CN108212154A - 以多肽为导向剂的1,3-丁二烯氧化制3,4-环氧丁烯高效银催化剂的制备方法 - Google Patents
以多肽为导向剂的1,3-丁二烯氧化制3,4-环氧丁烯高效银催化剂的制备方法 Download PDFInfo
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- CN108212154A CN108212154A CN201711485879.3A CN201711485879A CN108212154A CN 108212154 A CN108212154 A CN 108212154A CN 201711485879 A CN201711485879 A CN 201711485879A CN 108212154 A CN108212154 A CN 108212154A
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Abstract
本发明公开了一种以多肽为三维导向剂的1,3‑丁二烯氧化制3,4‑环氧丁烯高效银催化剂的制备方法，该方法包括：1)向可溶性银盐溶液中加入草酸溶液得到草酸银沉淀；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)取多肽加入到步骤2)得到的溶液中，得到含有多肽的混合溶液；4)草酸银沉淀加入到含有多肽的混合溶液中，制得澄清的络合溶液；5)向络合溶液中添加助剂制成浸渍液；6)将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；本发明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元素的膜状分布。
Description
技术领域
本发明涉及一种以多肽为三维导向剂的1,3-丁二烯氧化制3,4-环氧丁烯高效银催化剂的制备方法，特别是提高1,3-丁二烯氧化制3,4-环氧丁烯催化剂活性、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。
背景介绍
在烯烃环氧化反应中，含有烯烃和氧的反应混合气与催化剂接触，在一定的反应条件下生产环氧化合物及少量的二氧化碳、水等副产物。
迄今为止，银催化剂仍然是工业上烯烃环氧化生产环氧化合物的唯一有效催化剂。在现有技术中，银催化剂除了包括银成分外，还通常具有一种或多种与其共沉积在载体上的其它元素，载体通常由耐高温的、具有合适比表面和孔结构的α-氧化铝组成。除银之外沉积在载体上的其它元素起到助剂或者共助剂的作用，用来提高银催化剂的催化性能。合适孔结构的α-氧化铝载体不仅可以促进活性组分在载体上的沉积，而且可以提高银催化剂的催化性能，这是因为合适的孔结构能够为烯烃环氧化反应提供足够的空间，使反应热及时扩散出去，另一方面也有利于目标产物环氧化合物及时脱附。因此，银催化剂的性能除和催化剂的组成和制备方法有重要的关系外，还和α-氧化铝载体的孔结构有重要的关系。
专利CN200780009922.7使用石油焦、聚烯烃、胡桃壳粉等可燃尽材料将孔引入α-氧化铝载体。但是，在可燃尽材料除去之后，会有金属氧化物残留在载体中，这些残留物可能大大地削弱催化剂的性能，而且残留物的实际成分批间变化相当大，致其可预测性不能令人满意。美国专利2004/0110973A1还批露了一种用于由两种α-氧化铝微粒来制备合适孔径的氧化铝载体的方法。中国专利CN102145306A选用粗、中、细不同粒度等级的三水氧化铝制备载体。专利申请CN102133544A中公开了一种α-氧化铝载体的制备方法，包括混合工业α-三水氧化铝、假一水氧化铝、0～30％的可烧尽含碳材料、0～2.5％的碱土金属盐、0～3％的氟化物、粘结剂和水，所述百分数均基于原料氧化铝的总质量，其中α-三水氧化铝与假一水氧化铝的重量比为1～4:1，粘结剂和水的总量为氧化铝原料总重量的15～30％；然后经过挤压成型、干燥和焙烧得到所述α-氧化铝载体。在该发明中，使用0～30％的可烧尽含碳材料释放的一氧化碳和/或二氧化碳气体进行扩孔；使用0～3％的氟化物作为矿化剂，以利于氢氧化铝向氧化铝的晶相转变。通过上述这些载体能够制备出催化性能可调的银催化剂。但是，由于银催化剂的主活性组分为银元素，为了提高催化剂的选择性和稳定性，就需要尽可能的是银晶粒在α-Al2O3表面分布均匀，且晶粒较小。最好是能控制银晶粒变大的进程。以上所述专利都没有解决该问题。
发明内容
针对目前用于1,3-丁二烯氧化制3,4-环氧丁烯的Ag/Al2O3催化剂选择性下降较快、稳定性不好等缺点，本发明提出了一种对1,3-丁二烯氧化制3,4-环氧丁烯反应具有选择性高、稳定性好、使用寿命长等优点的Ag/Al2O3催化剂的制备方法。
鉴于上述现有技术的状况，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1,3-丁二烯氧化制3,4-环氧丁烯时，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：
本发明提供了一种以多肽为三维导向剂的1,3-丁二烯氧化制3,4-环氧丁烯高效银催化剂的制备方法，包括如下步骤：
1)将可溶性银盐溶液和草酸溶液混合得到草酸银沉淀或直接称取草酸银固体；
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；肽以肽键计算，所述多与银的摩尔比为0.01-2，优选为0.1-1；
该催化剂以α-Al2O3为载体，银为活性组分，碱金属和/或碱土金属和/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。
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。
本发明上述制备方法中，催化剂优选活性组分银的质量百分含量为1～50％，更优选15～25％，碱金属和/碱土金属助剂组分含量为10～1000ppm，优选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1,3-丁二烯氧化制3,4-环氧丁烷银催化剂，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1,3-丁二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。
由于1,3-丁二烯氧化制3,4-环氧丁烯是一个强放热反应，因此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。
本发明所述催化剂在以1,3-丁二烯含量为40～60％为原料，在反应压力1-2.5MPa，反应温度150-250℃、1,3-丁二烯原料气气体空速500-1500h-1的条件下的催化性能评价测试，评价结果显示1,3-丁二烯转化率为18％左右，3,4-环氧丁烷选择性不低于95％。催化剂寿命延长30％以上。
本发明的技术的显著优点是：(1)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1,3-丁二烯氧化制3,4-环氧丁烯的选择性；(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)1,3-丁二烯氧化制3,4-环氧丁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11.5g溶于40ml去离子水中得到硝酸银溶液，草酸4.6g溶于15ml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并添加以谷氨酰胺和赖氨酸缩合脱水形成的二肽4.6g和水的混合溶液中，制得澄清的浅棕色络合溶液。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110℃烘干6h，260℃空气气氛下活化45min，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：22.1％，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1,3-丁二烯环氧化反应性能测试。反应条件为：原料气含1,3-丁二烯50％，原料气的总体积空速为4000h-1，反应压力为1.8MPa，反应温度为220℃，进行1,3-丁二烯氧化的连续反应。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12.0g，将所称草酸银溶于乙二胺与乙醇胺体积比为3:1以及以天冬酰胺和组氨酸、丙氨酸二次缩合而成的多肽4.45g和水的混合溶液中，制得浅黄绿色络合溶液。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10h，再于120℃烘干4h，280℃空气气氛下焙烧60min，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：21.4％、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13.0g，草酸铵7.3g溶于100.0g加热至50℃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并添加两个赖氨酸和丝氨酸脱水缩合而成的多肽6.27g和水的混合溶液中，制得浅蓝黑色透明络合溶液。称取硝酸钠0.032g、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100℃烘干20h，300℃空气气氛下焙烧10min，得催化剂成品C。
催化剂C的组成为：Ag-Na-Re-Zr/Al2O3，其中各组分以氧化物计的质量百分含量为：Ag2O：18.3％，Na2O：0.05％，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连续反应60天后，对1,3-丁二烯氧化制3,4-环氧丁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1,3-丁二烯氧化制反应数据表
Claims (5)
1.一种以多肽为三维导向剂的1,3-丁二烯氧化制3,4-环氧丁烯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)得到的含多肽的混合溶液中，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/或碱土金属和/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，以肽键计算，所述多肽与银的摩尔比为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所述的高效银催化剂，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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