CN1088776C - 溶胀粘土的活化和使用活化粘土的方法 - Google Patents
溶胀粘土的活化和使用活化粘土的方法 Download PDFInfo
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- CN1088776C CN1088776C CN97192857A CN97192857A CN1088776C CN 1088776 C CN1088776 C CN 1088776C CN 97192857 A CN97192857 A CN 97192857A CN 97192857 A CN97192857 A CN 97192857A CN 1088776 C CN1088776 C CN 1088776C
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- Prior art keywords
- bentonite
- chelating agent
- activation
- activated
- salt
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- 238000000034 method Methods 0.000 title claims description 30
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 33
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- 239000002738 chelating agent Substances 0.000 claims description 24
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- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
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- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 1
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- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910000280 sodium bentonite Inorganic materials 0.000 description 1
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- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/18—Compounding ingredients for liquefying the batches
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S106/00—Compositions: coating or plastic
- Y10S106/04—Bentonite
Abstract
使用柠檬酸钠或其它有机螯合剂作为活化剂能活化碱土膨润土。提供一种活化剂和膨润土的干混合料。
Description
本发明涉及膨润土的活化和活化膨润土在造纸中的应用。最初，膨润土通常是作为碱土化合物制备的，例如钙和/或镁形式的膨润土。为了使它们能令人满意的例如用于造纸，需要通过离子交换使膨润土活化，由此用钠或其它碱金属或铵离子交换出钙和/或镁。
进行这种离子交换的常规方法是使碱土膨润土粘土与含有碱金属或铵化合物的活化水溶液混合。例如可提供碱土金属粘土和碱金属或铵化合物预混合料粉末形式的粘土，使这种预混合料与水混合并放置足够长的时间进行离子交换，然后稀释便可使用。另外，在搅拌下可将采石场的碱土膨润土直接加入到活化水溶液中。
实际上，通常使用的活化化合物是碳酸钠或碳酸氢钠，一般用量以粘土的重量为量约为5-10％(重量)。活化是在中性pH的分散液中进行的，pH值约为10。
JP-A-6445754中公开了加入其它类的电解质，用来促进分散。人们也已知US4613542和4624982中公开了聚丙烯酸钠。EP485124和US5266538和5391228中也公开了膨润土与各种碱金属化合物的浓缩物。加入到这些浓缩物浆料中的膨润土最初是以钠膨润土的形式存在的，但是EP485124和US5391228也提及了通过将钙膨润土和碳酸钠活化剂与水和氯化钠混合来制备浆料。EP373306和US5015334中还公开了使用膨润土和阴离子有机聚合物的造纸方法。
已知活化膨润土(例如市售的活化膨润土粉末)的一个问题是膨润土中存在的碳酸钠或其它活化剂会使膨润土(当与水混合时)具有较高的pH值，例如达到pH9以上，常常达到约pH10。因此，用产生pH值达到约pH10的有关物质处理膨润土时必须小心。
另一个问题是常规的碳酸钠活化剂在活化过程中进行离子交换形成碳酸钙，结果可形成片状物并从这些活化膨润土的含水组分中沉积下来。当分散膨润土的水本身较硬时，这个问题尤为突出。
已知活化膨润土粉末的另一个难点是有时发现要制备稳定的含水粉末分散液相当困难。而且，已经发现要实现稳定分散的这些困难随着水的硬度的增加而增加。因此，当使用较硬的水例如硬度约为10°dH，通常为15-50°dH的水时，会带来各种问题。
另外，膨润土的性能(尤其是当在造纸中使用时)在低pH值下要比高pH值下的效率低，尤其是按常规方法活化的膨润土在酸性造纸方法(例如当纤维素悬浮液的pH低于6.5，通常为4.2-5.5时)中使用的效率要比悬浮液具有较高pH值的低。
目前，我们已经发现了一种新的活化剂，这种活化剂能改善性能。
根据本发明的第一方面，我们提供了一种干粘土组合物，包含碱土膨润土溶胀粘土和活化量的螯合剂的碱金属或铵盐的混合料，所述螯合剂选自膦酸酯、羟基羧酸、氨基羧酸和多元羧酸。
根据本发明的第二方面，我们提供了一种将碱土膨润土溶胀粘土活化成碱金属膨润土溶胀粘土的方法，包括使碱土溶胀粘土与活化水溶液混合，所述活化水溶液含有选自膦酸酯、羟基羧酸、氨基羧酸和二-或三-(或更高)元羧酸螯合剂的铵盐或碱金属盐。
在本发明的两个方面中，螯合剂最好以钠盐的形式加入。
在本发明的两个方面中，螯合剂最好是柠檬酸钠。
所得到的活化膨润土具有几个优点。它们易于处理，因为它们是弱碱性的。它们的性能要比在约pH10下用碳酸钠进行常规活化的相同膨润土的好。它们在造纸方法中的使用效率更高，而在这种造纸方法中常规活化膨润土因pH值或存在的硬性盐致使使用效率降低。因此，当纤维素悬浮液的pH低于约6.5，例如为4.2-5.5时，常规膨润土的使用效率低，而本发明制备的活化膨润土在这种悬浮液中的使用效率极高，不会明显地降低活性。
当采用较硬的水，例如硬度约为10°dH，通常为15-50°dH的水制备纤维素悬浮液时，常规活化膨润土的性能也会变差。在这种硬质水中，使用本发明制备的活化膨润土的性能会得到改善。通过改进排水速率或降低片状物沉积或通过这两种措施可显示出这种改进。
分别向水中加入溶胀粘土和螯合剂活化剂，例如向活化剂的溶液中加入溶胀粘土或向溶胀粘土的分散液中加入活化剂来进行活化过程。在这些改变的每一种方法中，溶胀粘土可以粉末或浆料的形式加入。
但是，最好使溶胀粘土和活化剂的预混合料与适量的水混合来进行这种活化过程。预混合料优选地是粉末，但是它们也可以是含有膨润土和活化剂的液态组合物。
活化过程中水的用量通常应使该过程中溶胀粘土的浓度达到2-8％，或者甚至达到10％。通常浓度至少为3％，优选不超过5或6％，优选4或5％。所述水量是碳酸钠活化方法中典型的用量并且其用量通常同样可用于本发明中。
但是，本发明中使用活化剂的另一个优点是它们还将在更宽的浓度范围内引起很好的活化并且在粘土浓度为8-14％或15％时可实现如此好的活化。尽管在该过程中粘土活化并由此有可能变得很粘稠，但是活化剂的优点是所制成的组合物的粘度仍然很低并且具有很好的易于处理的液体流动特性。
也可在甚至更高的粘土浓度下，例如15-40％的范围内进行活化。我们在我们的共同未决PCT申请……(参见与要求GB9604950.7优先权同一日期提出的PRL03666WO)中公开了粘土浓度为15-40％的浓缩物，并且该浓缩物含有活化量的柠檬酸钠。
螯合剂的作用可能是与碱土离子发生交换，固定经交换的钙或镁离子，以使它们不能发生交换而返回到膨润土中。当优选使用通过离子交换引入到膨润土中的阳离子螯合剂时，通常使用钠形式的螯合剂。但是，必要时也可使用其它的活化阳离子，例如钾或铵。
合适的可用作螯合剂的膦酸酯可选自任何一种用于螯合碱土金属离子的膦酸酯，它们是，例如商品名为Dequest的市售物质。
可使用的合适的羟基羧酸包括诸如酒石酸钠或葡糖酸钠的物质，但是优选的物质是柠檬酸钠。必要时可优选使用游离酸，而不使用水溶性盐。
合适的氨基羧酸包括诸如DTPA、NTA和EDDHA和EDTA的物质。
可使用的二-或三-(或更高级)羧酸包括丙二酸、琥珀酸、戊二酸、己二酸和草酸，通常是以钠盐形式使用。这些酸(和所有的螯合剂)优选低分子量的物质，例如具有的分子量低于500并且通常是单体。在EP485124和4613542和4624982中已经公开了在浆料中使用高分子量的聚丙烯酸钠，但是，这些专利未提及本发明的优点。
螯合剂的用量应足以使指定的体系活化，其用量通过常规的实验即可确定。其用量以膨润土的干基重量为基通常为1-20％(重量)，优选3-15％(重量)。
所有的这些用量是假定在组合物中只有螯合剂是有效的活化物质。可使用一种或多种螯合剂的混合物，必要时可使用一种或多种螯合剂与其它有用活化剂例如碳酸钠的混合物。如果有碳酸钠存在，那么可降低螯合剂的要求用量。如果有不需要的任何显著量的组分例如氯化钠存在，那么必须显著地增加螯合剂的用量，因此，优选地是无需有意地添加电解质，例如氯化钠、硫酸钠或硝酸钠。
作为膨润土，可使用任何一种通常称为膨润土型粘土或称作膨润土的阴离子溶胀粘土。它们通常是绿土或蒙脱石，但优选蒙脱石。合适的绿土或蒙脱石粘土包括怀明娥膨润土和漂白土和包括那些已知的化学术语为锂蒙脱石和膨润土的各类粘土。粘土将以碱土形式存在，通常则以钙或钙和镁的形式存在。
众所周知，在用于各种目的的造纸方法中都使用膨润土，本发明可应用于所有的这些造纸方法。例如可将膨润土作为树脂分散剂使用。
可应用本发明的一种造纸方法是将膨润土加入到纤维素悬浮液中，其用量通常为0.02-2％干重，随后通常是在高剪切的最后位置(例如在即将排水前刚好在流浆箱之前)之后加入中等或高分子量(例如约500000)的聚合物助留剂。高分子量聚合物可以是非离子、阴离子或阳离子聚合物。纤维素悬浮液可以由比较纯的纸浆或具有比较高阳离子需求的纸浆制成。
特别有用的这类方法是那些纸浆具有比较高的阳离子需求，聚合物基本上是非离子或阴离子型聚合物以及纸产品优选地是白报纸或波纹中号纸的方法。US4305781和EP-A-17353公开了这种类型的方法，其总的填料量较低，其中还进一步详细描述了合适的非离子或低离子聚合物和合适的纤维素悬浮液，该文献引入本文作为参考。可使用更高级的阴离子或阳离子聚合物。当纤维素悬浮液含有脱墨废液时，这些方法是特别有用的。EP-A-608989和AU-A-63977/86还公开了合适的聚合物和填料(当填充纸浆时)。
当在微粒保留法中实施本发明时，本发明是特别有价值的，其中向含水悬浮液中加入聚合物助留剂，使该悬浮液进行剪切，然后在剪切后，通常是在高剪切的最后位置之后例如在即将排水前刚好在流浆箱之前加入膨润土。聚合物可以是非离子或阴离子聚合物，但是常常优选阳离子型聚合物。
阳离子聚合物可以是天然物质例如阳离子淀粉，但是主要优选直链合成的阳离子聚合物，其具有的分子量约为500000。在剪切时分散液中存在的阳离子聚合物的量应足以使通过添加聚合物形成絮凝物，并且通过剪切破坏絮凝物而形成微絮凝物，该微絮凝物通过剪切阻止进一步降解，而是携带足够的电荷与膨润土发生相互作用，形成的保留和/或组织要比在高剪切的最后位置后单独添加聚合物时形成的好。
剪切可能仅仅是由于湍流单独通过管道或由于湍流通过中心筛、泵或其它产生剪切的装置引起的。
优选的方法包括由申请人提供的商标为Hydrocol的商业化方法以及例如US4753710、4913775和4969976中公开的优选方法，所有的这些文件引入本文作为参考。对于任何特定的方法来说，聚合物的最佳用量可通过常规实验手段确定，并将尤其取决于是否低分子量阳离子聚合物，中等分子量阳离子聚合物，和/或干强树脂在某一早期阶段加入到悬浮液水溶液中。
在任何使用活化膨润土的地方可使用本发明的活化膨润土，例如在纸浆脱水、造纸污泥脱水、液固分离方法、废水澄清、墨黑的废水澄清和树脂固着(pitch fixing)(在造纸方法中)中使用。也可在使用活化膨润土的其它领域中使用活化膨润土，例如在用膨润土的铁矿造粒的制备中或其它矿物加工中使用。
下面是一些实施例。
实施例1
将5份重量的钙膨润土在95份重量的含有活化剂的水溶液中活化，活化剂的用量详细描述如下。
在每个实施例中，活化剂的用量以膨润土的干基重量为基的百分比表示。使用的产品如下。
A-碳酸钠 6％
C-柠檬酸钠 17％
D-乙二胺四乙酸钠 21％。
实施例2
在按US4753710描述的实验室模拟的造纸方法中使用实施例1制备的活化膨润土。尤其是向0.5％漂白的牛皮纸纤维配料(Kraft FibreFurnish)的稀纸浆液中加入500g/t的高分子量(特性粘度为6dl/g)阳离子聚丙烯酰胺，所述聚丙烯酰胺是由40％(重量)氯代甲烷季铵化(quarternised)的二甲基氨基乙基丙烯酸酯和60％(重量)丙烯酰胺制备的。使纤维素悬浮液以1500rpm的速度剪切60秒钟，然后加入指定剂量的活化膨润土，在带隔板的Britt瓶中缓慢混合悬浮液，记录从1000ml的稀纸浆液中排出700ml时的Schopper Riegler排水时间。在该实验中，最短的可能排水时间得出了最好的结果，优选地是膨润土的用量较低。
在下表中，头行标记的“膨润土”数字是用g/t表示的干基重量，用字母标记的行中的数字是使用指定量实施例1中的活化膨润土时按秒计的排水时间。
在下表中，头行Ca表示使用未活化钙膨润土的结果。
表1
| 膨润土 | Ca | A | C | D |
| 0 | 63 | 63 | 63 | 63 |
| 500 | 64 | 41 | 37 | 56 |
| 1000 | 62 | 25 | 25 | 49 |
| 2000 | 61 | 18 | 15 | 36 |
| 4000 | 58 | 14 | 11 | 20 |
该数据表明：就排水时间而言，用柠檬酸酯活化(C行)得到的结果与用碳酸钠活化时的一样好，甚至要比用碳酸钠活化的好，使用EDTA(D行)可得到满足要求，但是不太令人满意的结果。
Claims (8)
1.一种干粘土组合物，包含碱土膨润土和活化量的螯合剂的碱金属盐或铵盐的混合料，所述螯合剂选自膦酸酯、羟基羧酸、氨基羧酸和二元或三元羧酸。
2.根据权利要求1的组合物，其中盐是钠盐。
3.根据权利要求1或2的组合物，其中螯合剂是柠檬酸钠。
4.碱土膨润土的活化方法，包括将碱土膨润土与活化水溶液混合，所述水溶液含有活化量的选自膦酸酯、羟基羧酸、氨基羧酸和二元或三元羧酸螯合剂的碱金属盐或铵盐。
5.根据权利要求4的方法，其中螯合剂是钠盐形式的螯合剂。
6.根据权利要求4的方法，其中螯合剂是柠檬酸钠。
7.根据权利要求4-6任一项的方法，是在膨润土浓度为2-14％的条件下进行的。
8.一种造纸方法，包括形成纤维素悬浮液，使活化膨润土分散液混合到悬浮液中，从悬浮液中排放出水，形成湿的薄片并干燥薄片，其中所述活化膨润土分散液是按权利要求4的方法制备的并任选地随后稀释或所述活化膨润土分散液是通过将权利要求1的组合物混到水中制备的。
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| JPS63230550A (ja) * | 1987-03-18 | 1988-09-27 | 野上 昭治 | 粘土鉱物の高純度精製方法 |
| US5266538A (en) * | 1990-12-21 | 1993-11-30 | Southern Clay Products, Inc. | Method for preparing high solids bentonite slurries |
| US5391228A (en) * | 1990-12-21 | 1995-02-21 | Southern Clay Products, Inc. | Method for preparing high solids bentonite slurries |
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| GB1497280A (en) * | 1974-12-10 | 1978-01-05 | Ass Portland Cement | Agglomerating suspended particulate material in aqueous systems |
| DE3065576D1 (en) * | 1979-03-28 | 1983-12-22 | Allied Colloids Ltd | Production of paper and paper board |
| US4624982A (en) * | 1985-04-05 | 1986-11-25 | American Colloid Company | Method of temporarily inhibiting the swellability of water swellable clays and compositions |
| US4613542A (en) * | 1985-04-05 | 1986-09-23 | American Colloid Company | Method of impregnating a water-penetrable article with a swell-inhibited water swellable clay slurry |
| DE3541163A1 (de) * | 1985-11-21 | 1987-05-27 | Basf Ag | Verfahren zur herstellung von papier und karton |
| GB8602121D0 (en) * | 1986-01-29 | 1986-03-05 | Allied Colloids Ltd | Paper & paper board |
| US4913775A (en) * | 1986-01-29 | 1990-04-03 | Allied Colloids Ltd. | Production of paper and paper board |
| SE8701252D0 (sv) * | 1987-03-03 | 1987-03-25 | Eka Nobel Ab | Sett vid framstellning av papper |
| GB8807445D0 (en) * | 1988-03-28 | 1988-05-05 | Allied Colloids Ltd | Pulp dewatering process |
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| GB9024016D0 (en) * | 1990-11-05 | 1990-12-19 | Allied Colloids Ltd | Clay compositions,their manufacture and their use in the production of paper |
| CA2108027C (en) * | 1991-07-02 | 1997-05-27 | Bruno Carre | A process for the production of paper |
| US5223463A (en) * | 1991-08-01 | 1993-06-29 | Ecc International Inc. | Process for producing a kaolin clay product |
| US5537934A (en) * | 1994-10-19 | 1996-07-23 | Engelhard Corporation | Cationically stabilized slurries of calcined kaolin clay |
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- 1996-03-08 GB GBGB9604927.5A patent/GB9604927D0/en active Pending
-
1997
- 1997-03-10 CA CA002247205A patent/CA2247205C/en not_active Expired - Fee Related
- 1997-03-10 NZ NZ331471A patent/NZ331471A/xx unknown
- 1997-03-10 ES ES97906288T patent/ES2169353T3/es not_active Expired - Lifetime
- 1997-03-10 AU AU21028/97A patent/AU721609B2/en not_active Ceased
- 1997-03-10 CN CN97192857A patent/CN1088776C/zh not_active Expired - Fee Related
- 1997-03-10 WO PCT/GB1997/000648 patent/WO1997033040A1/en active IP Right Grant
- 1997-03-10 DK DK97906288T patent/DK0885327T3/da active
- 1997-03-10 EP EP97906288A patent/EP0885327B1/en not_active Expired - Lifetime
- 1997-03-10 DE DE69709854T patent/DE69709854T2/de not_active Expired - Fee Related
- 1997-03-10 HU HU9902143A patent/HU223695B1/hu not_active IP Right Cessation
- 1997-03-10 CZ CZ19982857A patent/CZ293232B6/cs not_active IP Right Cessation
- 1997-03-10 PT PT97906288T patent/PT885327E/pt unknown
- 1997-03-10 SK SK1226-98A patent/SK122698A3/sk unknown
- 1997-03-10 AT AT97906288T patent/ATE211516T1/de not_active IP Right Cessation
- 1997-03-10 JP JP9531594A patent/JP2000506113A/ja not_active Ceased
- 1997-03-10 PL PL97329369A patent/PL190372B1/pl not_active IP Right Cessation
- 1997-03-10 RU RU98118376A patent/RU2144592C1/ru not_active IP Right Cessation
- 1997-03-10 KR KR10-1998-0707065A patent/KR100489647B1/ko not_active IP Right Cessation
- 1997-03-10 US US09/142,220 patent/US6024790A/en not_active Expired - Fee Related
- 1997-03-10 BR BR9707830A patent/BR9707830A/pt not_active IP Right Cessation
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1998
- 1998-09-07 NO NO984108A patent/NO984108L/no unknown
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| US4309222A (en) * | 1980-10-09 | 1982-01-05 | Pfizer Inc. | Kaolin clay slurries of reduced viscosity |
| JPS61118499A (ja) * | 1984-11-14 | 1986-06-05 | 株式会社 ネオス | スプレ−洗浄用洗浄剤 |
| JPS63230550A (ja) * | 1987-03-18 | 1988-09-27 | 野上 昭治 | 粘土鉱物の高純度精製方法 |
| US5266538A (en) * | 1990-12-21 | 1993-11-30 | Southern Clay Products, Inc. | Method for preparing high solids bentonite slurries |
| US5391228A (en) * | 1990-12-21 | 1995-02-21 | Southern Clay Products, Inc. | Method for preparing high solids bentonite slurries |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100536823C (zh) * | 2003-04-03 | 2009-09-09 | 高露洁-棕榄公司 | 组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9902143A2 (hu) | 2000-02-28 |
| EP0885327B1 (en) | 2002-01-02 |
| JP2000506113A (ja) | 2000-05-23 |
| SK122698A3 (en) | 1999-06-11 |
| CZ285798A3 (cs) | 1999-03-17 |
| KR100489647B1 (ko) | 2005-08-31 |
| US6024790A (en) | 2000-02-15 |
| WO1997033040A1 (en) | 1997-09-12 |
| HUP9902143A3 (en) | 2003-12-29 |
| CN1213420A (zh) | 1999-04-07 |
| PL190372B1 (pl) | 2005-12-30 |
| NO984108D0 (no) | 1998-09-07 |
| RU2144592C1 (ru) | 2000-01-20 |
| KR19990087616A (ko) | 1999-12-27 |
| BR9707830A (pt) | 1999-07-27 |
| DK0885327T3 (da) | 2002-04-22 |
| PL329369A1 (en) | 1999-03-29 |
| HU223695B1 (hu) | 2004-12-28 |
| NZ331471A (en) | 2000-01-28 |
| NO984108L (no) | 1998-09-07 |
| AU2102897A (en) | 1997-09-22 |
| CA2247205C (en) | 2005-06-28 |
| AU721609B2 (en) | 2000-07-13 |
| CA2247205A1 (en) | 1997-09-12 |
| EP0885327A1 (en) | 1998-12-23 |
| DE69709854T2 (de) | 2002-08-29 |
| GB9604927D0 (en) | 1996-05-08 |
| ES2169353T3 (es) | 2002-07-01 |
| DE69709854D1 (de) | 2002-02-28 |
| PT885327E (pt) | 2002-05-31 |
| CZ293232B6 (cs) | 2004-03-17 |
| ATE211516T1 (de) | 2002-01-15 |
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