CN1120832A - 涂敷过碳酸钠颗粒及其生产方法和含此颗粒的洗涤剂、清洁剂及漂白剂组合物 - Google Patents
涂敷过碳酸钠颗粒及其生产方法和含此颗粒的洗涤剂、清洁剂及漂白剂组合物 Download PDFInfo
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Abstract
过碳酸钠通常以涂敷颗粒形式使用,以增加其在洗涤剂中的贮存稳定性。根据本发明涂敷的过碳酸钠颗粒的涂层含有四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液反应的产物。涂敷过碳酸钠颗粒通过将上述反应产物的溶液涂敷到过碳酸盐颗粒上来制备。含有根据本发明涂敷的过碳酸钠颗粒的洗涤剂、漂白剂和清洁剂组合物具有很高的贮存稳定性。
Description
本发明涉及涂敷的过碳酸钠颗粒,其涂层含过氧化的硼化合物,它赋予过碳酸钠高的贮存稳定性。本发明也涉及生产该涂敷的过碳酸钠颗粒的方法,通过将一种或多种涂层组分,尤其以其水溶液形式涂敷到待涂敷的过碳酸钠上及涂敷到含有根据本发明的涂敷的过碳酸钠颗粒的洗涤剂、清洁剂及漂白剂组合物中。
过碳酸钠(2Na2CO3.3H2O2)在洗涤剂、漂白剂及清洁制剂中用做活性氧组分。考虑到过碳酸钠在潮湿环境中及在洗涤剂、清洁制剂中各种组分的存在下的贮藏稳定性差,必须提高过碳酸钠的稳定性以减少活性氧(Oa)的损失。稳定化的主要方法是将过碳酸钠颗粒涂敷上一层稳定组分。如已有的将过碳酸钠涂敷上石蜡或聚乙二醇。但遗憾的是,这种方法不仅使其在水中的溶解度大大降低,而且也不能获得足够长期的稳定性。即使碱金属硅酸盐涂敷到过碳酸钠的颗粒上,正如DE—OS 2652776中建议的,也不能达到足够的稳定性,另外还引入了不需要的不溶性组分。在DE—OS2417572和DE—OS 2622610所述的方法中,用硫酸钠和碳酸钠或硫酸钠、碳酸钠和硅酸钠做涂层组分。在这些方法中,将涂层组分的溶液喷洒在流化床干燥塔中的过碳酸钠颗粒上。获得足够的稳定性需要大量的涂敷物,从而相应使活性氧含量大大降低。
尽管从DE—PS 2800 916中了解到,含有偏硼酸、原硼酸和四硼酸中至少一种硼化合物的涂敷物能用于稳定过碳酸钠,但是,正如比较实施例中所示的DE—OS 3321082中把用这种方法获得的稳定效果看成是不够。然而,具有含硼酸钠的壳层的过碳酸钠被认为是有有利的。但是,正如本申请书的发明人在重复DE—OS33 21082的实施例时所发现的,为了获得足够的稳定性,硼酸盐及非必须的其它涂敷物组分不得不大量地存在于涂层中,以致使得以稳定的过碳酸钠的有效活性氧含量总是低于14wt%。在EP—A 0487256中进一步发展了使用硼酸盐的稳定化方法,尽管这里公开的涂敷方法至少包括两步,所以在技术上是复杂的。
最后,DE—AS 2458326中描述了一种稳定过碳酸钠的方法,即使是它与清洁剂掺和的情况下该方法也能提高纯过碳酸钠的贮存稳定性。在该法中,用加有过硼酸钠粉末的憎水有机化合物液涂敷过碳酸钠。该方法的弊端在于:为使工艺易于操作,作用的这种憎水液态有机化合物需要用低级醇稀释。另外,涂敷化合物的使用量十分高,即按过碳酸钠计5~20wt%的过硼酸钠和5~10wt%的憎水有机化合物。
DE—PS 2651442中介绍的涂敷过碳酸钠颗粒由过碳酸钠核及通式为NaBO2·H2O2·nH2O的过硼酸钠涂层构成,其中n小于3。按照DE—PS 2712139,涂层还可以含硅酸钠和其它加水粘合的物质。为了生产上述涂敷过碳酸钠颗粒,首先将过碳酸钠用水或硅酸钠水溶液湿润,水或溶液的用量极少以使过硼酸钠不至于转化成四水化合物,随后将湿润的过碳酸钠涂敷上一层无水过硼酸钠。DE—PS 2810379中介绍了上述方法的进一步改进,其中包括将过硼酸钠水溶液和硅酸钠溶液在40~60℃下喷洒在过碳酸钠上,其中过硼酸钠水溶液浓度为每升溶液中含50~500g四水过硼酸钠,然后全部或部分地除去过碳酸钠颗粒上引入的水份。
如迄今未出版的德国专利申请P 4306399.3中公开的,上述方法可以相当程度地得到简化,即在固/液分离器中部分分离湿法生产过碳酸钠产生的母液后,用过硼酸钠(NaBO2·H2O2)溶液冲洗上述湿法生产的过碳酸钠。尽管所需的涂敷物量很少,但在过碳酸钠的贮存中可以获得高的活性氧稳定性,这种过碳酸钠与典型的含沸石的洗涤剂塔粉混和。
含一水或四水过硼酸盐的涂敷物优于含硼酸盐或硼酸的过碳酸钠涂敷物,前者几乎不影响过碳酸钠颗粒中活性氧含量。
本发明论述的问题是使用新型含过氧的硼化合物进一步提高过碳酸钠的稳定性,并且提供了新型的涂敷的过碳酸钠颗粒,在相同的硼含量下,该颗粒比已知的有过硼酸盐涂层的过碳酸钠颗粒,在与洗涤剂组份混合贮存时,具有更高的活性氧稳定性。
因此,本发明涉及一种涂敷的过碳酸钠颗粒,它包含核和涂层,其核基本上为过碳酸钠,涂层至少含一种含过氧的硼化合物,其特征在于,从四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液反应得到的一种或多种反应产物用做含过氧的硼化合物。
涂敷颗粒的核基本上由过碳酸钠组成。“基本上”意味着过碳酸钠中还可能含有生产过程中加入的其它组成,例如苏打和少量的氯化钠以及结晶抑制剂,如偏磷酸盐或多羧酸以及常用的稳定剂,如镁盐和硅酸钠。术语“基本上”也意指过碳酸钠已经具有稳定组分涂层,例如膦酸盐、磷酸盐、苏打、水玻璃、镁盐、氨基羧酸盐和氨基膦酸盐以及羟基羧酸盐(hydroxycarboxylates)聚合物中任一种。一般来讲,已提出的任何涂敷组分甚至都可以是常见的硼化合物,尽管在要生产低硼含量的、涂敷的过碳酸钠颗粒的场合下,这看来是不适当的。
本发明方法中使用的过碳酸钠已经可以用标准方法生产。标准生产方法尤其包括所谓的湿法,其中苏打和过氧x氢在水相中发生反应,随后过碳酸钠结晶;以及所谓的喷淋法,其中含苏打及过氧化氢的水溶液喷淋到流化床干燥塔中的过碳酸钠颗粒上;还有所谓的干法,其中过氧化氢浓溶液与无水苏打反应。如果需要,标准生产方法之后还有标准涂敷方法。
按照本发明,涂敷的过碳酸钠颗粒中起稳定作用的壳层内含过氧化物的反应产物,该产物来源于四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液的反应,并且在与涂敷过碳酸钠颗粒相应的标准干燥条件下部分或全部地除去了水份。干燥及除水阶段可能伴随着熔融过程。
至今仍不知道生成的含过氧的硼化合物是否是过氧化氢与四硼酸盐或五硼酸盐的纯加合物。或含—B—O—O—H或—B—O—O—B—结构单元的化合物。甚至有可能含过氧的四或五硼酸盐在与生产相关的干燥过程中经历了部分的歧化过程,因此硼酸和从所谓的一水过硼酸钠中了解到的含结构单元的过硼酸盐可能在涂层中同时存在。
根据Ullmann’s Encyclopedia of Industrial Chemistry,5thEdition(1985),Vol.A4,270,用于形成上述含过氧的硼化合物的四硼酸盐和五硼酸盐具有以***离子结构:
四硼酸盐和五硼酸盐含有锂、钠或钾阳离子,优选钠阳离子。
优选的涂敷的过碳酸钠颗粒含通式为:Na2B4O7·nH2O2·mH2O的所谓的过四硼酸钠,其中n是1到4的整数,m是0到9的整数,做为涂层中的含过氧的硼化合物。优选每摩尔四硼酸盐结合2到4摩尔过氧化氢和0到2摩尔水。在特别优选的实施方案中,涂层基本上是Na2B4O7·4H2O2。
除了依照本发明的含过氧的硼化合物,尤其是相应的通式为Na2B4O7·4H2O2的过四硼酸钠外,涂层还可以含有均匀分布的其它已知起稳定作用的涂敷组分,如前面提到的那些稳定剂。如果需要,本发明中涂层外还可以包敷有其它几层含除本发明中使用的含过氧的硼化合物之外的其它稳定剂的涂层,以及非必须地包敷有含通用洗涤剂和清洁剂组合物中各组分如沸石的涂层。另外的这些涂层可以通过标准方法,尤其是通过喷淋、混合及造粒过程涂敷到根据本发明涂敷的过碳酸钠颗粒上。
根据本发明涂敷的过碳酸钠颗粒的涂敷量范围很宽,尽管按过碳酸钠计,1~30wt%的涂层量都可行,但实际证明使用1~10wt%,优选2~6wt%的涂敷量更有利。一方面,这些限定量的涂敷物提供给过碳酸钠以足够的稳定性以抵抗在潮湿环境中在与通常的洗涤剂、清洁剂和漂白剂组合物混合贮存时活性氧的损失;另一方面,涂敷的过碳酸钠的硼含量保持在低水平。
正如已经提到的,根据本发明的过碳酸钠颗粒的单层或多层涂层中可以含有除过氧化氢与四硼酸酸或五硼酸盐反应的产物之外的其它涂敷组分。有利的是,整个涂层含大于50wt%,尤其是大于70wt%的前面提到的过氧化氢与四硼酸盐或五硼酸盐的反应产物和小于50wt%,尤其是小于30wt%的其它稳定化合物。根据本发明涂敷的具有单涂层的过碳酸钠颗粒,该涂层基本上是本发明中使用的含过氧的硼化合物,在洗涤剂塔粉(Tower Powder)存在时表现出非常高的贮存稳定性,这种稳定剂是仅使用标准的过硼酸盐所达不到的,尽管硼含量保持一样。这点令人十分惊奇,因为分子式为Na2B4O7·4H2O2的过四硼酸钠不如一水过硼酸钠这么稳定。
根据本发明涂敷的过硼酸钠颗粒可以用以下方法制备,将至少一种含过氧的硼化合物和,如果需要,其它涂敷组分、优选使用其水溶液,涂敷到基本上为过碳酸钠的颗粒上,以及如果需要,再干燥生成的湿颗粒。该方法的特征在于,一种或多种由四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液得到的反应产物用做含过氧的硼化合物。
涂敷组分优选以其水溶液的形式涂敷到过碳酸钠颗粒上。从四硼酸盐或五硼酸盐与过氧化氢反应得到的反应混合物最好直接使用。
如果需要,含活性氧的硼化合物可以从反应混合物中回收,即将反应混合物溶液进一步浓缩或者甚至是部分或完全蒸发掉存在的水份使之成为固体,并且可以就这样用于本发明方法中。反应混合物最好照此方法直接制备以使含过氧的硼化合物保持所需的浓度。由于四硼酸盐或五硼酸盐与过氧化氢的反应产物其溶解度高,可以获得高浓度的含过氧的硼化合物溶液。这类溶液的好处在于,当它们通过喷淋嘴喷洒到过碳酸钠颗粒上时,不会产生喷嘴堵塞,因此不会出现故障。同时,在干燥过程中只需除去少量的水份。在制备这种反应混合物时,反应物的使用量要保证硼与活性氧的原子比为1∶0.2到1∶1.5。但优选硼与活性氧的原子比为1∶0.5到1∶1.25,尤其优选其原子比为1∶1或1:基本为1。在一特别优选的实施方案中,涂敷的过碳酸钠颗粒上的溶液含通式为Na2B4O7·nH2O2的过四硼酸钠,其中n为1到4的整数,优选2到4,更优选约为4的整数。在使用含Na2B4O7·4H2O2的溶液的场合下,如果溶液中另含有少量过量过氧化氢,使硼原子与活性氧的原子比约为1∶1.05~1.15,则是有利的。通过搅拌将四硼酸钠加入到过氧化氢水溶液中,很容易就得到了这种溶液。用这种方法可制备含有例如20~50wt%,尤其是25~40wt%的分子式为Na2B4O7·nH2O2的过四硼酸钠溶液,其中n为2到4的整数,用于本发明的方法。
本发明方法中使用的含过氧的硼化合物可以使用标准方法一步或分几步以连续或间断的方式涂敷到主要成份为过碳酸钠的颗粒上。待涂颗粒可以是干燥的或含有生产过程中残留的水份的过碳酸钠。因此,甚至可以使用如离心含水的或部分干燥的过碳酸钠。根据本发明涂敷的过碳酸钠颗粒可以通过将表面含水的过碳酸钠与粉末状的过四硼酸钠混合来制备,如果需要,随后进行干燥。但更有利的是将涂层组分溶液涂敷到过碳酸钠颗粒上。合适的方法有:例如,将溶液喷淋到颗粒上,同时进行混合;合适的混合器有:例如喷淋混合器如转筒、滚桶混合器、盘式造粒机等。在上述实施方案的替换实施方案中,湿法生产的过碳酸钠用本发明中的含过氧的硼化合物水溶液处理,该过程在如固/液分离器的清洗装置中进行,除去过量的溶液后,所得产物进行干燥。该实施方案相当于迄今尚未出版的德国专利申请书P4306399·3中的实施方案,不同的是在较早的申请书的方法中,使用了含过硼酸钠(NaBO2·H2O2)的溶液。在本发明的一特别优选的实施方案中,将水溶液喷洒在流化床中处于流化状态的待涂颗粒上。被喷洒的溶液加湿的颗粒同时或随后被干燥。如果使用流化床装置,通入加热到干燥温度的流化空气,可以同时进行喷淋和干燥。
含有依照本发明使用的含过氧的硼化合物及非必须的其它涂敷组分的溶液在喷淋过程中的温度可以是室温或直到约60℃的温度。在使用浓度特别高的溶液的场合下,最好将其加热,优选加热至30~50℃。在使用的溶液是通过四硼酸盐或五硼酸盐与过氧化氢反应得到的场合下,该溶液即将使用前的温度受着溶解热与反应热的影响大约位于所述的范围内。代替从反应物制备该溶液,该溶液也可以通过用水溶解经验式为Na2B4O7·4H2O2的过四硼酸钠来制备,正如DE—PS 548432中描述的;室温下1升水中可溶解过四硼酸钠达1kg。
用喷淋法获得的的湿的涂敷的过碳酸钠在通常干燥过碳酸钠的条件下进行干燥。因此,干燥温度在30~90℃范围内,优选50~80℃,更优选50~70℃。干燥温度应理解为待干燥颗粒的温度。因此,在一特别优选的实施方案中,该过程在流化床干燥器中进行的场合下,流化床温度在上述温度范围内。因此进入流化床干燥塔的干燥空气的温度高于流化床温度。
根据本发明涂敷的过碳酸钠颗粒可以做洗涤剂、清洁剂和漂白剂组合物中的漂白组份。根据本发明涂敷的过碳酸钠颗粒的突出优点是,其中的过碳酸钠具有意想不到的高贮存稳定性,因此通常条件下在这些组合物的贮存期间,活性氧的损失十分缓慢。在涂敷物用量相当及起始Oa含量高的情况下,所述组合物中根据本发明涂敷的过碳酸钠的贮存稳定性超过已知的其它涂敷过碳酸钠的水平。
含有根据本发明涂敷的过碳酸钠的洗涤剂、清洁剂和漂白剂组合物中,1~99wt%为该涂敷过碳酸钠,剩余的(配平至100wt%)为该组合物中常用的其它组份。虽然洗涤剂中过碳酸钠含量一般不超过20wt%,但漂白剂和清洁剂组合物中的过碳酸钠含量可以高得多。
含有根据本发明的涂敷的过碳酸钠的洗涤剂、清洁剂和漂白剂组合物中除上述的活性氧化合物之外,还含有一般浓度的其它常用组份。所述的其它组份特别包括以下成份:1.阳离子型、阴离子型、非离子型或两性表面活性剂;2.无机和/或有机增洁剂,其主要功能是螯合或络合影响水硬度的金属离子,例如沸石、多磷酸盐、氨基多乙酸和氨基多膦酸和聚羟羧酸;3.碱和无机电解质,如链烷醇胺和硅酸盐、碳酸盐和硫酸盐;4.N—酰基化合物和O—酰基化合物类的漂白活性剂,如;四乙酰乙二胺;5.组合物可能含的其它组分是:过氧化物稳定剂(尤其是镁盐)、污垢再沉积抑制剂、光亮剂、消泡剂、酶、消毒剂、防腐蚀剂、香料、染料和PH值调节剂、1到5类中各化合物的特例可以在DE—OS3321082的14—30页上到找到。
本发明涂敷的过碳酸钠颗粒在单独贮存或与洗涤剂、清洁剂和漂白组合物混合贮存时都表现出惊人的活性氧稳定性。仅使用过碳酸钠百分之儿的涂敷物量就能获得这种惊人的稳定程度。虽然知道硼酸、硼酸盐和过硼酸钠作涂敷组分是十分有效的,但本发明中优选的含过氧硼的化合物的有效性超过上述已知的硼化合物的有效性。本发明方法的实施十分简单:由于本发明中使用的过四硼酸钠和其它含过氧的硼化合物的溶解度很高,一步即可得到有效的涂层。另外,也不存在喷嘴阻塞产生的故障。干燥的耗能也保持很低的水平。
本发明通过以下实施例来说明。实施例1
通过苏打与过氧化氢在水相中反应得到的活性氧(Oa)含量为14.2wt%的过碳酸钠在一混合器内用含有通式为Na2B4O7·4H2O2的过四硼酸钠的溶液涂敷:
该涂敷溶液用以下步骤制备:将100.2g四硼酸钠(Na2B4O7·10H2O)溶于115.4g 35wt%的过氧化氢水溶液中,并加以搅拌及自生缓慢加热。该溶液含41wt%的Na2B4O7·4H2O和2.2wt%的H2O2。溶液中硼与活性氧的原子比为1∶1.13。
在实验用犁式混合器内将183g上述溶液喷洒到1500g过碳酸钠上,湿产品在流化床干燥塔内60℃下进行干燥。
涂敷过碳酰钠的Oa含量为14.4wt%;硼含量为0.61wt%,数据由Na2B4O7·4H2O2的使用量并以涂敷的过碳酸钠为基础计算的。表中列出涂敷的过碳酸钠加入到工业用含沸石的洗涤剂塔粉(Persil Supra TP)(其中15wt%为涂敷的过碳酸钠,85wt%为塔粉)后,在潮湿环境中混合物在洗涤剂包中贮存时的Oa稳定性。实施例2
在流化床干燥塔中将含过四硼酸钠(Na2B4O7·4H2O2)的溶液喷涂到过碳酸钠(依照实施例1)上,同时进行干燥。
该溶液是将四硼酸钠溶于19.5wt%的H2O2溶液而制得。Na2B4O7·4H2O2含量为31.2wt%;硼与活性氧的原子比为1∶1。将该溶液在50℃流化床温度下(干燥气体的入口温度110℃)通过一双组份喷嘴喷涂到过碳酸盐上。喷涂量为每100g份重过碳酸钠使用5份重过四硼酸钠;涂敷的过碳酸钠中的Oa含量为14.2wt%。表中列出了添加到粉状洗涤剂中的过碳酸钠Oa稳定性(塔粉和混合比同实施例1)。实施例3
重复实施例2,但不同的是喷涂溶液含分子式为Na2B4O7·2H2O2的过四硼酸钠;其含量为28.7wt%;硼与活性氧的原子比为1∶1。
涂敷量为过碳酸钠量的5wt%。涂敷过碳酸钠中的Oa含量为14.0wt%。洗涤剂塔粉中Oa稳定性也列于表中(塔粉和混合比同实施例1)。实施例4
离心含水的过碳酸钠(通过在水相在氯化钠及六偏磷酸钠存在下苏打与过氧化氢反应并结晶而制得)在离心机中后处理,即除去母液后用过四硼酸钠溶液(Na2B4O7·4H2O2的33wt%)洗涤,随后在流化床干燥塔中干燥。Na2B4O7·4H2O2的涂敷量为过碳酸钠的2.5wt%。硼含量约为0.3wt%。涂敷过碳酸钠的Oa含量为14.2wt%。其贮存稳定性列于表中。比较实施例1
使用DE—PS 2800916中的方法(见该说明书的实施例A6)用5wt%的原硼酸涂敷过碳酸钠。该涂敷的过碳酸钠的Oa含量为13.4wt%;硼含量为涂敷的过碳酸钠的0.83wt%。在洗涤剂混合物中贮存时的稳定性数据列于表中。比较实施例2
在一混合器内(同实施例1)将四硼酸钠水溶液(浓度为35wt%)喷涂到过碳酸钠上,每100份重过碳酸钠喷涂四硼酸钠的数量为5份重。所得物随后在70℃下进行干燥。
Oa含量为13.5wt%;涂敷的过碳酸盐中硼含量为0.55wt%,数据由涂敷的四硼酸钠计算出,其中假设干燥过程中四硼酸钠转化成Na2B4O7·5H2O。比较实施例3
依照DE—PS 2810379,用过硼酸钠和水玻璃涂敷的过碳酸钠。涂敷量为6wt%的一水过硼酸钠和1wt%水玻璃。涂敷的过碳酸钠的Oa含量为14.3wt%;硼含量为0.62wt%(数据由涂敷的NaBO2·H2O2量计算出)。在洗涤剂组合物中的稳定性数据列于表中。
为了估价稳定性,上述实施例及比较实施例中涂敷的过碳酸钠与工业用无磷酸盐但含沸石的洗涤剂塔粉(Persil Supra TP)混合(混合比为15∶85)后贮存于密封的洗涤剂包装袋中(0.4l),置于恒温30℃、相对湿度为80%的气候试验箱中。贮存开始及贮存2、4和8周后,以一般方法对混合物中的活性氧进行了测定,测定结果列于表中。对于几乎相同的硼含量来说,依照本发明涂敷的过碳酸钠颗粒显示了比用硼酸、四硼酸钠或一水过硼酸盐涂敷的过碳酸钠颗粒有更高的贮存稳定性。
表 贮存稳定性
实施例号 | 涂敷物量(wt%) | 涂敷的过碳酸钠的堆积密度(克/升) | 在洗涤剂组合物中过碳酸钠的绝对Oa含量(wt%) | 8周后Oa剩余量(%) | |||
开始 | 2周 | 4周 | 8周 | ||||
1234比较实施例CE 1CE 2CE 3 | Na2B4O7·4 H2O25%Na2B4O7·4 H2O25%Na2B4O7·2 H2O25%Na2B4O7·4 H2O22.5%B(OH)35%Na2B4O7·1O H2O5%NaBO2·H2O26% | 1050970990920970960940 | 14.414.214.014.213.413.514.3 | 13.813.913.313.912.712.313.3 | 13.712.612.912.811.311.912.8 | 12.511.511.210.98.39.610.0 | 86.880.98076.761.97170 |
Claims (10)
1.包含一种核和一种涂层的、涂敷的过碳酸钠颗粒,其核基本上为过碳酸钠且其涂层含有至少一种含过氧的硼化合物,其特征在于,由四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液反应的一种或多种反应产物为该含过氧的硼化合物。
2.根据权利要求1的涂敷的过碳酸钠颗粒,其特征在于,涂层中的含过氧的硼化合物是通式为Na2B4O7·nH2O2·mH2O的过四硼酸钠,其中n为1到4,优选2到4的整数;m为0到9,优选0到2的整数。
3.根据权利要求1或2的、涂敷的过碳酸钠颗粒,其特征在于,涂层量为过碳酸钠的1~10wt%,优选2~6wt%。
4.根据权利要求1到3的、涂敷的过碳酸钠颗粒,其特征在于,涂层含大于50wt%、优选大干70wt%的过氧化氢与四硼酸盐或五硼酸盐的反应产物及小于50wt%、优选小于30wt%的其它起稳定作用的化合物。
5.一种生产包含一种核和一种涂层的、涂敷的过碳酸钠颗粒的方法,该颗粒的核基本上是过碳酸钠,涂层含有一种或多种涂敷组分,其中包含至少一种含过氧的硼化合物,该方法包括,将至少一种含过氧的硼化合物和,如果需要,其它涂敷组分、优选以其水溶液形式,涂敷到基本上为过碳酸钠的颗粒上,如果需要的话,干燥其湿颗粒,该法的特征在于,由四硼酸二碱金属盐或五硼酸碱金属盐与过氧化氢水溶液反应的一种或多种反应产物作为该含过氧的硼化合物。
6.根据权利要求5的方法,其特征在于,所述的反应产物以其水溶液形式使用,优选以反应混合物的水溶液形式使用,所述的溶液含有硼和活性氧,其硼与活性氧的原子比为1∶0.2到1∶1.5,优选1∶0.5到1∶1.25,更优选的为1:实质上的1。
7.根据权利要求5或6的方法,其特征在于,涂敷的溶液含通式为Na2B4O7·nH2O2的过四硼酸钠,其中n为1到4的整数,优选2到4的整数。
8.根据权利要求5至7任一项的方法,其特征在于,涂敷的溶液含20~50wt%、尤其是25~40wt%通式为Na2B4O7·nH2O2的过四硼酸钠,其中n为2到4的整数,尤其是4。
9.根据权利要求5至8中任一项的方法,其特征在于,在一混合器或流化床干燥塔中将含过氧的硼化合物的水溶液喷涂到主要成份为过碳酸钠的颗粒上,得到的湿颗粒同时或随后在30~90℃、优选50~80℃下进行干燥。
10.含有根据权利要求1至3或根据权利要求4至9的方法制得的、涂敷的过碳酸钠颗粒的洗涤剂、清洁剂和漂白剂组合物。
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-
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- 1993-04-10 DE DE4311944A patent/DE4311944A1/de not_active Withdrawn
-
1994
- 1994-02-28 KR KR1019950704418A patent/KR100308473B1/ko not_active IP Right Cessation
- 1994-02-28 CA CA002159991A patent/CA2159991A1/en not_active Abandoned
- 1994-02-28 TW TW083101684A patent/TW265320B/zh active
- 1994-02-28 US US08/525,782 patent/US5658873A/en not_active Expired - Lifetime
- 1994-02-28 ES ES94909085T patent/ES2106515T3/es not_active Expired - Lifetime
- 1994-02-28 CZ CZ952498A patent/CZ249895A3/cs unknown
- 1994-02-28 DE DE59403562T patent/DE59403562D1/de not_active Expired - Lifetime
- 1994-02-28 CN CN94191734A patent/CN1120832A/zh active Pending
- 1994-02-28 PL PL94311035A patent/PL173925B1/pl unknown
- 1994-02-28 AT AT94909085T patent/ATE156096T1/de active
- 1994-02-28 AU AU62078/94A patent/AU6207894A/en not_active Abandoned
- 1994-02-28 JP JP52265894A patent/JP3599737B2/ja not_active Expired - Fee Related
- 1994-02-28 EP EP94909085A patent/EP0693039B1/de not_active Expired - Lifetime
- 1994-02-28 WO PCT/EP1994/000576 patent/WO1994024044A1/de not_active Application Discontinuation
- 1994-04-04 TR TR00294/94A patent/TR27402A/xx unknown
- 1994-04-07 SI SI9400166A patent/SI9400166A/sl unknown
-
1995
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101270232B (zh) * | 2008-04-22 | 2011-04-20 | 浙江时代金科过氧化物有限公司 | 一种颗粒型包膜过碳酸钠的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR960701801A (ko) | 1996-03-28 |
EP0693039B1 (de) | 1997-07-30 |
KR100308473B1 (ko) | 2002-07-02 |
TW265320B (zh) | 1995-12-11 |
FI954808A (fi) | 1995-10-09 |
EP0693039A1 (de) | 1996-01-24 |
TR27402A (tr) | 1995-02-28 |
ES2106515T3 (es) | 1997-11-01 |
DE4311944A1 (de) | 1994-10-13 |
WO1994024044A1 (de) | 1994-10-27 |
CA2159991A1 (en) | 1994-10-27 |
DE59403562D1 (de) | 1997-09-04 |
AU6207894A (en) | 1994-11-08 |
PL173925B1 (pl) | 1998-05-29 |
FI954808A0 (fi) | 1995-10-09 |
JPH08508707A (ja) | 1996-09-17 |
US5658873A (en) | 1997-08-19 |
SI9400166A (en) | 1994-12-31 |
PL311035A1 (en) | 1996-01-22 |
JP3599737B2 (ja) | 2004-12-08 |
ATE156096T1 (de) | 1997-08-15 |
CZ249895A3 (en) | 1996-04-17 |
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