CN102489312B - 基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 - Google Patents
基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法 Download PDFInfo
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- CN102489312B CN102489312B CN2011103787941A CN201110378794A CN102489312B CN 102489312 B CN102489312 B CN 102489312B CN 2011103787941 A CN2011103787941 A CN 2011103787941A CN 201110378794 A CN201110378794 A CN 201110378794A CN 102489312 B CN102489312 B CN 102489312B
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Abstract
本发明提供一种基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法,本发明的催化剂是以有机凝胶为模板,通过溶胶凝胶法制备得到;以金属组分为核,多孔材料为壳;其中金属组分包括第一种金属组分Co,第二种金属组分为Ce、La、Zr中的一种,第三种金属组分Pt、Ru、Rh、Re中的一种;在成品催化剂中,各金属组分的重量百分比为:第一种金属组分:10~35%,第二种金属组分:0.5~10%;第三种组分:0.02~2%,余量为载体;载体为多孔材料,其组分是纳米二氧化硅或氧化铝,形状为球形;其孔径在1~20nm,比表面积为300~500m2/g,其中活性组分的粒径在0.5~20nm。本发明的核壳结构钴基多孔催化剂具有甲烷选择性低,催化反应活性高,C5+选择性好,以柴油和石蜡为主要产物。
Description
技术领域
本发明涉及催化合成、纳米材料应用领域,具体地指一种基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法。
背景技术
近年来,随着世界石油资源的萎缩和石油价格的上涨,寻求使用替代品的相关研究和技术进步方兴未艾。以煤、石油气和生物质气化获得合成气(CO+H2),然后通过费托合成将合成气转变成碳氢化合物受到广泛的关注。费托合成是指合成气(CO+H2)在催化剂上转化生成烃类的反应,其合成产物主要是具有较高碳数的重质烃(C5+),通过产物蜡的精制和裂解可以获得高品质的柴油和航空煤油,这些产物中几乎不含硫化物和氮化物,是非常洁净的马达燃料。它是1923年德国化学家Frans Fischer和HansTropsch发明的。费托合成技术是增加液体燃料供给最有效的途径之一,有望在不久的将来成为生产发动机燃料的主要渠道之一,具有重要的经济意义和商业价值。
活性金属粒子的类型、尺寸、分散度、可还原性对反应性能的影响,载体的孔道效应(限域效应、择形效应等)和助剂的促进作用等都与费托反应机理的问题相关,这些因素对反应机理中的具体步骤产生影响,并从而影响反应活性以及产物的类型和分布。众多的研究结果表明,催化材料的构筑,包括活性组分的分散程度、活性中心结构、微环境、落位、载体的孔道结构等,极大地影响其在合成气转化反应中的活性和选择性。孙予罕等制备了具有核壳结构的易于还原,活性相稳定的催化剂Co3O4MCM-41。他们首先利用热分解法制备了Co3O4粒子,采用PVP作为两亲试剂,设计制备了介孔硅包裹Co3O4粒子核壳结构的钴基催化剂,该催化剂可抑制钴活性中心的相互团聚。但其制备工艺复杂,催化材料的金属组分单一,CO转化率较低,产物主要是轻质烃,甲烷选择性高。(孙予罕,化工进展,2010,380)
专利CN 101698152A提供一种钴基费托合成催化剂及其制备方法和应用,该催化剂包括载体和金属组分,载体采用球形粉体氧化铝;金属组分包括第一种金属组分Co,第二种金属组分为Ce、La、Zr中的一种,第三种金属组分Pt、Ru、Rh、Re中的一种,该催化剂适应于鼓泡浆态床或连续搅拌浆态床反应器。但这种材料价格昂贵,活性中心易团聚,失活。
微囊反应器是近年来在纳米组装和催化领域中提出的一个新概念,它解决了传统纳米催化剂存在的难回收、稳定性差、选择性差等问题。对于该反应器而言,在反应过程中不仅客体分子可以选择性的进入囊内空腔,并与囊内活性物种发生催化反应,而且其产物也将选择性地扩散离开微反应器。
发明内容
本发明的目的就是借鉴了微囊反应器制备催化剂的优点,结合多孔材料限域的纳米催化剂的优点提供一种基于多孔材料限域的费托合成钴基纳米催化剂及其制备方法。使催化剂的制备方法简单,成本低,甲烷选择性低,催化反应活性高,C5+选择性好,以柴油和石蜡为主要产物。
本发明的技术方案:本发明的基于多孔材料限域的费托合成钴基纳米催化剂是以一种有机凝胶为模板,通过溶胶凝胶法制备得到;以金属组分为核,多孔材料为壳;其中金属组分包括第一种金属组分Co,第二种金属组分为Ce、La、Zr中的一种,第三种金属组分Pt、Ru、Rh、Re中的一种;在成品催化剂中,各金属组分的重量百分比为:第一种金属组分:10~35%,第二种金属组分:0.5~10%;第三种组分:0.02~2%,余量为载体;载体为多孔材料,其组分是纳米二氧化硅或氧化铝,其形状为球形;其孔径在1~20nm,比表面积为300~500m2/g,其中活性组分的粒径在0.5~20nm。
优选金属组分重量百分比为:第一种金属组分:15~30%,第二种金属组分1%~5%;第三种金属组分:0.05%~2%,余量为载体。
为了获得主要产物为轻质烃,所述的载体多孔材料优选孔径在1~10nm,比表面积为300~400m2/g,其中活性组分的粒径在0.5~5nm。
为了获得主要产物为中间馏分(C5-C18),所述的载体多孔材料优选孔径在10~15nm,比表面积为400~500m2/g,其中活性组分的粒径在6nm~15nm。
为了使产物中C18+产物含量较高,所述的载体多孔材料优选孔径在10~20nm,比表面积为400~500m2/g,其中活性组分的粒径在16~20nm。
所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其制备方法采用有机凝胶模板法,包括如下步骤:
1)原料选取:按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的水溶性盐类、第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐及凝胶模板剂备用;
2)将模板剂溶解在极性溶剂中,然后在恒温下向上述溶液中加入含有各种金属盐的水溶液,加入适量氨水调节pH值到8~10,恒温搅拌0.1~3小时;
3)向上述溶液中加入计算量的正硅酸乙酯或硝酸铝,并继续恒温搅拌3-24小时;
4)对上述反应物在90~150℃下进行喷雾干燥,得到有机-无机杂化材料;
5)将喷雾干燥后的粉末放入马弗炉中,在300~750℃焙烧3h-12h,制得成品催化剂。
优选地,步骤4)利用溶胶凝胶模板法制备得到的凝胶在110~150℃喷雾干燥得到有机-无机杂化材料。
优选地,步骤5)将喷雾干燥后的粉末放入马弗炉中,在350~700℃焙烧5h~10h,制得成品催化剂。
优选地,所用的凝胶模板剂是含有胺基的两亲性线形高分子。
优选地,配置溶液时,所用的第一种活性金属组分钴的盐为硝酸钴、乙酸钴或碳酸钴;第二种金属组分的盐为金属的硝酸盐;第三种金属组分的盐为金属的硝酸盐。
本发明所涉及的催化剂具有以下优点:
1.本发明涉及的费托合成催化剂起主要催化作用的活性金属是Co,理论上来说,在分散度相同的情况下,Co的含量越高,催化剂的活性就越高,但实际上载体的比表面积,孔径和孔道等性质限制了Co的最大负载量;同时如果Co的负载量过大,则很容易聚集成团,反而会降低催化剂活性。所以,本领域技术人员一直在尝试添加助剂以改善Co在催化剂载体上的分散,从而尽可能的发挥Co的催化作用。本发明中,通过选择合适的有机凝胶模板剂、反应时间及反应物的量,可以得到形状、粒径和孔径可控的多孔纳米催化剂,由于活性组分在多孔材料中均匀分散,抑制了活性组分的相互团聚,有助于提高催化剂的催化活性、反应产物的选择性。同时,通过添加助剂可进一步改善催化剂的反应活性和选择性。利用这种方法可以降低金属活性组分的含量,降低催化剂的成本。该催化剂适用于鼓泡浆态床或连续搅拌浆态床反应器。
2.费托合成产物分布过宽,合成的产物从甲烷一直到分子量很大的石蜡,选择性差是该反应的一个缺点。催化材料中钴颗粒的大小不仅明显改变费托反应的活性而且改变产物选择性。本发明通过选用特定孔径和比表面积的多孔材料为载体,可调节费托合成的产物分布,生成的产物中柴油和石蜡组分的选择性高。我们通过研究发现,核壳结构纳米催化剂的核具有催化活性,壳对核层有稳定作用,而且由于壳层结构的存在,其封闭的内腔将形成一个微环境,在催化反应过程中,内腔往往通过对反应物的积累而形成局部的高浓度,促进反应更高效地进行,提高催化剂的整体活性,也可明显改善产物的选择性,以及提高催化剂抗积碳、抗烧结、水热稳定性等性能,当催化剂活性组分粒径在0.5~20nm,比表面积在300~500m2/g时,更有利于生成柴油和石蜡组分。
3.本发明涉及的多孔材料限域的钴基纳米催化剂是通过溶胶凝胶法原位生成,因而催化剂活性组分和作为载体的多孔材料可同步合成,制备流程简单,便于操作,更适合工业化生产。
本发明借鉴了微囊反应器制备催化剂的优点,结合多孔材料限域的纳米催化剂的优点发明了新的催化剂,本发明的催化剂以有机凝胶为模板,活性组分在模板表面生长,设计制备的核壳结构钴基多孔催化剂具有高反应活性,甲烷选择性较低,以柴油和石蜡为主要产物。与专利CN101698152A相比该催化剂中各活性组分更易于在多孔载体中均匀分散,从而导致材料的活性更高,CO转化率高,甲烷选择性更低。同时,本发明中加入较少的贵金属助剂便可实现高的催化性能,因而成本更低。
附图说明
图1为本发明中基于多孔材料限域的费托合成钴基纳米催化剂制备方法的工艺流程图。
具体实施方式
本发明的基于多孔材料限域的费托合成钴基纳米催化剂是以一种有机凝胶为模板,通过溶胶凝胶法制备得到;以金属组分为核,多孔材料为壳;其中金属组分包括第一种金属组分Co,第二种金属组分为Ce、La、Zr中的一种,第三种金属组分Pt、Ru、Rh、Re中的一种;在成品催化剂中,各金属组分的重量百分比为:第一种金属组分:10~35%,第二种金属组分:0.5~10%;第三种组分:0.02~2%,余量为载体;载体为多孔材料,其组分是纳米二氧化硅或氧化铝,其形状为球形;其孔径在1~20nm,比表面积为300~500m2/g,其中活性组分的粒径在0.5~20nm。
优选地,金属组分重量百分比为:第一种金属组分:15~30%,第二种金属组分1%~5%;第三种金属组分:0.05%~2%,余量为载体。
优选地,为了获得主要产物为轻质烃,所述的催化剂载体为多孔材料,其孔径在1~10nm,比表面积为300~400m2/g,其中活性组分的粒径在0.5~5nm。
优选地,为了获得主要产物为中间馏分(C5-C18),所述的催化剂载体为多孔材料,其孔径在10~15nm,比表面积为400~500m2/g,其中活性组分的粒径在6nm~15nm。
优选地,为了使产物中C18+产物含量较高,所述的催化剂载体为多孔材料,其孔径在10~20nm,比表面积为400~500m2/g,其中活性组分的粒径在16~20nm。
所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其制备方法采用有机凝胶模板法,包括如下步骤:
1)原料选取:按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的盐类、第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐或及凝胶模板剂备用;
2)将模板剂溶解在极性溶剂中,然后在恒温下向上述溶液中加入含有各种金属盐的水溶液,加入适量氨水调节pH值到8~10,恒温搅拌0.1~3小时;
3)向上述溶液中加入计算量的正硅酸乙酯或硝酸铝,并继续恒温搅拌3-24小时;
4)对上述反应物在90~150℃下进行喷雾干燥,得到有机-无机杂化材料;
5)将喷雾干燥后的粉末放入马弗炉中,在300~750℃焙烧3h-12h,制得成品催化剂。
优选地,步骤4)利用溶胶凝胶模板法制备得到的凝胶在110~150℃喷雾干燥得到有机-无机杂化材料。
优选地,步骤5)将喷雾干燥后的粉末放入马弗炉中,在350~700℃焙烧5h~10h,制得成品催化剂。
优选地,所用的凝胶模板剂是含有胺基的两亲性线形高分子。
优选地,配置溶液时,所用的第一种活性金属组分钴的盐为硝酸钴、乙酸钴或碳酸钴;第二种金属组分的盐为金属的硝酸盐;第三种金属组分的盐为金属的硝酸盐。
为了更好地解释本发明,以下结合图1和具体实施例进一步阐明本发明的主要内容,但本发明的内容不仅仅局限于以下实施例。
实施例1:
称取20g的聚乙烯亚胺,在80℃温度下将其溶解在100mL乙醇中。称取93.8g六水合硝酸钴,39.1g六水合硝酸镧,2.32g硝酸铂,溶解在100mL去离于水中,搅拌使之充分溶解并与溶剂1混合均匀,加入5mL氨水,恒温温搅拌2h后将计算量的正硅酸乙酯加入反应液中,最后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢升温至400℃干燥6h,获得多孔材料限域的用于费托合成的钴基纳米催化剂。制得的纳米催化剂组成为:Co∶La∶Pt∶SiO2=15∶10∶0.5∶74.5。
纳米催化剂活化在加压固定床反应器上进行:取制备好的纳米催化剂100g,装入反应器中,纯H2(纯度>99.9%)为还原气体,体积空速为1000h-1,升温速率为2℃/min,活化温度为350℃,活化压力为0.5MPa,活化时间为4h。
催化反应在浆态床反应器上进行:取活化好的催化剂50g在无水无氧的条件下转移入浆态床反应器中,以聚烯烃为反应介质,通入合成气,合成气中H2∶CO=1.5,调节流量使空速为1000h-1,调节反应器内压力为3.0MPa。设定升温程序,使反应温度以3℃/min的速率从室温升至150℃,然后以2℃/min的速率升温至220℃,在220℃进行反应。得到产物选择性(wt%)结果如下:C1,6.1;C2-4,7.3;C5-11,32.2;C12-18,29.5;C18+,24.9.CO转化率达到81.5。
实施例2:
称取20g的聚乙烯亚胺,在80℃温度下将其溶解在100mL乙醇中。称取53.6g六水合硝酸钴,1.7g六水合硝酸铈,5.9g亚硝酰基硝酸钌,溶解在100mL去离于水中,搅拌使之充分溶解并与溶剂1混合均匀。恒温搅拌2h后将计算量的硝酸铝加入反应液中,最后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢升温至550℃干燥3h,获得多孔材料限域的用于费托合成的钴基催化剂。制得的催化剂组成为:Co∶Ce∶Ru∶Al2O3=10∶0.5∶1.5∶88。
催化剂活化在加压流化床反应器上进行:取制备好的催化剂100g,装入反应器中,纯H2(纯度>99.9%)为还原气体,体积空速为1000h-1,升温速率为2℃/min,活化温度为350℃,活化压力为1.5MPa,活化时间为4h。
催化反应在浆态床反应器上进行:取活化好的催化剂50g在无水无氧的条件下转移入浆态床反应器中,以聚烯烃为反应介质,通入合成气,合成气中H2∶CO=1.5,调节流量使空速为1000h-1,调节反应器内压力为3.0MPa。设定升温程序,使反应温度以3℃/min的速率从室温升至150℃,然后以2℃/min的速率升温至220℃,在220℃进行反应。得到产物选择性(wt%)结果如下:C1,6.8;C2-4,7.9;C5-11,27.2;C12-18,28.6;C18+,29.5.CO转化率达到85.3。
实施例3:
称取20g的聚乙烯亚胺,在80℃温度下将其溶解在100mL乙醇中。称取53.6g六水合硝酸钴,1.7g六水合硝酸铈,5.9g亚硝酰基硝酸钌,溶解在100mL去离于水中,搅拌使之充分溶解并与溶剂1混合均匀。恒温搅拌2h后将计算量的正硅酸乙酯加入反应液中,最后将室温搅拌过夜后用喷雾干燥的方法得到的粉末放置在马弗炉中缓慢升温至450℃干燥3h,获得多孔材料限域的用于费托合成的钴基催化剂。制得的催化剂组成为:Co∶Ce∶Ru∶SiO2=10∶0.5∶1.5∶88。
催化剂活化在加压流化床反应器上进行:取制备好的催化剂100g,装入反应器中,纯H2(纯度>99.9%)为还原气体,体积空速为1000h-1,升温速率为2℃/min,活化温度为350℃,活化压力为1.5MPa,活化时间为4h。
催化反应在浆态床反应器上进行:取活化好的催化剂50g在无水无氧的条件下转移入浆态床反应器中,以聚烯烃为反应介质,通入合成气,合成气中H2∶CO=1.5,调节流量使空速为1000h-1,调节反应器内压力为3.0MPa。设定升温程序,使反应温度以3℃/min的速率从室温升至150℃,然后以2℃/min的速率升温至220℃,在220℃进行反应。得到产物选择性(wt%)结果如下:C1,5.6;C2-4,7.1;C5-11,23.9;C12-18,29.8;C18+,33.6.CO转化率达到76.3。
实施例4:
作为对比,根据专利CN 101698152A的方法制备了钴基费托合成催化剂
称取适量的Al2O3载体,预先在马弗炉中于550℃焙烧4h后取其中100g备用。称取53.6g六水合硝酸钴,1.7g六水合硝酸铈,5.9g亚硝基酰基硝酸钌,溶解在去离子水中,搅拌使之充分溶解并混合均匀,将溶液体积稀释至110mL。采用满孔浸渍法,将溶液浸渍到计算量的Al2O3载体上。将浸渍好的催化剂在80℃下水浴抽真空干燥,然后放置在室温下老化24h。老化后放置在马弗炉中缓慢升温至120℃下干燥6h,然后升温至500℃焙烧8h。制得的催化剂组成为:Co∶Ce∶Ru∶Al2O3=10∶0.5∶1.5∶88。
催化剂活化在加压流化床反应器上进行:取制备好的催化剂100g,装入反应器中,纯H2(纯度>99.9%)为还原气体,体积空速为1000h-1,升温速率为2℃/min,活化温度为350℃,活化压力为1.5MPa,活化时间为4h。
催化反应在浆态床反应器上进行:取活化好的催化剂50g在无水无氧的条件下转移入浆态床反应器中,以聚烯烃为反应介质,通入合成气,合成气中H2∶CO=1.5,调节流量使空速为1000h-1,调节反应器内压力为3.0MPa。设定升温程序,使反应温度以3℃/min的速率从室温升至150℃,然后以2℃/min的速率升温至220℃,在220℃进行反应。得到产物选择性(wt%)结果如下:C1,9.3;C2-4,9.1;C5-11,27.8;C12-18,21.2;C18+,32.6.CO转化率达到71.3。
从以上实施例1~3可以看出:本发明的催化剂活性较高,在合成气空速为1000h-1的条件下,即使Co含量只有10%,CO转化率仍能达到80%以上,说明本方法制备的钴基费托合成催化剂各金属组分的作用明显。在所有实施例中,甲烷选择性较低,C5+以上选择性好。实施例2与实施例4相比,本方法制备得到的催化剂成本较低,甲烷选择性较低,C5+以上选择性更好,特别是C12+以上选择性优势更大。
实施例5-12:
根据本发明的具体实施方法,制备了系列多孔材料限域的费托合成钴基纳米催化剂,其催化性能如表1所示:
表1:钴基纳米催化剂在费托合成中的催化性能
Claims (9)
1.一种基于多孔材料限域的费托合成钴基纳米催化剂,其特征在于:它以聚乙烯亚胺为有机凝胶模板,通过溶胶凝胶法制备得到;以金属组分为核,多孔材料为壳;其中金属组分包括第一种金属组分Co, 第二种金属组分为Ce、La、Zr中的一种,第三种金属组分Pt、Ru、Rh中的一种;在成品催化剂中,各金属组分的重量百分比为:第一种金属组分:10~35%,第二种金属组分:0.5~10%;第三种金属组分:0.02~2%,余量为载体;载体为多孔材料,其组分是纳米二氧化硅或氧化铝,其形状为球形;载体孔径在1~20nm,载体比表面积为300~500m2/g,其中活性组分的粒径在0.5~20nm。
2.根据权利要求1所述的基于多孔材料限域的费托合成钴基纳米催化剂,其特征在于:金属组分重量百分比为:第一种金属组分:15~30%,第二种金属组分1%~5%;第三种金属组分:0.05%~2%,余量为载体。
3.根据权利要求1或2所述的多孔材料限域的用于费托合成的钴基催化剂,其特征在于:所述的载体为多孔材料,其孔径在1~10nm,比表面积为300~400m2/g,其中活性组分的粒径在0.5~5nm。
4.根据权利要求1或2所述的基于多孔材料限域的费托合成钴基纳米催化剂,其特征在于:所述的载体为多孔材料,其孔径在10~15nm,比表面积为400~500m2/g,其中活性组分的粒径在6nm~15nm。
5.根据权利要求1或2所述的基于多孔材料限域的费托合成钴基纳米催化剂,其特征在于:所述的载体为多孔材料,其孔径在10~20nm,比表面积为400~500m2/g,其中活性组分的粒径在16~20nm。
6.权利要求1~5任意一项所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其制备方法采用有机凝胶模板法,包括如下步骤:
1)原料选取:按各组份重量百分比选取正硅酸乙酯或硝酸铝、第一种金属钴的水溶性盐类、第二种金属组分和第三种金属组分的硝酸盐或亚硝酰基硝酸盐及有机凝胶模板剂聚乙烯亚胺备用;
2)将模板剂溶解在极性溶剂中,然后在恒温下向上述溶液中加入含有各种金属盐的水溶液,加入适量氨水调节pH值到8~10,恒温搅拌0.1~3小时;
3)向上述溶液中加入计算量的正硅酸乙酯或硝酸铝,并继续恒温搅拌3-24小时;
4)对上述反应物在90~150oC下进行喷雾干燥,得到有机—无机杂化材料;
5)将喷雾干燥后的粉末放入马弗炉中,在300~750oC焙烧3h-12h,制得成品催化剂。
7.根据权利要求6所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其特征在于:
步骤4)利用溶胶凝胶模板法制备得到的凝胶在110~150oC喷雾干燥得到有机—无机杂化材料。
8.根据权利要求6或7所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其特征在于:
步骤5)将喷雾干燥后的粉末放入马弗炉中,在350~700oC焙烧5h~10h,制得成品催化剂。
9.根据权利要求6或7所述的基于多孔材料限域的费托合成钴基纳米催化剂的制备方法,其特征在于:配置溶液时,所用的第一种金属组分钴的盐为硝酸钴或乙酸钴;第二种金属组分的盐为金属的硝酸盐;第三种金属组分的盐为金属的硝酸盐。
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JP5947912B2 (ja) | 2016-07-06 |
AP2014007678A0 (en) | 2014-06-30 |
US9266097B2 (en) | 2016-02-23 |
MY166549A (en) | 2018-07-16 |
AU2012343061B2 (en) | 2016-04-28 |
KR101625987B1 (ko) | 2016-05-31 |
JP2014534068A (ja) | 2014-12-18 |
AU2012343061A1 (en) | 2014-06-12 |
EP2783750A4 (en) | 2015-08-05 |
BR112014012492B1 (pt) | 2020-01-21 |
CN102489312A (zh) | 2012-06-13 |
EP2783750A1 (en) | 2014-10-01 |
ZA201404572B (en) | 2015-09-30 |
WO2013075559A1 (zh) | 2013-05-30 |
KR20140097266A (ko) | 2014-08-06 |
MX2014006257A (es) | 2014-09-22 |
RU2624441C2 (ru) | 2017-07-04 |
MX366574B (es) | 2019-07-12 |
SG11201402557PA (en) | 2014-09-26 |
BR112014012492A2 (pt) | 2017-06-06 |
CA2856748A1 (en) | 2013-05-30 |
RU2014124012A (ru) | 2015-12-27 |
US20140256535A1 (en) | 2014-09-11 |
IN2014MN00970A (zh) | 2015-04-24 |
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