CN1391534A - 含铈iii的铈化合物胶态分散体、其制备方法及其应用 - Google Patents
含铈iii的铈化合物胶态分散体、其制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及一种含有铈III的铈化合物胶态分散体。该分散体的特征在于，其铈氧化物的浓度至少为50g/l，其相对于总铈含量的铈III含量至少为0.5％，其电导率最大为5mS/cm，其pH值为4－8，其特征还在于，其是由平均直径最大为15nm的颗粒构成。该分散体是由如下方法得到，其中，至少一种铈III盐在酸的存在下与碱反应，所述酸的量应使H+/Ce的比值大于1，然后将由前述反应得到的沉淀物再分散于水中。这类分散体可用于催化，润滑剂，陶瓷，发光体化合物或聚合物膜的制备，化妆品，并用作抗腐蚀剂。
Description
本发明涉及含铈III的铈化合物胶态分散体。
铈溶胶，更具体而言，四价铈溶胶是众所周知的。它们在例如化妆品工业及发光体领域是非常重要的。但是，这些应用要求溶胶要相当浓，稳定并且纯净。但是，溶胶制备方法是很复杂的，特别是它们需要使用离子交换树脂。采用一种容易的路线获得这类溶胶是令人感兴趣的。
本发明的目的是克服上述困难，并用更简单的路线制备足够浓的纯净溶胶。
为实现该目的，本发明提供一种铈化合物胶态分散体，其特征在于，其铈氧化物的浓度至少为50g/l，其相对于总铈含量的铈III含量至少为0.5％，其电导率最大为5mS/cm，其pH值为4-8，其特征还在于，该胶态分散体是由平均直径最大为15nm的颗粒构成。
本发明还提供一种制备所述胶态分散体的方法，其特征在于，至少一种铈III盐在酸的存在下与碱反应，所述酸的量应使H+/Ce的比值大于1，然后将由前述反应得到的沉淀物再分散于水中。
本发明方法是简单的，因为其本质上包括使盐和碱反应，并且可以采用简单的装置来进行。其由铈III化合物出发，在本发明的分散体中可以发现部分铈III化合物，并且这种分散体具有需要的纯度。
从下面的描述和用来举例说明本发明的各非限定性实施例可以清楚了解本发明的其它特征，细节和优点。
在本说明书中，铈化合物的“胶态分散体”或“溶胶”是指这样的体系，其由悬浮于含水液相中的基于铈氧化物和/或水合氧化物(氢氧化物)的胶体尺寸的细固体颗粒构成，所述颗粒可能还含有残余量的结合的或吸附的离子，例如硝酸根，乙酸根，柠檬酸根或铵离子。应该指出，在这样的分散体中，所述的铈可以完全以胶体形式存在，或者同时以离子形式和胶体形式存在。
第一个特征，本发明的分散体的浓度至少为50g/l。更具体地，该浓度可以至少为100g/l，进一步更具体地，该浓度可以至少为150g/l。该浓度是以铈氧化物CeO2的等效浓度表示。它是在空气中干燥并煅烧给定体积的分散体后测定的。
本发明分散体的第二个特征是其铈III的量。该量至少为0.5％，更优选该量至少为1％，进一步更优选该量至少为1.5％。一般地，该量最多为50％，更优选该量最多为10％。它是以CeIII/Ce的总原子比值表示的。所述分散体还包括以铈IV形式存在的铈。
本发明分散体的第三个特征是其纯度。该纯度是通过分散体的电导率测定的。所述电导率最大为5mS/cm。电导率可以低于这一数值，并且优选最大为2mS/cm，更优选最大为1mS/cm。进一步更优选地，电导率可以低于0.3mS/cm。
另外，本发明分散体的pH值可以较高，例如为4-8。这样的接近中性的pH值，可以使本发明分散体用于重要的应用中。
构成本发明溶胶的胶体颗粒是微细的。因此平均直径最大可以为15nm，优选为2-15nm，更优选为2-6nm。该直径是采用HRTEM分析法(高分辨率透射电子显微镜)，通过光度评价测定的。
在一个优选的变例中，本发明的分散体是非常纯的(就硝酸根阴离子来讲)。更准确地说，以胶体颗粒中硝酸根阴离子的重量计的分散体中硝酸根阴离子的量低于80ppm。
最后，本发明的分散体可以是连续相为水的含水分散体，或连续相为水/与水混溶溶剂的分散体，或连续相为有机溶剂的分散体。
更优选地，所述有机溶剂可以是与水混溶的溶剂。可以提及的实例是醇，例如甲醇或乙醇；二元醇，例如乙二醇；二元醇的乙酸酯衍生物，例如乙二醇单乙酸酯；二元醇醚；多元醇或酮。
现在阐述制备本发明分散体的方法。
所述方法包括第一步，其中铈III盐在酸的存在下，与碱反应。
所述碱可以是氢氧化物型产品。可以提及的有碱金属，碱土金属和铵的氢氧化物。也可以使用二级、三级或四级胺。但是，胺和氨是优选的，因为它们减少了碱金属或碱土金属阳离子污染产品的危险。
可以被特别提及的铈III盐是铈III的乙酸盐、氯化物和硝酸盐及这些盐的混合物，例如乙酸盐/氯化物混合物。
本发明方法的一个特征是，所述铈盐在酸的存在下与碱反应。
可以使用的酸包括无机酸和/或有机酸，更优选那些相应于在反应中使用的铈III盐的酸。因此，可以提到乙酸或盐酸。
在反应中存在或使用的酸的量应使H+/Ce的摩尔比大于1，优选大于1.5，更优选至少为2。该量是指与碱开始反应时存在的酸的量。
所述碱可以与铈盐连续反应，这意味着向反应介质中同时加入反应物。该反应可以在空气中，在空气和氮气气氛中，或在氮气中进行。
反应介质的pH值一般为7.5-9.5。
反应后得到沉淀物。该沉淀物可以采用任何已知的方法，例如通过离心分离，从液体介质中分离出来。然后，得到的沉淀物可以被吸收进水悬浮体，从而制备出本发明的分散体。
有利地是，可以洗涤从所述反应得到的沉淀物。该洗涤可以通过向沉淀物中加入水，然后在搅拌后，通过例如离心分离从液体介质中分离出固体来进行。如果需要，该操作可以重复数次。
在本发明的一个变例中，吸收进水悬浮体后得到的分散体可以通过超滤进行纯化。
如果需要，所述分散体还可以通过例如超滤进行浓缩。
洗涤和超滤可以在空气中，在空气和氮气气氛中，或在氮气中进行。进行这些操作的气氛，扮演了使铈III转化为铈IV的角色。
在部分或全部分散体是在非水溶剂介质中的情况下，该分散体可以由含水分散体制备，即向含水分散体中加入有机溶剂，然后蒸馏以除去水，或者用超滤膜处理以逐渐地除去水。
本发明的分散体可用于各种应用中。特别可以提到催化作用，更具体是汽车后燃，在这种情况下所述分散体被用于制备催化剂。所述分散体还可以用于润滑，陶瓷和制备发光体化合物。还可以利用所述分散体的抗紫外线性能，例如制备聚合物膜(例如丙烯酸或聚碳酸酯型)或用于化妆品组合物，特别是用于制备抗紫外线膏霜。最后，它们可以用作抗腐蚀剂的基材。
现在给出实施例。在这些实施例中，采用CDM 83电导仪(RadiometerCopenhaguen)及其CDC 304型池测定电导率。
实施例1
本实施例涉及由铈的乙酸盐、氯化物及盐酸的混合物制备铈分散体。
将含有49.29％CeO2氧化物的334g乙酸铈(III)(0.957摩尔铈)和含有45.90％CeO2的89.9g CeCl3(即0.24摩尔铈)加入到烧杯中，然后加入已经用500ml软化水稀释的357g 36％的浓盐酸(即3.52摩尔HCl)。开始搅拌，用软化水补充至2000ml。继续搅拌直至得到肉眼看上去为澄清的溶液。得到的混合物的浓度为约0.6M Ce，并且(H/Ce)摩尔比为2.9。
在包括下列部分的连续装置中沉淀出固体：
·一个装配有桨式搅拌器的1升反应器，搅拌器转速调节为400转/分钟，该反应器带有一个0.5升的水槽，和一个pH值调节泵设定为pH值8.7的电极；
·两个加料漏斗，一个装有上述的铈盐溶液，另一个装有10N的氨水溶液。
乙酸铈溶液的流速固定为约500ml/min，调节氨水的流速以调节pH值。用243分钟时间加完2000ml铈盐混合物和600ml 10N氨水。
Ce沉淀反应的收率经测定为约91％。
以4500转/分钟离心分离10分钟，从母液中分离出所述沉淀物。在1000℃煅烧样品，使得所测CeO2氧化物含量为27.7％。
加入软化水分散所述沉淀物，得到0.25M的Ce分散体。搅拌15分钟后再离心分离。连续重复两次该操作。
用软化水将100ml 0.25M的Ce分散体稀释到300ml。采用3KD膜进行超滤，将其浓缩至100ml。进行三次超滤。在最后一次超滤时，通过超滤至体积为34ml以进一步浓缩。
得到的分散体样品蒸发并在1000℃煅烧，使最终分散体中CeO2浓度为60g/l。
所述胶态分散体外观是澄清的。该分散体的pH值为5。NO3含量低于80ppm。总的CeIII/Ce的比值为1.8％(采用化学方法测定)，分散体的电导率为0.7mS/cm。
实施例2
本实施例涉及由铈的乙酸盐与乙酸制备铈分散体。
将含有49.29％CeO2氧化物的416.5g乙酸铈(III)(1.19摩尔铈)加入到烧杯中，然后加入已经用100ml软化水稀释的144g浓乙酸(即2.4摩尔乙酸)。开始搅拌，用软化水补充至2400ml。继续搅拌直至得到肉眼看上去为澄清的溶液。得到的混合物的Ce浓度为约0.5M，并且(H/Ce)摩尔比为2。
在实施例1所述的连续装置中沉淀出固体。
用270分钟时间加完2400ml乙酸铈溶液和2120ml 3N氨水。
Ce沉淀反应的收率经测定为约95.7％。
以4500转/分钟离心分离10分钟，从母液中分离出所述沉淀物。在1000℃煅烧样品，使得所测CeO2氧化物含量为23.4％。
加入软化水分散所述沉淀物，得到0.25M的Ce分散体。搅拌15分钟后再离心分离。连续重复两次该操作。
用软化水将100ml 0.25M的Ce分散体稀释到300ml，并在空气气氛下搅拌过夜。采用3KD膜进行超滤，将其浓缩至100ml。进行三次超滤。在最后一次超滤时，通过超滤至体积为34ml以进一步浓缩。
得到的分散体样品蒸发并在1000℃煅烧，使最终分散体中CeO2浓度为57g/l。
所述胶态分散体外观是澄清的。该分散体的pH值为4.7。
NO3含量低于80ppm。总的CeIII/Ce的比值为1.9％，分散体的电导率为0.9mS/cm。胶粒大小为3nm。
实施例3
本实施例阐述本发明分散体的抗紫外线性能。测量作为波长的函数的直接透光率。
这些透光率是采用带有样品厚度为2mm的石英池的Perkin Elmerλ900 UV-可见分光光度计测定的。通过测量相对于参比样(不含胶态分散体的起始储槽)的透射强度，测定直接透光率值。
用软化水稀释所述胶态分散体样品，以使最终的CeO2浓度为3％(重量)。
得到的透光率曲线具有下列特征值：
400nm，10％透光率。
418nm，50％透光率。
455nm，80％透光率。
Claims (14)
1.一种铈化合物的胶态分散体，其特征在于，其铈氧化物的浓度至少为50g/l，其相对于总铈含量的铈III含量至少为0.5％，其电导率最大为5mS/cm，其pH值为4-8，其特征还在于，它由平均直径最大为15nm的颗粒构成。
2.根据权利要求1的分散体，其特征在于，其浓度至少为100g/l。
3.根据权利要求1或2的分散体，其特征在于，其铈III含量至少为1％。
4.根据前述权利要求任意一项的分散体，其特征在于，其硝酸根阴离子的含量低于80ppm。
5.根据前述权利要求任意一项的分散体，其特征在于，其电导率最大为2mS/cm，更优选最大为1mS/cm。
6.根据前述权利要求任意一项的分散体，其特征在于，连续相为水。
7.根据权利要求1-5的任意一项的分散体，其特征在于，连续相为水/与水混溶溶剂的混合物，或为有机溶剂。
8.一种制备根据前述权利要求任意一项的胶态分散体的方法，其特征在于，至少一种铈III盐在酸的存在下与碱反应，所述酸的量应使H+/Ce的摩尔比大于1，然后将由前述反应得到的沉淀物再分散于水中。
9.根据权利要求8的方法，其特征在于，所述沉淀物再分散于水中后，通过超滤纯化得到的分散体。
10.根据权利要求8或9的方法，其特征在于，所述铈III盐是乙酸盐或氯化物。
11.根据权利要求8-10的任意一项的方法，其特征在于，所述酸是乙酸或盐酸。
12.根据权利要求8-11的任意一项的方法，其特征在于，所述反应是在连续工艺中进行的。
13.一种制备胶态分散体的方法，其中连续相为水/与水混溶溶剂的混合物或为有机溶剂，所述方法的特征在于，将有机溶剂加入到根据权利要求8-12的任意一项的方法得到的含水分散体中，然后蒸馏以除去水，或者用超滤膜处理该分散体以逐渐地除去水。
14.一种分散体的应用，该分散体是权利要求1-7的任意一项所定义类型的分散体，或由根据权利要求8-13的任意一项的方法得到的类型的分散体，用作抗腐蚀剂的基材、用于制备聚合物膜、化妆品组合物、催化，特别是用于汽车后燃、润滑剂或陶瓷。
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| FR9914576A FR2801298B1 (fr) | 1999-11-19 | 1999-11-19 | Dispersion colloidale d'un compose de cerium et contenant du cerium iii, procede de preparation et utilisation |
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| FR2831177B1 (fr) | 2001-10-22 | 2005-02-18 | Rhodia Elect & Catalysis | Dispersion colloidale et poudre colorees de cerium ou de cerium et de titane, de zirconium, d'aluminium ou d'une terre rare, leur procede de preparation et leur utilisation |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| US7235142B2 (en) | 2002-01-04 | 2007-06-26 | University Of Dayton | Non-toxic corrosion-protection rinses and seals based on cobalt |
| EP1472319A1 (en) | 2002-01-04 | 2004-11-03 | University Of Dayton | Non-toxic corrosion protection pigments based on cobalt |
| DE10337199A1 (de) * | 2003-08-13 | 2005-03-10 | Degussa | Ceroxidpulver |
| JP5013671B2 (ja) * | 2004-12-28 | 2012-08-29 | 日揮触媒化成株式会社 | 金属酸化物ゾルの製造方法および金属酸化物ゾル |
| US10041176B2 (en) | 2005-04-07 | 2018-08-07 | Momentive Performance Materials Inc. | No-rinse pretreatment methods and compositions |
| FR2905371B1 (fr) * | 2006-08-31 | 2010-11-05 | Rhodia Recherches & Tech | Composition a reductibilite elevee a base d'un oxyde de cerium nanometrique sur un support, procede de preparation et utilisation comme catalyseur |
| KR101773543B1 (ko) | 2015-06-30 | 2017-09-01 | 유비머트리얼즈주식회사 | 연마 입자, 연마 슬러리 및 연마 입자의 제조 방법 |
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| US4800072A (en) * | 1988-01-14 | 1989-01-24 | Rhone Poulenc, Inc. | Anhydrous cerous nitrate-ammonium nitrate complex and a process for its preparation from ceric ammonium nitrate |
| FR2724331B1 (fr) * | 1994-09-12 | 1996-12-13 | Rhone Poulenc Chimie | Dispersions colloidales d'un compose de cerium a ph eleve et leurs procedes de preparation |
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| MXPA02004948A (es) | 2003-10-14 |
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| NO20022374L (no) | 2002-07-11 |
| EP1265815A1 (fr) | 2002-12-18 |
| CA2391946A1 (fr) | 2001-05-25 |
| KR20020070284A (ko) | 2002-09-05 |
| CN1212882C (zh) | 2005-08-03 |
| DE60017948D1 (de) | 2005-03-10 |
| EP1265815B1 (fr) | 2005-02-02 |
| BR0015685A (pt) | 2002-08-06 |
| JP3950691B2 (ja) | 2007-08-01 |
| ATE288403T1 (de) | 2005-02-15 |
| CA2391946C (fr) | 2007-01-23 |
| RU2228295C2 (ru) | 2004-05-10 |
| NO20022374D0 (no) | 2002-05-16 |
| KR100487453B1 (ko) | 2005-05-06 |
| FR2801298A1 (fr) | 2001-05-25 |
| JP2003514744A (ja) | 2003-04-22 |
| WO2001036331A1 (fr) | 2001-05-25 |
| FR2801298B1 (fr) | 2002-05-03 |
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