中国无磷助剂——4A沸石的发展

无磷助剂是发展趋势，4A沸石+碳酸钠+聚羧钠复合助剂具有与磷酸盐相同的洗涤效果，4A沸石是当前无磷助剂的主要成分，国产沸石的性能可与世界品牌媲美。     

洗涤助剂4A沸石的制备技术及市场趋势分析

概述了4A沸石结构、性能，着重介绍了其制备技术的进展，并简要分析了市场发展趋势。4A沸石是无磷洗涤助剂优秀品种，其生产、消费会有较大发展。     

浅谈洗涤助剂的性能及作用机理

综述了洗涤助剂的开发进展，主要对三聚磷酸钠、4A沸石、层状结晶二硅酸钠、聚丙烯酸钠、丙烯酸和马来酸酐共聚物等助剂的性能及作用机理进行了探讨，为开发理想的无磷洗涤助剂提供了思路。     

层状复合硅酸钠的合成及性能测试

详细介绍了层状复合硅酸钠（LCS）的生产方法及其在洗衣粉中的应用，用LCS制得的洗衣粉，去污力优于无水偏硅酸钠、层状结晶硅酸钠和4A沸石，试验表明LCS是目前应用效果较好的无磷洗涤助剂。     

进一步开发洗涤剂用4A沸石

洗涤助剂三聚磷酸钠因其对水体造成的“过肥化”引起了一系列环境问题，在国外已经被其它无磷助剂所取代，其中4A沸石作为优良的代磷助剂得到广泛应用，而在国内仍未能推广。4A沸石生产工艺不完善、洗涤剂配方不成熟、成本高等是阻碍4A沸石助剂发展的主要原因，通过完善4A沸石合成技术、提高质量、降低成本、规范市场，并承着国家相应环保法规的颁布，4A沸石在洗涤剂行业的应用将有更大发展。     

代磷洗涤助剂的性能及应用前景

概括介绍了各种代磷洗涤助剂的应用性能及作用机理。目前工业上大量使用的无磷洗涤助剂是4A沸石,而层状结晶硅酸钠将成为洗涤剂工业的新宠。同时,简要阐述了各种新型代磷洗涤助剂的发展方向。     

新型洗涤助剂—4A沸石

一、前言三聚磷酸钠是合洗成涤剂中使用较早,效果良好的助剂。由于磷酸盐会引起水域污染,特别是地表水的富营养化,世界各国都在寻求它的代用品,以期实现合成洗涤剂的低磷化和无磷化。研究资料表明,沸石、氮川三醋酸钠、柠檬酸钠、聚丙烯酸盐、聚丁烯酸盐等助剂都可在一定程度上代替三聚磷酸钠,其中尤以4A 沸石的效果最为理想。因为4A 沸石具有较强的硬水软化能力、吸附能力和一定的缓冲容量。七十年代,西德已经有50%的磷酸盐被4A 沸石所取代,并拟定逐步用沸石取代三聚磷酸钠生产无磷洗涤剂;八十年代末,日本沸石年产量已经超过10万吨,其中90%用于洗涤剂工业。     

山西榆次昶力高科有限公司10万吨4A沸石生产线正式投产

2005年8月6日,山西榆次昶力高科有限公司年产10万吨的4A沸石生产线正式投产,这标志着其已经成为我国重要的无磷洗涤助剂-4A合成沸石的生产基地之一.     

十二烷基苄磺基甜菜碱作为代磷助剂的性能研究

研究了N-十二烷基-N,N-二甲基-N-苄磺基甜菜碱(DBSB)作为代磷助剂的性能。结果表明,DBSB的钙皂分散指数为3%,与十二烷基苯磺酸钠(LAS)二元复配后,可提高复配体系的钙离子稳定性,当DBSB占二元体系的质量分数为15%时,体系承受的钙离子浓度从5 mmol·L-1升高到30 mmol·L-1。以DBSB替代4A沸石加入到无磷模拟洗衣粉配方中,可保持较好的去污力,且DBSB的加入可大幅度提高配方的抗硬水性能。通过正交试验得到优化配方5,其在250和400 mg·L-1硬水中的去污力均优于4A沸石无磷模拟配方(配方6),且灰分残留量较少,具有低泡性,pH、总活性物含量及游离碱含量符合国标要求。     

丙烯酸-马来酸酐共聚物在碱性无磷洗涤剂中的应用研究

去掉磷酸钠后 ,洗涤剂的去污力有所降低 ,而其他碱性助剂如硅酸钠、碳酸钠、 4A沸石等的大量加入又会使洗涤剂pH值升高 ,灰分沉积严重。研究了丙烯酸 马来酸酐共聚物 (AA -MA)在碱性无磷洗涤剂中的应用 ,证明丙烯酸 马来酸酐共聚物具有很好的螯合性能和分散性能 ,应用在洗涤剂中能缓冲pH值 ,有效防止灰分沉积     

新型洗涤剂助剂——亚胺磺酸盐代磷复配洗衣粉的研究

作为一种洗涤剂助剂，亚胺磺酸盐具有良好的物理化学性质，表面活性及复配性能。试验表明，它的去污力可与三聚磷酸钠相当。通过试验设计和方差分析，筛选出以亚胺磺酸盐取代三聚磷酸钠的优化的复配洗衣粉的配方组成。样品的主要性能（去污力）达到或超过国内市售产品。     

木质素磺酸钠的改性及其作为洗涤助剂的研究

对木质素磺酸盐(LSs)的理化性能和其作为洗涤助剂的应用潜力进行了研究,讨论了其在洗涤配方中的作用及其机理。实验结果表明:木质素磺酸钠改性产物(GLS)比木质素磺酸钠(LS)具有更好的乳化力、起泡力和钙皂分散力;经过漂白处理后,LS的漂白产物(LSW)白度保持值为91.93%,而GLS的漂白产物(GLSW)白度保持值可达99.37%,基本对标准白布不造成沾污,消除了其对洗涤过程的负面影响;将LS及其改性产物应用于衣物洗涤剂配方中具有明显的增强皮脂去污力特性,为洗涤用品原料的选择提供了一个新的方向。     

地沟油生产无磷洗衣粉的研究

研究对脱色后地沟油皂化产物用于生产无磷洗衣粉的工艺做了探索。以地沟油脱色后的皂化产物、对环境无害的新型无磷复配洗涤助剂和表面活性剂为原料,制成无磷洗衣粉。经正交实验优选出适用于宾馆、饭店洗涤棉织物为主的重垢型无磷洗衣粉的最佳配方。测试结果表明,优选配方的性能和市售洗衣粉的性能相当,主要技术指标符合国家标准。本研究以脱色后地沟油的皂化产物为原料,降低了产品的成本,又缓解了地沟油对环境保护带来的压力。     

Detergency of binary mixtures of LAS/STPP and LAS/Zeolites: influence of (Ca++) on the washing liquor

The influence of sodium tripolyphosphate (STPP) or zeolites on the detergency performance of linear alkylbenzene sulfonate (LAS) has been evaluated at different water hardness levels. This study demonstrates that STPP or zeolite behaves either as a sequestrant or through an important synergism with LAS, showing a minimum and a maximum in detergency performance, depending on the water hardness level. There is an optimum LAS/builder ratio for each individual water hardness level. This optimum has to be determined experimentally as it will not always necessarily coincide with the highest surfactant and/or builder concentrations.     

衣康酸-丙烯酸共聚物助洗性能的研究

研究了衣康酸-丙烯酸共聚物(IA-Co-AA)的助洗性能,并与马来酸-丙烯酸共聚物(MA-Co-AA)和三聚磷酸钠(STPP)进行了比较.结果表明:IA-Co-AA的钙皂分散力和pH缓冲能力高于STPP和MA-Co-AA.MA-Co-AA的表面活性比IA-Co-AA和STPP的高,但它们都与十二烷基苯磺酸钠(LAS)具有较好的协同作用,以至它们的存在能显著降低LAS溶液的表面张力.IA-Co-AA取代STPP制得的洗衣粉的去污能力和抗污垢再沉积能力比用MA-Co-AA取代STPP制得的洗衣粉的强.IA-Co-AA较易生物降解,而MA-Co-AA难生物降解.     

Microemulsion Formation and Detergency with Oily Soil: V. Effects of Water Hardness and Builder

In this study, the impact of water hardness and builder on the phase diagrams of motor oil microemulsions and the detergency of oil removal from a polyester/cotton blend was investigated. Water hardness and builder were found to have insignificant effects on the microemulsion phase diagram with motor oil. A mixed surfactant system of two parts C_14–15(PO)₃SO₄Na, and 98 parts C_12–14H_25–29O(EO)₅H of the total actives at 4% salinity was used to study the effect of water hardness and builders sodium tripolyphosphate (STPP) or ethylenediaminetetraacetic acid (EDTA) on detergency at 30 °C at a total active concentration of 0.3%. This formulation is in the Winsor Type III microemulsion regime. The microemulsion-based formulation resulted in better detergency than a leading commercial liquid laundry detergent at all concentrations up to 0.5% actives. The microemulsion-based formulation showed a plateau in detergency at >80% oil removal above 0.1% actives. The total oil removal decreased with increasing water hardness while the interfacial tension increased. When hard water was used in laundering, the total oil removal improved with increasing concentrations of STPP or EDTA up to stoichiometric levels, with STPP being slightly more effective than EDTA on a molar basis. Even high builder concentration could not improve hard water detergency to that of soft water. A significant fraction of oil removal occurred in the rinse steps vs. the wash step. Increasing water hardness reduced this fractional oil removal in the rinse steps, but it was still over half of total oil removal at 1,000 ppm water hardness.

马来酐—丙烯酸共聚物钠盐的合成及助洗剂性能研究

以水为溶剂合成了马来酐－丙烯酸共聚物钠盐（简称内共聚物钠盐）对其螯合性能、分散性能及复配成洗衣粉的去污效果进行了研究。结果表明：马丙共聚物钠盐具有良好的螯合能力和分散能力,与４Ａ沸石复配后得到的洗衣粉去污指数高于以ＳＴＰＰ为助剂的标准粉。     

马来酸酐-丙烯酸共聚物的合成

以马来酸酐和丙烯酸为单体 ,以过硫酸钠为引发剂 ,以亚硫酸氢钠为还原剂 ,采用水溶液聚合法 ,合成了用作洗衣粉代磷助剂的马来酸酐 -丙烯酸共聚物。m(马来酸酐 )∶m(丙烯酸 ) =1∶2 ,引发剂和还原剂分别为单体质量的 4.0 %和 1.9% ,聚合反应温度 90℃ ,保温 1h。产物为黏度较低的透明液体 ,分散性好 ,色泽浅 ,螯合力为 5 18mgCaCO3/g     

Detergent enzymes: Developments during the last decade

The decade of the seventies saw dramatic changes in the formulation of heavy duty laundry detergents. The reduction in the STPP content in laundry product formulations was a notable example. During the early 1970s, heavy duty liquid laundry detergents were introduced and today represent an estimated 20% of the heavy duty laundry detergent market. A significant trend during this decade toward lower wash temperatures also appeared. These developments in home laundry products and washing trends have been followed by collateral developments in detergent enzyme technology. During the 1970s, a new generation of high alkaline, active detergent enzymes were developed. This new group of alkaline proteases were characterized by greater activity and stability under conditions of alkalinity between pH 10.5 to near 12, thus favoring phosphate-free detergent formulations. These enzymes also were found to exhibit superior stability in nonbuilt liquid laundry detergent systems. Safety considerations at the plant operation level have resulted in a continual improvement in the quality of coated and encapsulated detergent enzyme granulates. During the past 10 years, detergent enzymes have passed through three generations of physical forms, from the powders to prills to encapsulates. The decade of the 1980s offers exciting possibilities for enzymatic laundry products. The trend toward lower wash temperatures, caused initially by the popularity of synthetic fabrics, is being compounded by a radical reappraisal of household energy consumption patterns. In this new atmosphere of energy conservation, detergent enzymes will offer energy-saving options in an assortment of laundry products. Finally, as we start this decade of the 1980s, the spiralling cost of petrochemical feedstocks will cause us to rethink laundry product formulations and here again, detergent enzymes offer an important alternative for the future.