力。
预处理溶液包含0.25%活性成分，在一些情况下包含至少0.5%、优选至少2%和更优选至少3%。术语"活性成分"指的是促进污物的软化、溶解和脱除的非惰性成分。这些活性成分包括任何碱性物/碱、酸、渗透剂(其包括表面活性剂)、助洗剂、氧化剂、催化剂和螯合掩蔽剂或螯合剂。在大多数实施方案中，水是溶液的剩余部分。典型地溶液含有不大于约15%、优选不大于约10%活性成分。对于大多数应用，优选是约1-10%的浓度；约1-3%的浓度适于大多数应用。
碱性或酸性成分
预处理溶液任选地和优选地包括碱性或酸性成分。合适碱源的例子包括碱性盐、胺、烷醇胺、碳酸盐和硅酸盐。特别优选的碱源包括NaOH(氢氧化钠)、KOH(氢氧化钾)、TEA(三乙醇胺)、DEA(二乙醇胺)、MEA(单乙醇胺)、碳酸钠、吗啉、偏硅酸钠和硅酸钾。
合适酸源伯例子包括无机酸(如磷酸、硝酸、硫酸)和有机酸(如乳酸、乙酸、羟基乙酸、柠檬酸、谷氨酸、戊二酸和葡萄糖酸)。
预处理溶液中碱性物或酸的量在一些情况下为至少0.25wt%和不大于10wt%。碱性物或酸的合适水平包括2-5wt%和0.5-1.5wt%。
渗透剂
渗透剂可以在预处理溶液中存在。可以将渗透与碱源或酸源在溶液中结合，或可以使用渗透剂而不使用碱源或酸源。优选地，渗透剂是水溶混的。
合适渗透剂的例子包括醇、短链乙氧基化醇和酚(含有1-6个乙氧基化物基团)。有机溶剂也是合适的渗透剂。用作渗透剂的合适有机溶剂的例子包括酯、醚、酮、胺、及硝酸化烃和氯代烃。
另一类优选渗透剂是乙氧基化醇。乙氧基化醇的例子包括烷基、芳基、和烷芳基烷氧基化物。这些烷氧基化物可以通过采用氯-、溴-、苄基-、甲基-、乙基-、丙基-、丁基-和烷基-基团封端而进一步改性。溶液中乙氧基化醇的优选含量为1-20wt%。
另一类渗透剂是脂肪酸。脂肪酸的一些非限制性例子是C6-C12直链或支化脂肪酸。优选的脂肪酸在室温下为液体。
用作渗透剂的另一类优选溶剂是水溶性二醇醚。二醇醚的例子包括二丙二醇甲基醚(以商品名DOWANOL DPM获自Dow Chemical Co.)、二甘醇甲基醚(以商品名DOWANOL DM获自Dow Chemical Co.)、丙二醇甲基醚(以商品名DOWANOL PM获自Dow Chemical Co.)和乙二醇单丁基醚(以商品名DOWANOL EB获自Dow Chemical Co.)。溶液中二醇醚的优选含量为0.5-20wt%。
表面活性剂也是用于预处理溶液的合适渗透剂。合适表面活性剂的例子包括非离子、阳离子和阴离子表面活性剂。优选是非离子表面活性剂。非离子表面活性剂改进污物脱除和可降低溶液在处理的表面上的接触角。合适非离子表面活性剂的例子包括烷基-、芳基-、和芳烷基-、烷氧基化物、烷基聚糖苷及其衍生物、胺及其衍生物、和酰胺及其衍生物。另外有用的非离子表面活性剂包括具有聚环氧烷聚合物作为表面活性剂分子一部分的那些。这些非离子表面活性剂例如包括脂肪醇的氯-、苄基-、甲基-、乙基-、丙基-、丁基-和其它类似烷基封端的聚氧亚乙基和/或聚氧亚丙基二醇醚；无聚环氧烷的非离子物如烷基聚糖苷；山梨聚糖和蔗糖酯及它们的乙氧基化物；烷氧基化乙二胺；羧酸酯如甘油酯、聚氧乙烯酯、脂肪酸的乙氧基化和二醇酯等；羧酸酰胺如二乙醇胺缩合物、单烷醇胺缩合物、聚氧乙烯脂肪酸酰胺等；和乙氧基化胺和醚胺和其它类似非离子化合物。也可以使用硅酮表面活性剂。
含有聚环氧烷聚合物部分的另外合适非离子表面活性剂包括如下的非离子表面活性剂：含有1-约20个环氧乙烷基团的C6-C24醇乙氧基化物；含有1-约100个环氧乙烷基团的C6-C24烷基酚乙氧基化物；含有1-约20个糖苷基团的C6-C24烷基聚糖苷；C6-C24脂肪酸酯乙氧基化物、丙氧基化物或甘油酯；和C4-C24单或二烷醇酰胺。
如果表面活性剂用作渗透剂，表面活性剂在预处理溶液中的量典型地为至少0.25%。表面活性剂的可接受水平包括0.4-8wt%和1-4wt%。
总体上，当存在碱源或酸源时，渗透剂在预处理溶液中的量为至少0.2wt%和不大于2.5wt%。当碱源或酸源存在时渗透剂的可接受水平包括0.4-2wt%；优选是1-2wt%。相对于当存在时的任何碱源或酸源，渗透剂的量通常为1:1-1:5。
对于不含碱源或酸源的预处理溶液，溶液中渗透剂为至少0.05wt%和不大于50%。通常该水平为0.1-25wt%。渗透剂的可接受水平包括0.5-10wt%和1-5wt%。
氧化剂
预处理溶液可包括氧化试剂或氧化剂如过氧化物或过氧酸。获得的溶液非常有效地对抗蛋白质和淀粉污物。此外，这些氧化合物与污物的反应，特别地当与碱源结合时，对污物和在污物中产生有力的机械作用，它提高污物的脱除超出由化学和漂白作用引起的。
合适的成分是氧化剂如亚氯酸盐、溴、溴酸盐、一氯化溴、碘、一氯化碘、磺酸盐、高锰酸盐、硝酸盐、硝酸、硼酸盐、过硼酸盐和气体氧化剂如臭氧、氧气、二氧化氯、氯气、二氧化硫及它们的衍生物。过氧化合物(其包括过氧化物和各种过羧酸(其包括过碳酸盐))是合适的。
过氧羧酸(或过羧酸)通常具有通式R(CO3H)n，其中例如R是烷基、芳烷基、环烷基、芳基或杂环基团，且n是1、2或3，及通过在母体酸之前加过氧而命名。R基团可以是饱和或不饱和的以及取代或未取代的。中等链过氧羧酸(或过羧酸)通常具有通式R(CO3H)n，其中R是C5-C11烷基、C5-C11环烷基、C5-C11芳烷基、C5-C11芳基或C5-C11杂环基团；且n是1、2或3。短链脂肪酸可具有通式R(CO3H)n，其中R是C1-C4且n是1、2或3。
一些过氧羧酸包括过氧戊酸、过氧己酸、过氧庚酸、过氧辛酸、过氧壬酸、过氧异壬酸、过氧癸酸、过氧十一烷酸、过氧十二烷酸、过氧抗坏血酸、过氧己二酸、过氧柠檬酸、过氧庚二酸、过氧辛二酸、它们的混合物等。
支链过氧羧酸包括过氧异戊酸、过氧异壬酸、过氧异己酸、过氧异庚酸、过氧异辛酸、过氧异壬酸、过氧异癸酸、过氧异十一烷酸、过氧异十二烷酸、过氧新戊酸、过氧新己酸、过氧新庚酸、过氧新辛酸、过氧新壬酸、过氧新癸酸、过氧新十一烷酸、过氧新十二烷酸、它们的混合物等。
典型的过氧化合物包括过氧化氢(H2O2)、过乙酸、过辛酸、过硫酸盐、过硼酸盐或过碳酸盐。
预处理溶液中氧化剂的量为至少0.01wt%和不大于1wt%。氧化剂的可接受水平是0.01-0.50wt%；0.3wt%是特别合适的水平。相对于任何酸源，氧化剂的合适水平通常为1:1-1:10、1:3-1:7或1:20-1:50。0.25-10wt%磷酸与50-5000ppm(0.005-0.5wt%)过氧化氢的溶液是特别合适的。例子预处理溶液包含0.75wt%磷酸和500ppm(0.05wt%)过氧化氢，它的氧化剂:酸比例为为1:15。
助洗剂
预处理溶液优选包括助洗剂。助洗剂包括螯合试剂(螯合剂)、多价螯合试剂(多价螯合剂)、洗涤剂助洗剂等。助洗剂通常稳定组合物或溶液。助洗剂的例子包括膦酸和膦酸盐、磷酸盐、氨基羧酸盐和它们的衍生物、焦磷酸盐、多磷酸盐、乙二胺和亚乙基三胺衍生物、羟基酸和单-、二-和三-羧酸盐和它们对应的酸。其它助洗剂包括铝硅酸盐、硝基乙酸盐(nitroloacetates)和它们的衍生物、及它们的混合物。进而其它助洗剂包括氨基羧酸盐，其包括乙二胺四乙酸(EDTA)、羟基乙二胺四乙酸(HEDTA)和二亚乙基三胺五乙酸的盐。优选的助洗剂是水溶性的。
特别优选的助洗剂包括EDTA(其包括EDTA四钠)、TKPP(多磷酸三钾)、PAA(聚丙烯酸)及其盐、膦酰基丁烷羧酸和葡萄糖酸钠。
预处理溶液中如果存在的助洗剂的量典型地为至少0.25wt%和不大于5wt%。助洗剂的可接受水平包括0.5-1.0wt%和1-2.5wt%。
预处理方法
本发明的方法涉及在常规CIP工艺之前施加预处理溶液到要清洗的表面。得到的CIP工艺要求较少的步骤和/或每个步骤较少的时间。例如，常规CIP工艺包括在初始水漂洗之后的五个步骤：常规碱(NaOH)洗涤以脱除污物、中间漂洗、常规酸洗涤以脱除矿物质和污垢、水漂洗和常规消毒步骤。这种方法可以在初始水漂洗之后由三步骤方法替代：预处理步骤、常规洗涤和水漂洗。
通过使用上面刚刚描述的两种预处理工艺的任一种，与常规五步骤工艺相比，用于采用预处理的整体清洗工艺的水量减少约30%或更多。与常规五步骤工艺相比，用于采用预处理的整体清洗工艺的时间量减少约30%或更多。具体的步骤数目、水的使用或减少的处理时间取决于预处理溶液的浓度和化学品。
再次参考图1，将预处理溶液在由40表示的设备中贮存。在这个工艺10中，罐42保持碱性预处理溶液和罐44保持包含过氧化物的酸性预处理溶液。
为清洗20，将罐20及其连接管线中可能存在的任何产品排出。可以包括水漂洗以脱除任何残余产品。在一个实施方案中，将来自罐42的碱性预处理溶液通过管道和进料管线25泵送入罐20。常规CIP施加设备如喷头施加预处理溶液到罐20的内表面上。预处理溶液逐级或另外向下流动到罐20的表面，从而软化污物。可以第二次施加预处理溶液，尽管通常不要求这样。
在预处理溶液施加和排出之后，使用来自工艺30和罐35的洗涤剂实施常规CIP工艺。CIP洗涤剂可以是酸性或碱性的。将来自罐35的洗涤剂通过罐20经过进料管线25、返回管线27和其它适当的管道再循环。
在另一个实施方案中，将来自罐44包含过氧化氢的预处理溶液通过管道和进料管线25泵送入罐20。在过氧化物预处理溶液施加和排出之后，使用来自工艺30和罐35的碱性洗涤剂如氢氧化钠实施常规CIP工艺。氢氧化钠活化在罐20壁上的任何残余过氧化物。
当将预处理溶液引入CIP工艺时，取决于设备的部件在具体的位置加入预处理溶液可能是有益的。例如，当处理HTST巴氏灭菌器时，优选在原料平衡罐引入预处理溶液。替代地，可以在增压泵的吸入侧或刚好在板组装之前在T或阀位置引入预处理溶液。当处理UHT巴氏灭菌器时，优选在水平衡罐引入预处理溶液。替代地，可以在产品平衡或原料罐或增压泵的吸入侧引入预处理溶液。当处理蒸发器时，优选在效果循环泵的吸入侧引入预处理溶液。替代地，预处理溶液可以在CIP平衡罐引入。最终，当处理啤酒蒸馏再沸器时，优选在锅炉循环泵的吸入侧引入预处理溶液。替代地，预处理溶液可以在循环泵和蒸馏塔或CIP平衡罐之间的阀门中引入。预处理溶液优选接近要清洗的表面注入。这通过避免预处理化学品由CIP供料罐和分布管线的整个体积的稀释，而允许更高的化学品浓度。
以下提供合适预处理步骤的各类例子。
在一个特定的实施例中，将10wt%NaOH的碱性预处理溶液喷淋到保持罐的内表面上和使其排出。在约20分钟之后，启动具有1%酸性溶液的的CIP工艺。
在第二个特定的实施例中，将1wt%磷酸的酸性预处理溶液循环到框中板框式换热器的内表面上。溶液包含0.1wt%H2O2。过氧化物也由随后的常规碱性CIP溶液催化活化，该CIP溶液引起进一步的泡腾、形成高氧化电势物质和污物脱除。
在第三个特定的实施例中，将含有约1.0wt%无机酸和1.0wt%溶剂渗透剂的酸性预处理溶液循环到蒸发器的换热表面上和从该表面排出。在约20分钟之后，启动CIP工艺。将含有大约0.5wt%活性NaOH的常规碱性洗涤物进料至蒸发器。碱与任何酸性残余物反应，从而产生促进污物脱除的热和机械作用。
尽管主要在清洗含有食品和饮料污物的表面的上下文中讨论了本发明，应理解的是本发明可用于需要清洗的应用，该清洗通常包括膜如螺旋膜、用于水过滤或脱盐及化学和制药工业中的换热表面的平关闭陶瓷膜。
为了更完全理解本发明，给出如下实施例以说明一些实施方案。应理解这些实施例和试验是说明性的和不是限制性的。除非相反地指示，所有的份数为重量份。
实施例
实施例1
测试过程
通过混合3克干燥奶粉和3克污物制备固体奶颗粒。将获得的混合物在模头中在10,000磅下压挤30秒，和然后加上更多的压力以再次施加10,000磅另外30秒。将该颗粒放入筛网中和浸入下述预处理溶液5分钟，取出和然后排液5分钟。将筛网和干燥颗粒放入120°F的0.5wt%NaOH的烧杯。(称为"无"的测试不具有预处理步骤；称为"无*"的测试不具有预处理步骤和使用在120°F下的3.0%NaOH而不是0.5%NaOH清洗)。采用在350rpm下旋转的大搅拌棒，将烧杯放置在设定到49℃(大约120°F)的电炉上。在30分钟之后，将筛网和颗粒从清洗溶液取出和轻轻地在去离子水中浸入和取出五次，和然后在50℃烘箱中干燥过夜。测试结果如下。
预处理1
制备10wt%活性NaOH溶液和该溶液用作预处理物。预处理物含有100,000ppm氢氧化钠(碱性清洗剂)。
预处理2
制备含有1360ppmEDTA四钠(助洗剂和/或螯合掩蔽剂)、3000ppm葡萄糖酸钠(助洗剂和/或螯合掩蔽剂)、2400ppm硅酸钾(碱性清洗剂)、7000ppm烷基聚糖苷(表面活性剂)和4200ppm氢氧化钾(碱性清洗剂)的预处理溶液。这个预处理2含有3.66%碱、0.43%助洗剂/螯合掩蔽剂和0.7%表面活性剂，从而提供4.79%活性成分。
预处理3
制备含有41550ppm多羧基化醇乙氧基化物(表面活性剂)、9540ppm氧化辛胺(表面活性剂)、25500ppm烷基聚糖苷(表面活性剂)和4150ppm2-乙基己醇乙氧基化物(渗透剂)的预处理溶液。这个预处理3含有0.4%渗透剂和7.6%表面活性剂，从而提供8%活性成分。
预处理4
制备含有1600pm氢氧化钾(碱性清洗剂)、9465ppm氢氧化钠(碱性清洗剂)、18500ppm聚丙烯酸(助洗剂和/或螯合掩蔽剂)和4625ppm膦酰基丁烷三羧酸(助洗剂和/或螯合掩蔽剂)的预处理溶液。这个预处理4含有1.10%碱和2.3%助洗剂/螯合掩蔽剂，从而提供2.9%活性成分。
结果表明当比较方法时清洗工艺的一致性和差异。结果指示NaOH的低含量好于高含量，及预处理溶液3和4优于预处理溶液1和2。但是，这个差异可能是由于使用的测试过程。测试1和2在一个电炉上进行，而测试3和4在第二个电炉上进行。可能的是这两个电炉没有同样保持120°F温度。
在重复测试之间看到较大的差异(即对于溶液4的61%和39%)；可能的是一个颗粒在其中含有裂纹，从而提供颗粒破裂的弱位置。高的暴露表面积会导致如果崩解时增加的速率。
在相同的电炉上进行测试以尝试确定是否在电炉的温度控制之间存在任何不一致性。结果见下表，在称为"预处理的颗粒损失wt%"的列中。
作为替代和对比方法，将1克预处理溶液加入315克0.5%NaOH清洗溶液中。因此不施加预处理化学品为单独的步骤，将预处理化学品加入清洗溶液中。结果见下表，在称为"无预处理的颗粒损失wt%"的列中。
| 预处理 | 预处理的颗粒损失wt% | 无预处理的颗粒损失wt% |
| 1 | 22.16% | 36.92% |
| 2 | 23.90% | 37.39% |
| 3 | 41.96% | 34.01% |
| 4 | 50.17% | 31.95% |
结果表明取消单独的预处理步骤和直接将化学品加入清洗溶液中加强两个效力较小溶液(1-10%NaOH；2-10%KX-3108)的性能和降低两个效力较大溶液(3-10%Quadexx400；4-10%Quadexx500)的性能。所有这些结果均好于不存在预处理时(它提供约29%的颗粒损失)。
实施例2
测试过程
在一侧含有污物的污染的不锈钢测试板通过如下方式制备：在烘箱中在120℃下将捣碎玉米固体的混合物干燥到板一侧上4小时。然后如下所述清洗污染的板。
对于测试(I)，采用预处理步骤将800克预处理溶液5放入1000ml烧杯。已经确定大约1克预处理溶液接触污染的板和保留在污染的板上。在预处理物中短暂浸入之后，将板在环境条件下挂5分钟。然后在污物侧向下的情况下将干燥的板放入1000ml烧杯(其具有750g的40℃水)。在30分钟之后，将板轻轻在去离子水中浸入和取出五次，和然后干燥板。测试结果如下。
对于测试(II)，未预处理测试板，但将该板在750g的40℃水中(向其中加入1g预处理5)中清洗。
对于测试(III)将测试板不预处理，但在750g的40℃水中清洗。
预处理5
制备含有400ppmEDTA四钠(助洗剂和/或螯合掩蔽剂)、4500ppm多磷酸三钾(助洗剂和/或螯合掩蔽剂)、3852ppm氢氧化钾(碱性清洗剂)、3000ppm聚乙烯苯酚醚磷酸盐(表面活性剂)、1000ppm偏硅酸钠(碱性清洗剂)、9000ppm乙二醇单丁基醚(渗透剂)和2400ppm二甲苯磺酸钠(表面活性剂)的预处理溶液。这个预处理5含有0.5%碱、0.5%助洗剂/螯合掩蔽剂、0.5%表面活性剂和0.9%渗透剂，从而提供2.4%活性成分。
| 测试方法 | 脱除污物的平均% |
| I | 99.12%(三次测试的平均值) |
| II | 14.14%(三次测试的平均值) |
| III | 14.12%(三次测试的平均值) |
以上结果表明仅将预处理化学品加入洗涤溶液中并不会改进从测试板的污物脱除。更合适的是预处理溶液和洗涤溶液的单独和逐步施加提供改进的污物脱除。
实施例3
实施例3测试各种不同预处理物和主要洗涤化学品对脱除玉米啤酒稀釜馏物浆的效力。对于这个测试，通过将3英寸乘5英寸不锈钢筛网称重制备玉米啤酒稀釜馏物浆污物。制备85%玉米啤酒稀釜馏物浆和15%去离子水的混合物和将筛网浸入混合物和放置以排出过量物质10分钟。然后将筛网在125℃下烘烤2小时。将筛网再浸入和烘烤另外2次，合计3次。再次将最终筛网称重。为了清洗，将1000mL表1的化学清洗溶液加热到180°F。将筛网插入清洗溶液。搅拌棒在清洗溶液中和对于整个测试设定在400rpm下(30分钟)。在30分钟之后，取出筛网和在称重之前允许其干燥。使用如下公式计算污物脱除百分比：
((污染的wt-之后的wt)/(污染的wt-初始wt))x100=%污物脱除
表1表明各种预处理物和主要洗涤化学品的污物脱除百分比。
表1对玉米啤酒稀釜馏物浆的预处理溶液效力
实施例4
实施例4比较各种氧化剂脱除玉米啤酒稀釜馏物浆的能力。对于这个实施例，筛网如在实施例3中所述由玉米啤酒稀釜馏物浆污染和清洗。表2显示各种氧化剂对污物脱除的影响。
表2氧化剂对玉米啤酒稀釜馏物浆脱除的影响
实施例5
实施例5比较使用本发明预处理溶液与仅使用氢氧化钠来清洗筛网所需的时间量。这个实施例测试清洗玉米啤酒稀釜馏物浆和全脂奶污物的时间。玉米啤酒稀釜馏物浆污物如在实施例3中所述制备和清洗。对于全脂奶污物，污物通过如下方式制备：称重要被污染的不锈钢圆盘和将圆盘附加到1.5英尺、3英寸直径不锈钢管的底部。将水浴加热到205°F至210°F和将具有圆盘的管子放入水浴。将1/3加仑全脂奶加入使用的每个管子中和允许放置4小时。在4小时之后，将圆盘取出和在称重之前干燥至少48小时。当清洗全脂奶污物时，将圆盘附加到顶部搅拌器上。使用电炉将所需的清洗溶液加热到180°F。将圆盘插入清洗溶液的1L烧杯中10分钟和将顶部搅拌器设定到50rpm。在10分钟之后，将圆盘从清洗溶液取出和放入去离子水的烧杯。将顶部搅拌器设定在200rpm下30秒。将圆盘取出和在称重之前干燥至少48小时。使用如下公式计算污物脱除百分比：
((污染的wt-之后的wt)/(污染的wt-初始wt))x100=%污物脱除
表3和4显示使用如下物质时脱除筛网或圆盘上100%污物所需的时间：单独的氢氧化钠、随后为氢氧化钠洗涤的StabicipOxi预处理、和随后为氢氧化钠洗涤的配制物A(74%过氧化氢(35%)、9.75%异丙苯磺酸钠(40%)、5.25%辛烷磺酸钠、3.50%羟基亚乙基二膦酸(60%)、3%甲磺酸、1%正丁基封端的醇乙氧基化物(5EO)和3.5%壬酸)。StabicipOxi是过氧化氢基组合物，商购自EcolabInc.(St.Paul,MN)。
表3清洗玉米啤酒稀釜馏物浆污物的时间
表3显示当与单独的氢氧化钠洗涤相比时，同时包含过氧化氢基预处理组合物以及氢氧化钠洗涤使得清洗玉米啤酒稀釜馏物浆的时间减半。
表4清洗全脂奶污物的时间
表4显示当与单独的氢氧化钠洗涤相比时，同时包含过氧化氢基预处理组合物以及氢氧化钠得清洗全脂奶污物的时间减半。当与单独的氢氧化钠洗涤相比时，使用配制物A以及氢氧化钠洗涤使清洗全脂奶污物的时间减少一半以上。
实施例6
实施例6测试各种不同预处理物和主要洗涤化学品对全脂奶污物脱除的效力。对于这个测试，全脂奶污物如在实施例5中所述制备和清洗。表5显示各种组合的脱除百分比。
表5预处理溶液对全脂奶的效力
本发明已经参考各种具体和优选的实施方案和技术进行描述。但是，应当理解可以在本发明的精神和范围内进行许多变化和改进。
Claims (10)
1.使用CIP工艺从工业设备清洗污物的方法，该方法包括：
(a)预处理步骤，其中向污物施加预处理溶液，所述预处理溶液包含至少0.25wt%活性成分，所述活性成分选自碱源、酸源、渗透剂、氧化剂和助洗剂；
(b)原位清洗步骤，其中在所述预处理溶液之后再循环第二溶液通过所述设备，所述第二溶液包含约0.5-3wt%的洗涤剂；和然后
(c)漂洗所述设备。
2.权利要求1的方法，其中所述预处理溶液中碱或酸的量为至少0.25wt%和不大于10wt%，其中所述酸选自磷酸、硝酸、硫酸、乳酸、乙酸、羟基乙酸、柠檬酸、谷氨酸、戊二酸和葡萄糖酸，和所述碱选自氢氧化钠、氢氧化钾、三乙醇胺、二乙醇胺、单乙醇胺、碳酸钠、吗啉、偏硅酸钠和硅酸钾。
3.权利要求1或2的方法，其中所述预处理溶液包含渗透剂，和所述渗透剂选自醇、酯、醚、酮、胺、酚、硝酸化烃、氯代烃、短链乙氧基化醇、脂肪酸、水溶性二醇醚以及非离子、阳离子和阴离子表面活性剂。
4.权利要求3的方法，其中所述脂肪酸选自C6-C12直链或支化脂肪酸。
5.权利要求1-4任一项的方法，其中所述预处理溶液进一步包含至少0.01wt%和不大于1wt%的氧化剂，和所述氧化剂选自亚氯酸盐、溴、溴酸盐、一氯化溴、碘、一氯化碘、碘酸盐、高锰酸盐、硝酸盐、硝酸、硼酸盐、过硼酸盐、臭氧、氧气、二氧化氯、氯气、二氧化硫、过氧化物和过氧羧酸。
6.权利要求5的方法，其中所述氧化剂选自过氧化氢、过乙酸、过辛酸、过硫酸盐、过硼酸盐和过碳酸盐。
7.权利要求6的方法，其中所述预处理溶液包含0.25-10wt%磷酸和0.05-0.5wt%过氧化氢。
8.权利要求7的方法，其中所述预处理溶液包含0.75wt%磷酸和0.05wt%过氧化氢。
9.权利要求1-8任一项的方法，其中所述预处理溶液进一步包含至少0.25wt%和不大于5wt%的助洗剂，和所述助洗剂选自膦酸、膦酸盐、磷酸盐、氨基羧酸盐、焦磷酸盐、多磷酸盐、乙二胺、羟基酸、单-、二-和三-羧酸盐和它们对应的酸、铝硅酸盐、和硝基乙酸盐。
10.权利要求9的方法，其中所述预处理溶液包含0.5-1.0wt%助洗剂或1-2.5wt%助洗剂。
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| CN113786735B (zh) * | 2021-09-18 | 2024-04-05 | 鞍钢栗田(鞍山)水处理有限公司 | 一种陶瓷膜清洗剂及其制备、清洗方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0615774B1 (pt) | 2017-02-14 |
| JP4927858B2 (ja) | 2012-05-09 |
| BRPI0615774A2 (pt) | 2011-05-24 |
| DK1948774T4 (en) | 2018-10-15 |
| AU2006306652A1 (en) | 2007-05-03 |
| EP1948774B2 (en) | 2018-07-11 |
| DK1948774T3 (en) | 2015-11-09 |
| EP1948774B9 (en) | 2015-11-18 |
| JP2009513339A (ja) | 2009-04-02 |
| EP1948774B1 (en) | 2015-09-02 |
| CN101283082A (zh) | 2008-10-08 |
| US20100236581A1 (en) | 2010-09-23 |
| US20080121250A1 (en) | 2008-05-29 |
| CA2619007C (en) | 2013-12-10 |
| AU2006306652B2 (en) | 2011-07-14 |
| CA2619007A1 (en) | 2007-05-03 |
| US8114222B2 (en) | 2012-02-14 |
| US20080105282A1 (en) | 2008-05-08 |
| US20060042665A1 (en) | 2006-03-02 |
| PL1948774T5 (pl) | 2018-10-31 |
| CN102794278B (zh) | 2015-04-29 |
| PL1948774T3 (pl) | 2016-02-29 |
| WO2007050291A1 (en) | 2007-05-03 |
| EP1948774A1 (en) | 2008-07-30 |
| NZ565897A (en) | 2011-03-31 |
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