CN101903473B - 二氧化钛基光催化复合材料及在偏高岭土载体上的衍生品 - Google Patents
二氧化钛基光催化复合材料及在偏高岭土载体上的衍生品 Download PDFInfo
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- CN101903473B CN101903473B CN2008801215111A CN200880121511A CN101903473B CN 101903473 B CN101903473 B CN 101903473B CN 2008801215111 A CN2008801215111 A CN 2008801215111A CN 200880121511 A CN200880121511 A CN 200880121511A CN 101903473 B CN101903473 B CN 101903473B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- RPFOZHPQAUXAOM-UHFFFAOYSA-N prop-2-enoic acid;silicic acid Chemical compound OC(=O)C=C.O[Si](O)(O)O RPFOZHPQAUXAOM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明描述一种光催化复合材料，其包括支撑于偏高岭土上的二氧化钛。与已知的实例相比，本发明的复合材料可得到具有高光催化效果的粘结剂及其衍生品，即使当所用光催化剂的量低于现有技术的用量。
Description
技术领域：
本发明涉及新光催化复合材料及其衍生品，其包括基于偏高岭土载体的二氧化钛。
背景技术：
晶型为锐钛矿型的二氧化钛是已知的光催化剂。在光照和空气湿度下，可以催化空气中所存在的各种氧化物，特别是降解和消除过程。
在建筑领域，已知水泥产品是传统的含二氧化钛的，二氧化钛存在水泥中或作为表面层(PCT/EP9704008，EP885857，EP1196359)。
二氧化钛的光催化可以防止水泥产品因环境污染而变色。另外，由此类产品建造的建筑物因原色保持久而具有更好的外观，无需频繁的表面清理循环。二氧化钛也被用在涂料、糊浆或其他涂层组合物，用于预制建筑物上以便于保持原始颜色(MI2007A001508)。
已有含二氧化钛的城市道路铺装材料，例如铺地材料、路面产品等等(PCT/EP2004/0015，PCT/EP2005/0529)。这些产品被普遍用于降低城市交通污染(氮氧化物、碳氢化物等等)：这些物质被吸附到产品的多孔表面上然后被氧化为可由雨水冲刷的非挥发性化合物。
虽然这些混凝土产品已经被证实有效，现在的研究仍在试图找到新的组合物和产品，其具有更好的光催化能力，或者在相同光催化能力下，使用更少的料。
后者对于混凝土领域非常重要，即使用大量具有非常低成本/重量比的产品：对于这些产品，添加精细化学添加剂，例如二氧化钛，会导致非常高的价格增长。这表明维持高水平光催化效果却使用更少量的光催化剂的重要性。
在所有前述产品中光催化剂与载体元件无特定交互；前述散装产品是通过简单物理混合各种组分而得，而涂层产品是通过在预制载体上层化光催化剂而得。在所有情况下，两成份之间的关系仅为相邻。
在光催化产品(以及对于水泥)领域，已知使用其它惰性无机材料，例如粘土、高岭土等。例如专利KR-A-20010074099描述一种粘土、高岭土和石墨基(Al2Si2O5(OH)4)光催化砖，其表面覆盖有二氧化钛层。专利CN-A-1696228描述一种含有二氧化钛、高岭土、硅石灰、碳酸钙和其它成分纳米颗粒的涂料。
发明内容：
本发明第一目的旨在提供一种新的光催化复合材料，其适于获得在使用少量光催化剂时具有高光催化效果的粘结剂及衍生品。本发明还旨在提高前述类型的复合材料，其中光催化剂与载体材料以强力稳定方式绑定。本发明再一目的是提供复合材料及其衍生品，其不仅在表面进行反应，也在内部，即非表面层反应。
这些目的地实现是通过基于本发明的新光催化复合材料及其衍生物(粘结剂、干燥预混产品、水泥质组合物以及最终成品)，该复合材料包括基于偏高岭土载体的二氧化钛；本发明还包括获得这些产品的方法及其工业应用。与本领域已知产品相比，基于本发明的复合材料即使在含有小量光催化剂(通常小于现有技术剂量)仍提供高效光催化粘结剂。
本发明的复合材料中二氧化钛以稳定的方法和特有的物理方式绑定到偏高岭土载体。
附图说明：
-图1是扫描电子显微镜(SEM)照片，其显示在氧化铝载体上TiO2晶粒。
-图2是扫描电子显微镜(SEM)照片，其显示在高岭土载体上TiO2晶粒。
-图3是扫描电子显微镜(SEM)照片，其显示在基于本发明的氧化铝载体上TiO2晶粒。
-图4、5是扫描电子显微镜(SEM)照片，其显示在基于本发明高岭土载体上TiO2晶粒；(50/50重量比)。
具体实施方式：
本发明的光催化复合材料包括位于偏高岭土载体上作为光催化剂的二氧化钛。
二氧化钛(TiO2)优选晶型为锐钛矿型。所用的TiO2为普遍型或唯一型：所谓“普遍”是指总TiO2中以重量计锐钛矿型TiO2含量至少为50％；所谓“唯一”或“总”是指100％；在本发明优选实施例中锐钛矿含量至少为90％。二氧化钛颗粒的比(BET)表面积优选为5-350m2/g，更优选为100-300m2/g。
用作载体的偏高岭土(Al2O32SiO2)为高岭土材料脱羟基后的形式，通常通过煅烧而得；偏高岭土市面有售(例如本申请实验部分所用的比表面积12.6m2/g的METASTAR 501)。
在这里，所谓“光催化”是指产品的特性，其在光线和空气存在下可以催化环境中的一个或多个无机或有机污染物的分解反应；这些污染物例如芳香族缩聚物、醛、可吸入颗粒烟尘，氮氧化合物(NOx)和硫氧化合物(SOx)。
优选，以重量计，本发明复合材料50％为二氧化钛，另50％是偏高岭土载体。然而本发明两个组分可以有不同的比例。
所述二氧化钛/偏高岭土复合材料是以″散装″存在，换句话说″散加″到混凝土，使得其不仅分散在混凝土表面，也进入内层。
所述复合材料可用于制备衍生品，例如粘结剂、干燥预混产品和即用型水泥质组合物(特别是糊浆、灰浆或混凝土混合物)：每个产品包括本发明一个特定实施例。
基于本发明的粘结剂包括混合有适宜的水硬性粘结剂的前述复合材料。基于本发明的粘结剂及其衍生品中，光催化复合材料基于前述定义是散装的。
所谓“水硬性粘结剂”是指在干燥状态下为粉末性固体材料，当其与水混合可形成塑性混合物并可定型硬化，包括在水下，这样的材料例如水泥。水硬性粘结剂例如符合ENV 197.1的水泥，以及No.595法规(1965年5月26日通过)定义的水硬性石灰，或其混合物。基于本发明的光催化粘结剂以重量计含有0.1-10％的二氧化钛，以TiO2相对于水泥的量计算；优选的，所述量可以维持在更低水平，例如0.1-4％，或0.1-2.5％，而得的优秀的光催化效果；这样光催化水泥产品可具有符合本发明目的的高效率/费用比。
将前述粘结剂与精细或粗制骨料以及其他可能的水泥产品添加剂混合，得的干性预混产品：其含有除水外形成光催化水泥质组合物的全部组分以备用(特别是糊浆、灰浆或混凝土混合物)。这些本领域常用并可存在于干性预混产品中的添加剂包括流化剂、超流化剂、充气剂、凝硬性添加剂、填料等。
通过将水添加入前述预混产品而得的水泥质组合物包括水泥糊浆，或粘结剂与水无骨料组成的混合物，也称混杂物，或者水、粘结剂和骨料构成的混合物。所谓“骨料”或“惰性物”或“惰性骨料”在本发明中是同义词，如UNI EN 206标准中的分类。它们可为精细骨料，例如砂，或粗制骨料。混杂物例如包括灰浆(粘结剂、水和精细骨料组成的混合物)，和水泥混合物(水、粘结剂、精细骨料和粗制骨料组成的混合物)。骨料含量，水/水泥比，以及形成水泥质组合物的混合方法是本领域常规的。
使用本发明混合物制得的光催化混凝土产品可以降低环境中无机和有机污染物，例如芳香族缩聚物、醛、可吸入颗粒烟尘、氮氧化合物(NOx)和硫氧化合物(SOx)。其对NOx.效果特别强烈。
因此，本发明另一目的是光催化水泥产品，其选自水泥混合物制备的建筑元件、铺地材料、路面产品、隧道或车库拱顶、铺路石、砌块、砖、涂料、抹灰饰面、抹灰、纪念碑元件、挤压制品、瓦。
本发明的光催化复合材料也可用于非水泥涂料产品，例如，硅酸钾、硅氧烷硅酸盐或丙烯酸硅酸脂酯等硅酸盐涂料饰面。本发明还包括降低环境污染物的方法，即，在光线和空气存在下将前述一个或多个产品与空气相接触。污染物优选自芳香族缩聚物、醛、可吸入颗粒烟尘、氮氧化合物(NOx)和硫氧化合物(SOx)。
用于制备前述复合材料的方法以及该方法获得的复合材料构成了本发明的另一目的。普遍接受的工艺包括将偏高岭土和TiO2或其前体之一(例如TiCl4、Ti(OH)4或TiOSO4或其它已知前体)接触。当直接起始于TiO2，可以直接用常规方法将其与偏高岭土混合。当起始于TiO2前体，优选添加到含偏高岭土的碱性悬浮液中，保持搅拌30-120分钟；混合条件(pH值，温度等等)选自TiO2前体水解的方法；这些条件是已知常规的，这些例如在实验部分所给出的；偏高岭土从悬浮液中重新获得的方法是采用已知常规方法，例如过滤和/或离心分离、干燥(例如在100℃)，然后进行热处理。为得的最好光催化效果，热处理温度应为300℃-700℃，优选350℃-650℃，持续1到5个小时，优选2到3个小时；这种处理也同样适用于从TiO2直接获得的复合材料。
下面给出非限制性示例及相应制备例，用于进一步解释本发明的特点和优点。
实验部分
1.制备本发明的催化剂(TCMC)
1.1沉淀TiCl
4
水溶液
试剂
用于沉淀的试剂如下：
-溶液1(Sol 1)：TiCl4(10ml TiCl4/100ml溶液.)；100ml TiCl4(氯化钛(IV)(Fluka公司产品)≥98.0％)加入到1升蒸馏水中。
-溶液2(Sol 2)：NH4HCO3 2M；158.1g NH4HCO3(碳酸氢铵-CarloErba公司产品)溶解于蒸馏水后加到1升。
-偏高岭土Metastar 501(商品名)。
光催化合成
为获得60克光催化产品(以重量计含50％TiO2)，30克偏高岭土被悬浮于750ml碱性溶液Sol 2，剧烈搅拌。420ml的Sol 1滴加大约60分钟。滴加末期测量pH在7左右，在这条件下水解完成。离心(或真空过滤)分离反应水。为消除可溶性盐，进行3-5次清洗，每次使用1.5升蒸馏水，温度为80℃左右。使用真空过滤或优选用大体积离心机离心分离洗涤液。
所得潮湿粉末在内通风炉105℃干燥，然后用旋转刀片均质器打散结块粉末。
最后在空气下在马弗炉中热处理，650℃，2.5小时，后将材料置于干燥器中快速冷却到室温。偏高岭土上的TiO2催化剂由此制得，其中锐钛矿型晶型超过90％。
1.2沉淀硫酸钛酰水性溶液(STMC01)
试剂
用于沉降的试剂如下：
-Sol 1：TiOSO4(10g TiO2/100ml溶液)；345g TiOSO4(硫酸氧钛(IV)水合物Riedel-de公司产品TiO2≥29％)溶解于蒸馏水中，加水到1升。
-Sol 2：NH4HCO3 2M；158.1g NH4HCO3(碳酸氢铵-Carlo Erba产品)溶解于蒸馏水中然后加水到1升。
-偏高岭土Metastar 501.
光催化合成
为获得60克光催化产品(以重量计含50％TiO2)，30克偏高岭土被悬浮于460ml碱性溶液Sol 2，然后剧烈搅拌。300ml Sol 1(二氧化钛前体)滴加60分钟.滴加末期测量pH在7左右，在这条件下水解完成。离心(或真空过滤)分离反应水。为消除可溶性盐，进行2阶段清洗，每次使用1.5升蒸馏水，温度为80℃左右。使用真空过滤或优选用大体积离心机离心分离洗涤液。
所得潮湿粉末在内通风炉105℃干燥，然后用旋转刀片均质器打散结块粉末。硫酸盐定量分析显示所得粉末中SO3含量少于1％。
最后在空气下在马弗炉中热处理，650℃，2.5小时，后将材料置于干燥器中快速冷却到室温。
1.3沉淀硫酸钛酰水溶液(STMC 02)
试剂
用于沉降的试剂如下：：
-Sol 1：TiOSO4(10g TiO2/100ml溶液)；345g TiOSO4(硫酸氧钛(IV)水合物Riedel-de
产品TiO2≥29％)溶解于蒸馏水，加水到1升。
-Sol 2：NaOH(14g/100ml)；140.0g NaOH(NaOH无水球RPE-Carlo Erba产品)溶解于蒸馏水，加水到1升。
-偏高岭土Metastar 501。
光催化合成
为获得60克光催化产品(以重量计含50％TiO2)，30克偏高岭土被悬浮于300ml碱性溶液Sol 2，然后剧烈搅拌。300ml Sol 1(二氧化钛前体)滴加60分钟。滴加末期测量pH在7左右，在这条件下水解完成。离心(或真空过滤)分离反应水。为消除可溶性盐，进行2次清洗，每次使用1.5升蒸馏水，温度为80℃左右。使用真空过滤或优选用大体积离心机离心分离洗涤液。
所得潮湿粉末在内通风炉105℃干燥，然后用旋转刀片均质器打散结块粉末。
硫酸盐定量分析显示所得粉末中SO3.含量少于1％。
最后在空气下在马弗炉中热处理，650℃，2.5小时，然后将材料置于干燥器中快速冷却到室温。
2.制备光催化水泥粘结剂
一系列制备是为获得光催化产品，其中TiO2/偏高岭土重量比为20/80、30/70和50/50。
对于TCMC产品(含50％二氧化钛)进行一些研究，将所得粉末以100℃干燥后，在250、350、450、550和650℃进行热处理。实验室制备的光催化水泥粘结剂是通过将52，5型白水泥(申请人位于Rezzato(Italbianco)的水泥工厂生产)与所制备的光催化粉末混合而得。在650℃热处理所得产品被用于制备含有0.1，0.3，0.5，1.0，1.5，2.0，2.5，3.3和4.0％TiO2(以在水泥中重量计)的粘结剂，而在100、250、350、450和550℃热处理的产品被用于制备含有3.3％TiO2的水泥。
对照催化剂分别由TiCl4水溶液中氧化铝和高岭土载体上制备。
3.基于TiO
2
在水泥中百分比的(污染物)减少
预先制备的光催化水泥被用于制备灰浆(CEN，UNI EN 196-1)样本，制成环形模(直径80mm，高10mm)，混合450g水泥和基于偏高岭土的TiO2(50/50％(重量比)，650℃热处理)，1350g惰性砂，225g水。控温控湿(T＝20℃，RH.＞95％)保持28天后样本进行光催化水泥评估测试，测试NO减少水平(UNI标准11247：2007)。依TiO2在水泥中百分比的结果显示在表1中。
表1
上表显示通过增加TiO2在水泥中的百分比，在相同载体上，60分钟时NO减少率在TiO2含量在大约2.5％时已经超过90％。因此即使低含量催化剂也可得到高NO减少水平。
4.基于复合材料热处理的(污染物)减少
在第二个测试中，NO减少百分比是对含有不同样本TiO2催化剂(偏高岭土载体，重量比50/50％)的灰浆进行测量的，其中复合材料在不同温度下被热处理，温度范围为100-650℃。所得结果显示在表2。所有样本的光催化活性结果都是相当可观的，超过350℃热处理对样本具有极佳效果。
表2
选择400℃处理TiO2(50％)/偏高岭土复合材料，制备一套灰浆样本分别含有0.5，1.0，2.0，3.0和4.0％TiO2。NO减少测试结果显示在表3并确认所述复合材料的高光催化活性。
表3
5.基于载体类型的(污染物)减少
在最后一项测试中，NO减少百分比是对由含3.3％TiO2的样本制成的灰浆进行测量的，其中TiO2施用在不同的载体上：偏高岭土、高岭土和氧化铝。同时对含有等量但无载体的TiO2的灰浆进行平行测试，其中TiO2分别是具有高光催化活性的商用锐钛矿型TiO2(PC105)，以及依前表所述催化剂方法制备的无载体TiO2。结果见表4，其证实只有本发明的基于偏高岭土载体的产品可以为水泥和TiO2物理混合物提供更高的光催化效果。含有基于高岭土载体(TCKA01)或氧化铝载体(TCAL01)的TiO2的对照样本显示出较低光催化活性。这显示TiO2与载体之间的绑定本身对于光催化活性本身无促进，只有那些基于偏高岭土载体的复合材料与无载体产品相比具有明显地提高。
表4
6.光催化分析
由电子显微镜对表4所用不同复合材料进行SEM图像分析。图1-3所示图像显示被测复合材料物理结构明显不同：对于氧化铝载体，TiO2结晶成薄片空隙(微孔)；对于偏高岭土载体，TiO2包裹载体颗粒外部；高岭土样本存在中间结构。图4和5显示基于本发明的TiO2/偏高岭土(50/50)复合材料进一步的TEM显微镜照片。这些照片证实TiO2是如何以结块颗粒存在于微量计簇中，没有观察到松散TiO2粉末。理论上没希望可被绑定，可认为图1-5所示TiO2黏附到载体上的形态显示在偏高岭土上对于光催化活性的改进。
Claims (27)
1.一种光催化复合材料用于制备具有光催化活性的水硬性粘结剂、干燥预混产品、水泥质组合物或水泥质产品的用途，其中所述复合材料包括通过热处理绑定到偏高岭土载体的二氧化钛。
2.如权利要求1所述的用途，其特征在于所述复合材料包括以重量计50％的二氧化钛和50％的偏高岭土。
3.如权利要求1所述的用途，其特征在于所述复合材料包括以重量计20％的二氧化钛和80％的偏高岭土。
4.如权利要求1所述的用途，其特征在于所述复合材料包括以重量计30％的二氧化钛和70％的偏高岭土。
5.如权利要求1-4中任一项所述的用途，其特征在于所述二氧化钛晶型为锐钛矿型。
6.如权利要求5所述的用途，其中所述二氧化钛的BET比表面积为5-350m2/g。
7.如权利要求1所述的用途，其中所述水泥质组合物是糊浆。
8.如权利要求1所述的用途，其中所述水泥质组合物是灰浆。
9.如权利要求1所述的用途，其中所述水泥质组合物是水泥。
10.如权利要求1所述的用途，其中进行所述热处理的温度为300℃-700℃。
11.如权利要求10所述的用途，其中进行所述热处理的温度为350℃-650℃。
12.如权利要求1或10所述的用途，其中进行所述热处理的时间为1-5小时。
13.一种光催化粘结剂，其包括混合有水硬性粘结剂的基于前述权利要求中一个或多个的复合材料。
14.如权利要求13所述的粘结剂，其特征在于以重量计其包括0.1-10％的二氧化钛。
15.如权利要求14所述的粘结剂，其特征在于以重量计其包括0.1-4％的二氧化钛。
16.如权利要求15所述的粘结剂，其特征在于以重量计其包括3.3％的二氧化钛。
17.如权利要求13-16中任一项所述的粘结剂，其特征在于所述水硬性粘结剂是水泥或石灰。
18.一种干燥预混产品，其特征在于其包括基于权利要求13-17中一个或多个所述的粘结剂、骨料和水泥添加剂。
19.一种水泥质组合物，包括基于权利要求1所述的光催化复合材料。
20.如权利要求19所述的组合物，其特征在于其为糊浆、灰浆或水泥。
21.一种制备基于权利要求1所述的复合材料的方法，包括以下步骤：使偏高岭土载体和二氧化钛或其前体之一相互接触，通过热处理将它们绑定。
22.如权利要求21所述的方法，其特征在于由所述接触而得的产品在300℃-700℃的温度下热处理1-5小时。
23.一种由基于权利要求19所述的水泥质组合物所制得的光催化水泥产品。
24.如权利要求23所述产品，选自建筑元件、铺地材料、路面产品、隧道或车库拱顶、砌块、喷水池、座椅和纪念碑元件。
25.如权利要求24所述产品，其中所述建筑元件为砖。
26.一种用于降低环境中存在的污染物的方法，其特征在于在光和空气存在下，由基于权利要求23-25所述的一个或多个产品与环境接触。
27.如权利要求26所述的方法，其中所述污染物选自芳香族缩聚物、醛、可吸入颗粒烟尘、氮氧化合物(NOx)和硫氧化合物(SOx)。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT002387A ITMI20072387A1 (it) | 2007-12-19 | 2007-12-19 | Compositi fotocatalitici e prodotti derivati a base di biossido di titanio supportato su metacaolino |
| ITMI2007A002387 | 2007-12-19 | ||
| PCT/EP2008/067728 WO2009080647A1 (en) | 2007-12-19 | 2008-12-17 | Titanium dioxide based photocatalytic composites and derived products on a metakaolin support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101903473A CN101903473A (zh) | 2010-12-01 |
| CN101903473B true CN101903473B (zh) | 2013-11-13 |
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| CN2008801215111A Expired - Fee Related CN101903473B (zh) | 2007-12-19 | 2008-12-17 | 二氧化钛基光催化复合材料及在偏高岭土载体上的衍生品 |
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| Country | Link |
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| US (1) | US8092586B2 (zh) |
| EP (1) | EP2242806B1 (zh) |
| CN (1) | CN101903473B (zh) |
| AT (1) | ATE520746T1 (zh) |
| CA (1) | CA2709352A1 (zh) |
| CY (1) | CY1112358T1 (zh) |
| DK (1) | DK2242806T3 (zh) |
| EG (1) | EG25732A (zh) |
| ES (1) | ES2371522T3 (zh) |
| HR (1) | HRP20110827T1 (zh) |
| IT (1) | ITMI20072387A1 (zh) |
| MA (1) | MA32015B1 (zh) |
| PL (1) | PL2242806T3 (zh) |
| PT (1) | PT2242806E (zh) |
| SI (1) | SI2242806T1 (zh) |
| WO (1) | WO2009080647A1 (zh) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| ITMI20072387A1 (it) * | 2007-12-19 | 2009-06-20 | Italcementi Spa | Compositi fotocatalitici e prodotti derivati a base di biossido di titanio supportato su metacaolino |
| CZ2008261A3 (cs) * | 2008-04-25 | 2009-11-04 | Rokospol A.S. | Komponenta náterové a/nebo stavební hmoty aktivní z hlediska katalýzy fotodegradace polutantu v ovzduší a náterová a/nebo stavební hmota na její bázi |
| IT1391093B1 (it) * | 2008-08-01 | 2011-11-18 | Italcementi Spa | Compositi fotocatalitici a base di titanio e calcare esenti da biossido di titanio. |
| IT1391427B1 (it) * | 2008-08-01 | 2011-12-23 | Italcementi Spa | Compositi fotocatalitici a base di titanio e calcare. |
| ES2331169B1 (es) * | 2008-12-10 | 2010-09-17 | Pavimentos De Tudela, S.L | Losa para pavimentos y procedimiento de obtenicion de la misma. |
| US8236101B1 (en) | 2011-04-21 | 2012-08-07 | Juarez Leroy | Swimming pool plaster enhancement |
| WO2013018111A1 (en) | 2011-08-02 | 2013-02-07 | C.I.M. CALCI IDRATE MARCELLINA SpA | Self-cleaning, anti-smog, anti-mould photocatalytic powdered water based paint |
| EP2597073A1 (de) | 2011-11-22 | 2013-05-29 | Steag Power Minerals GmbH | Titandioxid und Flugasche enthaltende Baustoffmischung sowie ein Verfahren zu deren Herstellung und deren Verwendung |
| US9598314B2 (en) * | 2012-05-07 | 2017-03-21 | The Regents Of The University Of California | Corrosion inhibiting cementitious compositions |
| KR102124188B1 (ko) * | 2013-03-13 | 2020-06-26 | 삼성전자주식회사 | 이미지를 처리하는 전자장치 및 방법 |
| CA2845980C (en) * | 2013-03-13 | 2021-06-22 | D&D Emulsions, Inc. | Embedding photocatalytic titanium dioxide in asphalt surfaces to reduce pollutants via photocatalytic reactions |
| CN103447043B (zh) * | 2013-08-16 | 2015-02-25 | 西南科技大学 | 一种用作矿物掺合料的负载钛偏高岭土的制备方法 |
| EP3216771A1 (en) | 2016-03-08 | 2017-09-13 | Technion Research & Development Foundation Limited | Compositions with increased photocatalytic activity |
| EP3501643A1 (en) | 2017-12-15 | 2019-06-26 | ITALCEMENTI S.p.A. | Photocatalytic composite based on kassite and perovskite and cementitious products containing it |
| RU2683321C1 (ru) * | 2018-09-13 | 2019-03-28 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет" (СПбГУ) | Способ получения фотоактивного композита с бактерицидными свойствами |
| CA3228027A1 (en) * | 2021-08-06 | 2023-02-09 | Alan Dumitras | Hydrophobic admixture and processes for making same |
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| IT1286492B1 (it) * | 1996-08-07 | 1998-07-15 | Italcementi Spa | Legante idraulico con migliorate proprieta' di costanza di colore |
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2007
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- 2008-12-17 CA CA2709352A patent/CA2709352A1/en not_active Abandoned
- 2008-12-17 CN CN2008801215111A patent/CN101903473B/zh not_active Expired - Fee Related
- 2008-12-17 SI SI200830442T patent/SI2242806T1/sl unknown
- 2008-12-17 WO PCT/EP2008/067728 patent/WO2009080647A1/en active Application Filing
- 2008-12-17 ES ES08864827T patent/ES2371522T3/es active Active
- 2008-12-17 US US12/747,948 patent/US8092586B2/en not_active Expired - Fee Related
- 2008-12-17 EP EP08864827A patent/EP2242806B1/en active Active
- 2008-12-17 AT AT08864827T patent/ATE520746T1/de active
- 2008-12-17 PL PL08864827T patent/PL2242806T3/pl unknown
- 2008-12-17 DK DK08864827.4T patent/DK2242806T3/da active
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2010
- 2010-06-16 EG EG2010061027A patent/EG25732A/xx active
- 2010-07-14 MA MA33014A patent/MA32015B1/fr unknown
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| US5152835A (en) * | 1991-05-08 | 1992-10-06 | Engelhard Corporation | Composite titania-calcined kaolin opacifying pigments and method for making and using same |
| KR20010054342A (ko) * | 1999-12-06 | 2001-07-02 | 곽영훈 | 금속산화물 복합 피복 이산화티탄 광촉매의 제조 방법 |
| EP1405835A1 (fr) * | 2002-10-03 | 2004-04-07 | Ciments Francais | Mélange granulaire photocatalytique pour mortier et béton et son utilisation |
| CN1751004A (zh) * | 2003-02-18 | 2006-03-22 | 伊泰莱塞蒙蒂股份公司 | 减少城区污染物的光催化铺筑路面所用的水泥基铺地块料 |
Also Published As
| Publication number | Publication date |
|---|---|
| MA32015B1 (fr) | 2011-01-03 |
| HRP20110827T1 (hr) | 2011-12-31 |
| SI2242806T1 (sl) | 2012-01-31 |
| PT2242806E (pt) | 2011-12-13 |
| CN101903473A (zh) | 2010-12-01 |
| ES2371522T3 (es) | 2012-01-04 |
| WO2009080647A1 (en) | 2009-07-02 |
| US20100266470A1 (en) | 2010-10-21 |
| CY1112358T1 (el) | 2015-12-09 |
| ATE520746T1 (de) | 2011-09-15 |
| US8092586B2 (en) | 2012-01-10 |
| PL2242806T3 (pl) | 2012-01-31 |
| DK2242806T3 (da) | 2011-11-21 |
| CA2709352A1 (en) | 2009-07-02 |
| EP2242806A1 (en) | 2010-10-27 |
| EG25732A (en) | 2012-06-16 |
| EP2242806B1 (en) | 2011-08-17 |
| ITMI20072387A1 (it) | 2009-06-20 |
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