CN102282112A - 催化方法的改进 - Google Patents
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Abstract
本发明涉及催化方法的改进。本发明公开了一种催化剂，包含承载于碳载体上的金纳米颗粒，所述催化剂基本上是无毒的，并对乙炔和氯化氢的反应具有活性以形成氯乙烯单体。
Description
技术领域
本发明涉及一种催化方法的改进和该方法所用催化剂的改进。更具体地，其涉及一种由乙炔制备氯乙烯单体（“VCM”）的方法和催化剂。
背景技术
目前现有技术中制备VCM的方法之一是在氯化铜的存在下将乙烯、氯化氢和氧气结合以形成二氯乙烯，该二氯乙烯在高温下被分解以形成VCM和HCl。从二十世纪早期开始的原始方法中，采用由碳化钙制得的乙炔（acetylene）通过汞基催化剂与HCl反应。这种原始方法仍在中国使用，在中国可通过经由丰富的煤炭资源得到的碳化钙获得廉价的乙炔。尽管这种原始方法资金和运行成本低，但是在中国以外已经被大量淘汰，转而倾向于所述乙烯法。
原始方法中使用的汞催化剂通常是载在活性炭上的8-10%的氯化汞，这种催化剂是高毒性的。该毒性在所述催化剂的生产期间以及催化剂装填和运行周期后除去催化剂期间因处理而产生问题。运行周期通常会持续为6个月的时间。在使用中汞催化剂的钝化和反应器中由于升华或挥发造成的HgCl2损耗可能是重要的问题。与乙烯法相比，使用汞基催化剂的乙炔法需要更低的设备投资；如果一种不易挥发且毒性小的催化剂可以替代汞催化剂，且不需要对现有设备设计进行重大的设备改变，这将具有明显的优势。
已经存在推荐用于乙炔-HCl反应的一种金基催化剂的大量学术研究和出版物，所述金基催化剂是对该反应最有活性的催化剂。尽管据说在碳上较高的金负载(>1wt％)会减弱钝化，但是金催化剂仍然会发生钝化。对金催化剂钝化的其它观察发现，高温和低温下都会发生钝化，并且低温钝化看起来是由结焦导致的，其可能是氯乙烯与乙炔表面反应的结果。
日本专利JP522136104，Denki Kagaku Kogyo KK,1977教导了采用负载在碳载体上的与铂卤化物或钯卤化物组合的金卤化物作为用于VCM生产中的催化剂。其中没有描述该催化剂的制备，所述方法或催化剂的商业应用也没有实现。
我们将现有技术理解为现有技术表明金属金（Au0）作为催化剂是不活泼的。
特别是在中国，仍然需要一种可用于新的或现有设备中由乙炔制备VCM的催化方法，所述的催化方法使用一种可以抗钝化，或与汞催化剂相比至少不会具有更差的寿命，并且拥有期望地更长有效使用寿命的催化剂，以及所述催化剂几乎没有或没有毒性。
发明内容
因此，本发明提供一种乙炔和HCl反应的方法，所述方法包括使反应物通过负载在碳载体上的催化剂，所述催化剂包含金属金颗粒，适宜地为金纳米颗粒。
本发明也提供一种应用于本发明方法的金基催化剂，该催化剂包含碳载体和金属金颗粒，适宜地为金纳米颗粒。“纳米颗粒”指的是直径为1－1000纳米的金属颗粒。
本发明的催化剂可以认为是包含具有含金属金的核和含包括Au3+的较高氧化态金物质的壳或表面层的金颗粒。所述的壳不必是完整的，但优选所述颗粒所有或几乎所有裸露的表面都具有较高氧化态金物质表面；例如如果金属金的部分表面被碳环绕，则所述的“壳”可以仅在裸露颗粒表面上扩展。存在于所述壳中的较高氧化态金物质不必仅为Au3+，例如还可以有Au1+。这种较高氧化态物质可通过卤化物稳定。核中含金属金（Au0），但其它金物质也可存在于核中。
不希望限制于任何理论，认为核中的金属金和壳中的Au3+和/或其它正氧化态物质有可能起到氧化还原对的作用，或者金属金在期望的反应中起到电子阱(electron sink)的作用。
当催化剂是新鲜的时候，金颗粒理想地分布在碳载体的表面上。使用一段时间后，金颗粒可以特别地负载在碳细纤维（fibrils）上。所述碳细纤维可以是碳纳米管。
本发明的催化剂以前从未被观察到或被描述。与以前金催化剂结焦导致钝化的观察所不同的是，我们相信在本发明中碳细纤维以使其保持活性并暴露于反应物的方式承载催化金颗粒，而不是活性金催化剂颗粒被埋没在焦炭型物质之下。
本发明的催化剂可以由高表面积的活性炭制备，所述活性炭优选表面积大于800m2/g，例如表面积为1300m2/g的碳挤出料。另外可以使用其它碳载体，包括粉末状或颗粒状或其它形式的碳。这些材料可商购获得。如果所述碳中含有作为潜在催化剂毒物的杂质，例如S、As和Fe，可采用洗涤方式，例如优选采用盐酸进行酸洗。已经发现，如果必要的话，将碳分散在浓度为3%的盐酸中，使之沸腾、排干，并用蒸馏水或去离子水洗涤是有效的。“高纯度”或“超高纯度”级别的碳挤出料是可商购的，并且这种级别通常被酸洗除去杂质。
催化剂可以采用本领域熟知的多种催化剂制备方法制备，例如浸渍，优选使用初湿含浸法(incipient wetness)、沉积法、沉淀法及其组合。可以将所述金由金前体如HAuCl4·xH2O或者水溶液施加至碳上，或者通过将金属金或其它前体溶解在硝酸和盐酸的混合物中，然后将该溶液添加到碳颗粒或挤出料中以将其施加至碳上，反之亦然，其中所述硝酸和盐酸的混合物通常称为“王水”。已观察到当使用王水溶液时，碳转变成金色，然后在几秒内就转变成暗褐色/黑色，并且观察到NOx烟雾生成。目前优选使用王水溶液。虽然我们不希望限制于任何理论，认为金最初作为金盐沉积，并且通过活性炭将该盐还原为金属金，但当暴露于王水溶液时，其或者保持原状或者形成包含包括Au3+的较高氧化态物质的壳。该被浸渍的载体可以在浸渍后洗涤以除去多余的王水溶液，从而降低在干燥中产生的NOx烟雾的量。已经发现用这种方法可能降低催化剂活性，因此目前并不优选在浸渍后包括该洗涤步骤。
金颗粒优选含基本上100%的金，但预期合金和/或复合物也可是所关注反应的活性催化剂。可能的合金和/或复合物可包括铜和/或银，它们也可以表现为有效的较高氧化态表面物质。
现在本发明将参考以下实施例以及附图进行描述。
附图说明
图1是本发明催化剂的EPMA图像。
图2是使用本发明催化剂和现有技术汞催化剂的乙炔转化率的曲线。
图3是使用本发明催化剂1a和1b的乙炔转化率的曲线。
图4是显示经过25天反应后样品上形成的大量纳米管的SEM显微照片。
图5是显示在纳米管末端和一个纳米管的开口端的金颗粒的SEM显微照片。
图6是催化剂样品的SEM显微照片。。
图7是使用对比催化剂1c和1d的乙炔转化率曲线。
图8是本发明催化剂的XPS图。
具体实施方式
实施例1a-1d——催化剂的制备
实施例1a 1%Au/C 挤出料：在150克规模下制备：
通过混合25毫升HNO3（69%）和50毫升HCl（37%）制备王水溶液。将其加入到83ml含有1.50gAu的HAuCl4水溶液中。按原状态使用碳挤出料，NoritTM ROX 0.8，其是通过蒸汽活化和酸洗制备的挤出0.8mm直径的活化碳，由Norit Nederland B.V.商购获得(150克)）。根据制造者的数据单，表面积(B.E.T.)是1225m2/g。采用初湿含浸法用该溶液浸渍该碳挤出料。静置后，水洗该材料两次，然后在105℃下干燥整夜。
实施例1b 1%Au/C 挤出料在150克规模下制备：
通过混合25毫升HNO3（69%）和50毫升HCl（37%）制备王水溶液。将其加入到83ml含有1.50gAu的HAuCl4水溶液。将碳挤出料（150克-同实施例1a）采用初湿含浸法用该溶液浸渍。静置后，将该材料在105℃下干燥整夜。
实施例1a的方法还用于制备载在直径3毫米的碳挤出料上的金催化剂。
附图中的图1显示了三种碳挤出料的EPMA图，该三种碳挤出料厚度约5.5毫米，具有采用本发明的方法沉积的金纳米颗粒（采用的机器为JEOL model JXA-8500F 场致发射电子探针显微分析仪）。金表现出明显沉积在一层厚度大约为100微米的表面薄层上。优选大多数金以最高200微米，更优选最高100微米厚的层形式沉积在碳载体上。
实施例1c （比较例） 1%Au/SiO
2
球形料在50克规模下制备：
通过混合25毫升HNO3（69%）、75毫升HCl（37%）和25毫升水制备王水贮液。将一等分试样（22毫升）加入到30ml含有0.50gAu的HAuCl4水溶液中。将二氧化硅球体（50克-280m2/g，直径1.1-2.4毫米）采用初湿含浸法用该溶液浸渍。静置后，干燥该材料，得到一种黄色产品。
实施例1d （比较例） 1%Au/SiO
2
球形料在50克规模下制备：
将含有0.50gAu的HAuCl4溶液用水稀释至50毫升，并用于采用初湿含浸法浸渍二氧化硅球体（50克-同实施例1c）。静置后，干燥该材料，得到一种黄色产品。
研究表明，在实施例1a和1b中，金为具有金属金核的纳米颗粒形式；但是在实施例1c和1d中，其作为二氧化硅球上的HAuCl4存在。即，在实施例1c和1d中， HAuCl4在所述载体上的简单吸附仅沉积作为Au3+的金，没有观察到金属金或金颗粒。
实施例2——VCM的制备
将5.05克如实施例1b制备的催化剂装填在直径2厘米的玻璃反应器中，床深度4厘米。将该玻璃反应器用填充有流动加热油的夹套包裹，以引发和维持反应。在预处理和反应阶段，将热电偶放置在所述床的中部和顶部以监视温度。从而下述温度是指催化剂床中部的温度。
首先，将催化剂在氮气气流（100毫升/分钟）中于100℃下干燥30分钟。此时，将氮气换成氯化氢气流（116毫升/分钟）并观察到持续数分钟的放热反应。放热减弱后，温度升至180℃，并继续氯化氢处理1小时。此时，用氮气吹洗反应器15分钟，温度降到90℃。然后使反应气体（氯化氢和乙炔）以1:1的标称摩尔比通过催化剂床。进入反应器之前，使气体经过气体混合器和预加热单元，其由一个装有玻璃珠的加热柱组成。为了避免放热过量（>180℃），谨慎提高气流和油浴温度，直到氯化氢和乙炔均达到114毫升/分钟的最高流速。典型地其需要45分钟，然后通过提高外部油温将所述床中部的温度维持在要求的温度（典型地为180℃）。
结果（图2）显示初期活性和钝化速率与在类似的条件下试验的市售氯化汞催化剂（10%HgCl2）（第一阶段钝化的催化剂）接近。在图形中部显示的活性急剧上升（“标记为X’）是由整夜运行中在HCl流量非有意但逐渐降低后将流速调整回114 ml min-1导致的。
实施例1a和实施例1b催化剂的乙炔转化率的对比图示于图3中。与实施例1a 的催化剂相比，没有采用最后的水洗步骤的实施例1b的催化剂活性更大，并且经过测试阶段后钝化明显更少。
如实施例2所述经过25天使用后，通过扫描电子显微镜研究由反应器上游部分得到的根据本发明的催化剂样品。表面呈现大量的碳细纤维。图4和图5显示了不同放大倍数的两幅SEM显微照片。图4是显示经过25天反应后样品上形成的大量纳米管的SEM显微照片。图5显示这些是碳纳米管，它们在其末端承载着金属金纳米颗粒。图5显示了在纳米管末端的金颗粒和一个纳米管的开口端。
更进一步的图像（图6）是从管式反应器中部取出的使用过的催化剂的样品，表明开始形成碳纳米管，是从碳载体表面生长的。
图7中的附加实验表明，使用实施例1c和1d中制备的二氧化硅上的金样品催化剂，乙炔转换为VCM的转化率明显比使用碳上金催化剂低（低于4%）。另外，沉积在二氧化硅上的催化剂在使用中表现出持续的钝化现象。
几个小时后在线收回催化剂样品，并用X射线光电谱（XPS）分析。图8表明所得的曲线含Au0导致的峰，和Au（III）导致的在较高结合能的峰。
Claims (15)
1. 一种使乙炔和HCl反应制备VCM的方法，包括使乙炔和HCl在气相下通过含有承载在碳载体上的金属金颗粒的催化剂。
2. 如权利要求1所述的方法，其中金颗粒沉积在碳载体的表层中。
3. 如权利要求2所述的方法，其中大多数金颗粒沉积在厚度不超过200μm的层中。
4. 如权利要求3所述的方法，其中大多数金颗粒沉积在厚度不超过100μm的层中。
5. 如权利要求1-4任一项所述的方法，其中所述金颗粒包括金属金核和含有包括Au3+的较高氧化态物质的部分或完整的壳。
6. 如权利要求1-5任一项所述的方法，其中所述金颗粒承载在碳细纤维上。
7. 如权利要求1-6任一项所述的方法，其中所述碳载体是一种高表面积的碳挤出料或粒料。
8. 一种用于由乙炔生产VCM的金基催化剂，包括承载在碳载体上的金颗粒，其中所述颗粒具有金属金核和包含包括Au3+的较高氧化态物质的壳。
9. 如权利要求8所述的催化剂，其中金颗粒沉积在载体的表层中。
10. 如权利要求9所述的催化剂，其中大多数金颗粒沉积在厚度不超过200μm的层中。
11. 如权利要求10所述的催化剂，其中大多数金颗粒沉积在厚度不超过100μm的层中。
12. 如权利要求8所述的催化剂，其中所述金颗粒承载在碳细纤维上。
13. 如权利要求12所述的催化剂，其中所述碳细纤维为碳纳米管。
14. 如权利要求8-13任一项所述的催化剂，其中所述碳载体为高表面积碳挤出料。
15. 一种制备根据本发明的催化剂的方法，包括将金从王水溶液沉积至碳载体上，并沉积具有金属金核和具有包含较高氧化态金物质的表面的金颗粒。
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