CN108160075A - 以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂的制备方法 - Google Patents
以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂的制备方法 Download PDFInfo
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- CN108160075A CN108160075A CN201711478150.3A CN201711478150A CN108160075A CN 108160075 A CN108160075 A CN 108160075A CN 201711478150 A CN201711478150 A CN 201711478150A CN 108160075 A CN108160075 A CN 108160075A
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Abstract
本发明涉及一种以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂的制备方法，制备时添加一定量的以两个或多个氨基酸形成的多肽为银活性组分、铯和/或铼等活性助剂的负载三维导向剂，使银等无机活性组分在α‑Al2O3表面选择性沉淀形成分布有均匀凸起的膜。本发明制备方法无需对现有的制备工艺及方式进行过于复杂的变更，就可实现银催化剂中活性组分银等的膜状分布。该方法操作简单、成本低廉、可控性强、易于制备，制备得到的银催化剂具有活性好、选择性高、稳定性好等优点。
Description
技术领域
本发明涉及一种以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂及其制备方法，特别是提高乙烯氧化制环氧乙烷催化剂活性、稳定性和选择性的催化剂制备方法，属于催化剂制备和应用领域。
背景技术
目前，EO主要通过乙烯直接氧气氧化法、在负载银催化剂作用下乙烯和氧气的气-固相催化选择性氧化反应生产。在该反应体系中，主要存在如下所示的反应网络，其中反应1为主反应，是生成EO的选择性氧化反应，反应2和3为主要副反应，分别为EO的深度氧化反应和乙烯的完全氧化反应。可以看出这是一个串并联共存的、较复杂的、强放热的反应体系。该工艺中，银催化剂是核心和关键，其性能直接决定着生产的物耗、能耗和经济性。
关于银催化剂的研究，更多地集中在催化剂助剂方面,研究较多的是碱金属助剂，尤其是Cs助剂，相关报导很多。在银催化剂中添加少量铯助剂可以提高催化剂的选择性，早已为人们所知。关于其作用机理，也有很多解释。Grant和Lambert 在单晶银上，对EO异化反应和乙烯环氧化反应进行了详细的研究，发现在银表面沉积少量的Cs助剂可以明显抑制EO的异构化反应，提高催化剂的活性和生成EO的选择性，他们认为，Cs助剂的添加促进EO生成的原因在于，Cs助剂的给电子作用抑制了EO异构化的开环一步反应，从而抑制了EO的深度反应，增加了EO的生成。 Compbell的研究表明，铯助剂提高了银表面上氧的覆盖度，这可能是催化剂选择性提高的重要原因。在负载银催化剂上，碱金属的添加可以抑制和降低载体表面酸性，可能也会对选择性产生影响。此外，Minahan等的研究表明，负载银催化剂中铯助剂主要存在于银于氧化铝载体之间，起着粘结剂的作用。
工业乙烯环氧化反应中，常常添加微量的有机氯化物(通常为1,2-二氯乙烷(EDC)或氯乙烷(EC))气体助剂，以提高催化剂的选择性，Grant等人认为其作用机理从根源上说主要是电子效应，氯通过和银表面的吸附态原子氧竞争电子，降低了吸附氧上的电子密度，有利于形成亲电氧，后者易于攻击乙烯而生成EO。目前这种观点已为大家所接受。
有报道，氮氧化物(NOx)也可用作气体助剂。Grant等研究发现，只有在银上有亚单层碱金属铯助剂共存时，才能明显提高催化剂的选择性，他们认为，反应中可能有氮氧阴离子生成并直接参与了乙烯环氧化反应。有关该方面的研究报道不多。
近些年，关于金属铼助剂的报道在壳牌公司的专利中时有出现，据称该催化剂具有较高的选择性。Yang Jun和Deng Jingfa对以铼为助剂的电解银催化剂上乙烯选择性氧化反应进行了详细的研究。他们发现在电解银上添加1.9-6.5ppm的微量铼助剂，可以提高反应活性，EO生成的选择性也由74％提高到78％以上，最高可达82％，有了明显的增加。他们认为，铼助剂通过与银表面的吸附氧竞争电子，降低了吸附氧的电子密度，使其更易于亲电反应生成EO，从而提高了反应的活性与选择性。袁晓红等人对添加了Re、Cs助剂的电解银上的乙烯环氧化反应进行了研究，也得到类似的结果。
工业用银催化剂一般同时含有多种助剂，这些助剂助剂之间存在协同作用，如Shell公司1996年的专利WO9613493中报道了一中银催化剂的制造方法，该催化剂含有银、碱金属和铼助剂以及选自硫、磷和铬等的铼的协同助剂。关于协同作用机理鲜有报道。
银催化剂由上世纪三十年代开始，经过几十年的发展到今天，形成了两个主要类型：一种是选择性75～82％的高活性催化剂；另一种是选择性82～89％的高选择性催化剂。这些进步既归功于银催化剂所用载体和生产工艺的改进，同时也归功于银催化剂制备方法的进步，主要包括助剂的使用，浸渍方法和活化工艺的改进。专利US2238474提出银催化剂中加入碱土金属能够起到很好的作用，由银和 2～40％的至少一种选自钡、锶和锂的氧化物、过氧化物和氢氧化物组成的催化剂能够提高催化剂性能。专利US4833261、US4761394公布了使用铼作为银催化剂助剂，揭开了现代高选择性银催化剂研究的序幕。专利US4766105、US4808738和US4820675在Ag-Re-Cs催化剂中加入了0.2～5mmol的选自S、Mo、W、Cr或其混合物的Re的共助剂，使选择性特别是初始选择性更高。专利CN105618047A公开了一种溶剂处理银催化剂来改善银催化剂性能的方法。专利CN1162416C公开了一种惰性气体处理银催化剂母体来调变银催化剂性能的方法。专利CN1142154C 发明了一种含锡的载体，通过将不同粒度的三水氧化铝与假一水氧化铝、锡化合物、造孔剂、助溶剂、氟化物、粘结剂与适量的水混合、成型、干燥、焙烧制得。浸渍银和碱金属制得的银催化剂活性和选择性同时得到改善。
发明内容
针对目前用于乙烯氧化制环氧乙烷的Ag/Al2O3催化剂选择性下降较快、稳定性不好等缺点，本发明公开了一种对乙烯氧化制环氧乙烷反应具有选择性高、稳定性好、使用寿命长等优点的Ag/Al2O3催化剂的制备方法。
本发明人在银催化剂及其制备工艺领域进行了广泛深入的研究，结果发现，在银催化剂的制备过程中，添加适量的多肽作为三维负载三维导向剂，可以使银等活性组分选择性沉淀，在α-Al2O3表面形成分布有均匀凸起的膜。有利于改善银催化剂的催化性能。由该方法制备的负载型银催化剂在用于催化乙烯氧化制环氧乙烷时，活性有所提高，更重要的是选择性得到明显改进，并且稳定性及寿命得到很大的提高。
本发明具体采用如下技术方案解决上述技术问题：
一种以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂的制备方法，其特征在于，
1)将可溶性银盐溶液和草酸溶液混合得到草酸银沉淀或称取草酸银固体；
2)将乙二胺与乙醇胺按体积比4-2:1混合后加水中得到溶液；
3)取多肽加入步骤2)得到的溶液中，得到含有多肽的混合溶液；
4)将步骤1)得到的草酸银沉淀加入到步骤3)得到的多肽溶液中，制得澄清的络合溶液；
5)向步骤4)得到络合溶液中添加助剂制成浸渍液；
6)将步骤5)得到的浸渍液倒入盛有载体的容器中在真空条件下过饱和浸渍，完成浸渍后，将过滤得到的浸渍后产物经陈化、干燥、活化后制得催化剂；
所述多肽为甘氨酸、天冬酰胺、赖氨酸、谷氨酰胺、丝氨酸、苏氨酸、半胱氨酸、组氨酸、精氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、苯丙氨酸、色氨酸、酪氨酸、天冬氨酸、谷氨酸、甲硫氨酸中的一种或多种发生一次或多次缩合脱水而成；所述多肽以肽键计算与银的摩尔比为0.01-2；
所述的催化剂以α-Al2O3为载体，银为活性组分，碱金属和/碱土金属和/或过渡金属为助剂，活性组分及助剂在载体表面形成分布有均匀凸起的膜。
在本发明制备方法中，所述多肽以肽键计算与银的摩尔比优选为0.1-1。
上述制备方法中，所述助剂优选为Na、K、Mg、Ca、Ba、Cs、Ce、Re、Zr 的可溶性盐溶液的一种或多种。
所述助剂为Na、K、Mg、Ca、Ba、Cs、Ce、Re、Zr的可溶性盐溶液的一种或多种。
所述的催化剂的活性组分银的质量百分含量优选为1～50％，更优选15～25％，助剂组分含量为10～1000ppm，更优选为100～300ppm。
步骤6)中的浸渍后产物干燥、活化可采用常规方法进行，优选在80～120℃下干燥，在200～400℃的流动空气中进行活化，流动空气流量为10～100L/h，活化时间5～300min。
经过如上步骤制备的乙烯氧化制环氧乙烷银催化剂，用电子探针、扫描电镜或透射电镜等表征手段进行催化剂截面晶粒形态及大小进行表征，可发现在α-Al2O3表面形成分布有均匀凸起的膜。通过热重、O2-TPD分析发现银催化剂吸脱附有利于发生乙烯环氧化反应的氧的能力增强。
通过刮取不同薄层进行XRF化学组分分析，结果表明，氧化银含量在催化剂中保持均匀分布，所刮取的薄层最大不超过0.5毫米。足够表明活性组分在催化剂中的含量分布均匀。
本发明催化剂用于乙烯氧化制环氧乙烷反应时，原料气中乙烯的含量一般不小于25％，反应的一般条件为反应压力：2～3MPa，反应温度200～300℃，乙烯气体空速为1500～3500h-1。
由于乙烯氧化制环氧乙烷是一个强放热反应，工业上一般更为注重此反应中目标产物的选择性，而使反应维持在较低的稳定的转化率水平。
本发明所述催化剂所适用的原料为乙烯含量在20～40％，在反应压力2～ 3MPa，反应温度200～300℃、乙烯原料气气体空速1500～3500h-1的条件下，乙烯转化率为10％左右，环氧乙烷选择性不低于89％。催化剂寿命延长25％以上，取得了令人满意的结果。
本发明的技术的显著优点是：(1)采用本发明催化剂的显著特点是用多肽作为三维负载导向剂，使银等组分在α-Al2O3晶面表面形成分布有均匀凸起的膜，能够提高催化剂的乙烯氧化制环氧乙烷的选择性；(2)采用多肽作为三维导向剂调控催化剂中Ag等组分的负载形貌，使得催化剂性能得到明显的改善。通过这两个方面的共同作用，保证了本发明提出的技术不同于已有发明和技术的特点：1)简单常规的催化剂制备技术；2)乙烯氧化制环氧乙烷的目标产物的选择性稳定；3)催化剂寿命较长。
具体实施方式
以下将通过具体实施例对本发明作进一步说明，但本发明并不局限于这些实施例。
实施例1
称取硝酸银13.5g溶于50ml去离子水中得到硝酸银溶液，草酸5.0g溶于20ml去离子水中得到草酸溶液，将溶好的硝酸银溶液缓慢倒入草酸溶液中，产生白色草酸银沉淀。将沉淀抽滤，滤饼洗至中性，溶于乙二胺与乙醇胺体积比为4:1以及谷氨酰胺和赖氨酸缩合脱水形成的二肽4.67g和水的混合溶液中，制得澄清的浅黄棕色络合溶液。称取硝酸铯0.5g溶于100ml去离子水中备用、称取0.25g高铼酸铵溶于 100ml去离子水中备用。量取1.8ml硝酸铯溶液、1.2ml高铼酸铵溶液倒入上述络合溶液中，摇匀。称取银载体A10g在抽真空条件下进行过饱和浸渍0.5h，然后将浸渍后的载体滤出，在室温陈化10h，再于100℃烘干6h，250℃空气气氛下活化30min，得催化剂成品A。
催化剂A的组成为：Ag-Cs-Re/Al2O3，其中各组分以氧化物计的质量百分含量为：Ag2O：25.3％，Cs2O：300ppm，ReO2：100ppm，其余为氧化铝。通过扫描电镜观察，发现在α-Al2O3晶面表面形成了有均匀凸起分布的膜状覆盖物。凸起部分当量粒径均匀，在20-30nm。
催化剂A的催化活性测试：采用10ml固定床微型反应评价系统，取10毫升研磨至20～40目的催化剂A装入内径为5mm的不锈钢反应器中进行乙烯环氧化反应性能测试。反应条件为：原料气含乙烯28％，原料气的总体积空速为6000h-1，反应压力为2.05MPa，反应温度为230℃，进行乙烯氧化的连续反应。每一个小时进行一次色谱取样分析，10个样为一组计算平均值。催化剂A的催化活性测试结果见表1。
实施例2
称取草酸银15.0g，将所称草酸银溶于乙二胺与乙醇胺体积比为3:1以及天冬酰胺和组氨酸、丙氨酸二次缩合而成的多肽3.72g和水的混合溶液中，制得浅黄色络合溶液。碱式碳酸锆1.2g配成1ml溶液倒入上述络合溶液中，量取取硝酸铯溶液 0.9ml、量取高铼酸铵溶液2.3ml同样注入上述溶液中。称取银载体A10g在抽真空条件下进行过饱和浸渍2h，然后将浸渍后的载体滤出，在室温陈化15h，再于110℃烘干4h，280℃空气气氛下焙烧10min，得催化剂成品B。
催化剂B的组成为：Ag-Cs-Re-Zr/Al2O3，其中各组分以氧化物计的质量百分含量为，Ag2O：25.5％、Cs2O：200ppm、ReO2：200ppm、ZrO2：0.3％，其余为氧化铝。通过扫描电镜观察，发现在α-Al2O3晶面表面形成了有均匀凸起分布的膜状覆盖物。凸起部分当量粒径均匀，在20-30nm。
催化剂B评价条件同实施例1，实验结果见表1。
实施例3
称取硝酸银17.0g，草酸铵8.6g溶于100.0g加热至40～60℃的去离子水配成草酸铵溶液，将称好的硝酸银缓慢溶于草酸铵溶液中，产生白色草酸银沉淀。将沉淀过滤出溶于乙二胺与乙醇胺体积比为4:1以及两个赖氨酸和丝氨酸脱水缩合而成的多肽3.97g和水的混合溶液中，制得浅蓝黑色透明络合溶液。称取硝酸钾0.05g、硝酸氧锆1.5g分别配成2ml溶液倒入上述络合溶液中，量取高铼酸铵溶液3.4ml同样注入上述溶液中。称取银载体A10g在抽真空条件下进行过饱和浸渍5h，然后将浸渍后的载体滤出，在室温陈化20h，再于120℃烘干2h，300℃空气气氛下焙烧60min，得催化剂成品C。
催化剂C的组成为：Ag-K-Re-Zr/Al2O3，其中各组分以氧化物计的质量百分含量为：Ag2O：25.3％，K2O：0.04％，ReO2：300ppm，ZrO2：0.25％其余为氧化铝。通过扫描电镜观察，发现在α-Al2O3晶面表面形成了有均匀凸起分布的膜状覆盖物。凸起部分当量粒径均匀，在20-30nm。
催化剂C评价条件与色谱分析同实施例1，反应性能结果见表1。
分析结果表明该系列催化剂在评价实验中连续反应100天后，对乙烯氧化制环氧乙烷的选择性没有明显的下降，表现出了很好的稳定性。
表1 不同催化剂的乙烯氧化制反应数据表
Claims (5)
1.一种以多肽为三维导向剂的乙烯氧化制环氧乙烷高效银催化剂的制备方法，其特征在于，
1)将可溶性银盐溶液和草酸溶液混合得到草酸银沉淀或称取草酸银固体；
2)将乙二胺与乙醇胺按体积比4-2:1混合后加水中得到溶液；
3)取多肽加入步骤2)得到的溶液中，得到含有多肽的混合溶液；
4)将步骤1)得到的草酸银沉淀加入到步骤3)得到的多肽溶液中，制得澄清的络合溶液；
5)向步骤4)得到络合溶液中添加助剂制成浸渍液；
6)将步骤5)得到的浸渍液倒入盛有载体的容器中在真空条件下过饱和浸渍，完成浸渍后，将过滤得到的浸渍后产物经陈化、干燥、活化后制得催化剂；
所述多肽为甘氨酸、天冬酰胺、赖氨酸、谷氨酰胺、丝氨酸、苏氨酸、半胱氨酸、组氨酸、精氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、苯丙氨酸、色氨酸、酪氨酸、天冬氨酸、谷氨酸、甲硫氨酸中的一种或多种发生一次或多次缩合脱水而成；所述多肽以肽键计算与银的摩尔比为0.01-2；
所述的催化剂以α-Al2O3为载体，银为活性组分，碱金属和/碱土金属和/或过渡金属为助剂，活性组分及助剂在载体表面形成分布有均匀凸起的膜。
2.根据权利要求1所述的制备方法，其特征在于，所述多肽以肽键计算与银的摩尔比为0.1-1。
3.根据权利要求1所述的制备方法，其特征在于，所述助剂为Na、K、Mg、Ca、Ba、Cs、Ce、Re、Zr的可溶性盐溶液的一种或多种。
4.根据权利要求1所述的制备方法，其特征在于，活性组分银的质量百分含量为1～50％，助剂组分含量为10～1000ppm。
5.根据权利要求1所述的制备方法，其特征在于，活性组分银的质量百分含量为15～25％，助剂组分含量为100～300ppm。
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