CN105618091A - 四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法 - Google Patents

四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法 Download PDF

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CN105618091A
CN105618091A CN201610173757.XA CN201610173757A CN105618091A CN 105618091 A CN105618091 A CN 105618091A CN 201610173757 A CN201610173757 A CN 201610173757A CN 105618091 A CN105618091 A CN 105618091A
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孟舒献
冯亚青
李玉龙
张宝
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Tianjin University
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Abstract

本发明涉及一种四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法。公开了一种用于从四氢糠醇在固定床中气固相催化合成吡啶的不同助催化剂改性的负载型复合氧化物催化剂制备及其应用方法，该催化剂组分之一为钼，负载量为载体质量的1％-20％；组分之二为镍，负载量为载体质量的1％-20％，组分之三为磷、硼、铜、锌和镁中的一种，负载量为载体质量的1％-10％，不同氧化物改性的负载在γ-Al2O3载体上的氧化钼-氧化镍催化剂。本发明的催化剂增加了吡啶的选择性，减少了高沸点副产物，提高了吡啶的总收率最高至88％，催化剂寿命能达50h保持吡啶收率在70％以上，催化剂再生后催化性能良好，催化剂制备方法简单易行。

Description

四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法
技术领域
本发明涉及化工领域，具体涉及一种四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法。
背景技术
吡啶不仅是含吡啶环类的农药和医药中间体的基础原料，也是日用化工、饲料、食品添加剂、子午轮胎工业的重要原料，而且在医药和工业领域中还可以作为特殊溶剂。早期的吡啶生产主要是从煤炼焦副产品中提取，此种方法产率低，所得产物纯度差。随着需求量的不断增大，这种方法已不适应大批量工业化生产，现在95％以上的吡啶由合成法生产，产量集中在美国、中国和印度。目前主要采用醛氨法合成吡啶，然而吡啶收率低、选择性不高，并且副产约1/3的3-甲基吡啶，原料成本高、毒性较大等缺点。通过四氢糠醇与氨气合成吡啶工艺的核心技术是提高催化剂的效率。US2543424公开了过渡金属Mo的氧化物或硫化物与醇脱水材料共同作为催化剂，提高了四氢糠醇气固相催化合成吡啶的收率。反应温度为503℃时，负载10％MoO2/γ-Al2O3催化剂吡啶摩尔收率为45％，相同反应条件下只有γ-Al2O3时，吡啶的摩尔收率为13.2％。US2963484公开了以氧化钴改性的氧化钼/活性氧化铝催化剂，提出氧化钴的加入可以大幅度降低催化剂的积炭量，但吡啶的收率降低约6％。US2979510公开了V2O5改性的活性氧化铝催化剂积炭量低于MoO3改性的活性氧化铝，但催化剂活性低于MoO3改性的活性氧化铝。经过V2O5、MoO3共同改性后，活性氧化铝催化剂活性降低仅为1％，积炭量却大幅度下降。US2972615公开了以四氢糠醇、氨气为原料，负载在活性氧化铝上的V2O5、(WO3、ZnO)为催化剂，气固相催化合成吡啶。US2972616公开了少量K2O改性的MoO3/γ-Al2O3催化剂，可以很大程度上减少积炭量，并不明显影响吡啶收率。US3238214公开了以Pd改性的活性氧化催化剂，Pd负载量为0.29％，反应温度为300℃时，吡啶的最高收率为80％，反应385h后吡啶和哌啶总收率降为50％，并且600～650℃再生后，Pd/γ-Al2O3催化剂仍能保持350h，吡啶和哌啶总收率大于65％。US3254089公开了ZnO改性的MoO3/γ-Al2O3催化剂，ZnMoO4的形成减缓了积碳形成的速率，延长了反应时间。CN1736588A公开了以四氢糠醇、氨气为原料，负载在活性氧化铝上的MoO3，V2O5及La、Ce、Cd的氧化物为催化剂，气固相催化合成吡啶。CN102553607A公开了以四氢糠醇、氨气为原料，负载在活性氧化铝上的NiO或K2O改性的MoO3催化剂，气固相催化合成吡啶。它们均存在吡啶选择性和收率不高，高沸点产物较多并且催化剂寿命较短的问题。
发明内容
本发明的目的在于克服现有催化剂收率不高，催化剂寿命短的问题，提供一种能提高吡啶收率，降低高沸点副产物，提高催化剂寿命的不同氧化物改性的生产吡啶用的催化剂。
本发明提供的用多种元素助催化的四氢糠醇气固相合成吡啶催化剂是以Mo、Ni为主，以B、P、Cu、Zn和Mg元素为助催化剂，负载在γ-Al2O3载体上的催化剂；催化剂载体为圆柱状γ-Al2O3，负载活性组分之一为氧化钼，其负载量为载体质量的1-20％；负载活性组分之二为氧化镍，其负载量为载体质量的1-20％；负载组分之三为磷、硼、铜、锌或镁的氧化物，负载量为载体质量的1％-10％。
优选上述的组分之一氧化钼的负载量为载体质量的5-15％；组分之二氧化镍的负载量为载体质量的5-15％；组分之三氧化磷负载量为载体质量的1-5％、氧化硼负载量为载体质量的1-5％、氧化铜负载量为载体质量的1-5％、氧化锌负载量为载体质量的1-5％或氧化镁负载量为载体质量的1-5％的任意一种选择。
本发明的四氢糠醇气固相催化合成吡啶的负载型催化剂制备方法，包括以下过程：
一种由四氢糠醇气固相催化合成吡啶的负载型催化剂，其特征在于，催化剂载体为圆柱状γ-Al2O3，负载活性组分之一为氧化钼，其负载量为载体质量的1-20％；负载活性组分之二为氧化镍，其负载量为载体质量的1-20％；负载组分之三磷、硼、铜、锌或镁的氧化物的一种，负载量为载体质量的1％-10％。
组分之一氧化钼的负载量为载体质量的5-15％。
组分之二氧化镍的负载量为载体质量的5-15％。
组分之三氧化磷、氧化硼、氧化铜、氧化锌或氧化镁负载量为载体质量的1-5％。
本发明的合成吡啶的负载型催化剂的制备方法，包括以下过程：
1)将质量比为0.9-1.1:1的蒸馏水和拟薄水铝石混合为面团状，挤压成圆柱状，在干燥箱中90-130℃干燥4-6h，置于马弗炉中以8-10℃/min升温速率升温至400-600℃焙烧4-6小时，得到载体γ-Al2O3；
2)将钼酸铵和硝酸镍溶解于蒸馏水中配制成溶液，再将磷酸二氢铵、硼酸、硝酸铜、硝酸锌、硝酸镁其中之一加入溶液；将步骤1)中的载体γ-Al2O3浸渍在上述溶液中，室温浸渍10-24h，得到湿的改性催化剂；
3)将步骤2)所得的湿的改性催化剂在温度90-130℃下，干燥6-12h,然后在500-600℃焙烧4-6h，冷却至室温，得到用于生产吡啶的催化剂。
本发明通过在γ-Al2O3上负载B、P、Cu、Zn和Mg氧化物，调节了催化剂表面酸中心的分布，保证了适当的酸中心和四氢糠醇、氨气反应，本发明中吡啶收率可达88％，催化剂寿命长达50h保持吡啶收率在70％以上，并且再生后效果良好。催化剂制备方法简单易行。
具有实施方式
包括步骤如下：
1)将质量比为0.9-1.1:1的蒸馏水和拟薄水铝石混合为面团状，挤压成圆柱状，在干燥箱中90-130℃干燥4-6h，置于马弗炉中以8-10℃/min升温速率升温至400-600℃焙烧4-6小时，得到载体γ-Al2O3；
2)将负载量为1-20％的钼酸铵和硝酸镍溶解于蒸馏水中配制成溶液，再将负载量为1-10％的磷酸二氢铵、硼酸、硝酸铜、硝酸镁、硝酸锌其中之一加入溶液；将1)中的载体γ-Al2O3浸渍在上述溶液中，室温浸渍10-24h，得到湿的改性催化剂；
3)将步骤2)所得的湿的改性催化剂在温度90-130℃下，干燥6-12h,然后在500-600℃焙烧4-6h，冷却至室温，得到用于生产吡啶的催化剂。
实施例1
1)将质量比为0.9-1.1:1市售的拟薄水铝石和蒸馏水，混合均匀并挤压成圆柱状，在干燥箱中100℃干燥5h，置于马弗炉中以8-10℃/min升温速率升温至500℃焙烧4h，得到载体γ-Al2O3；
2)将12.26克(NH4)6Mo7O24·4H2O，38.95克Ni(NO3)·6H2O，1.62克NH4H2PO4溶解于200ml水中，然后将1)中γ-Al2O3载体100g放入溶液中浸渍24h，使溶液均匀吸附到载体的微孔中。
3)所得催化剂前驱体在温度100℃下，干燥箱中干燥6h，然后在550℃焙烧5h，冷却至室温，得到用于生产吡啶的催化剂。催化剂中含有氧化钼10％，氧化镍10％，氧化磷1％。
4)在固定床反应管内装入上述催化剂20g，四氢糠醇气化后与预热过的氨混合，混合气体通过装填20g催化剂，内径为1.3cm的反应管。产品用气相色谱进行分析，反应结果如下表所示。
反应温度 反应压力 反应气空速 四氢糠醇与氨气摩尔比 吡啶产率 催化剂寿命
550℃ 1atm 600h-1 1:10 86％ 45h
实施例2
制备步骤和方法与实施例1相同。该催化剂含有10％氧化钼、10％氧化镍，1％氧化锌。将制备的催化剂应用于四氢糠醇气固相催化合成吡啶反应。反应条件同实施例1，反应条件及反应结果如下表所示
反应温度 反应压力 反应气空速 四氢糠醇与氨气摩尔比 吡啶产率 催化剂寿命
550℃ 1atm 600h-1 1:10 88％ 50h
实施例3
制备步骤和方法与实施例1相同。该催化剂含有10％氧化钼、10％氧化镍，5％氧化硼。将制备的催化剂应用于四氢糠醇气固相催化合成吡啶反应。反应条件同实施例1，反应条件及反应结果如下表所示
反应温度 反应压力 反应气空速 四氢糠醇与氨气摩尔比 吡啶产率 催化剂寿命
550℃ 1atm 600h-1 1:10 85％ 48h
实施例4
制备步骤和方法与实施例1相同。该催化剂含有10％氧化钼、10％氧化镍，8％氧化铜。将制备的催化剂应用于四氢糠醇气固相催化合成吡啶反应。反应条件同实施例1，反应条件及反应结果如下表所示
反应温度 反应压力 反应气空速 四氢糠醇与氨气摩尔比 吡啶产率 催化剂寿命
550℃ 1atm 600h-1 1:10 87％ 45h
本发明公开和提出的四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法，本领域技术人员可通过借鉴本文内容，适当改变条件路线等环节实现，尽管本发明的方法和制备技术已通过较佳实施例子进行了描述，相关技术人员明显能在不脱离本发明内容、精神和范围内对本文所述的方法和技术路线进行改动或重新组合，来实现最终的制备技术。特别需要指出的是，所有相类似的替换和改动对本领域技术人员来说是显而易见的，他们都被视为包括在本发明精神、范围和内容中。

Claims (5)

1.一种由四氢糠醇气固相催化合成吡啶的负载型催化剂，其特征在于，催化剂载体为圆柱状γ-Al2O3，负载活性组分之一为氧化钼，其负载量为载体质量的1-20％；负载活性组分之二为氧化镍，其负载量为载体质量的1-20％；负载组分之三磷、硼、铜、锌或镁的氧化物的一种，负载量为载体质量的1％-10％。
2.如权利要求1所述的催化剂，其特征在于，组分之一氧化钼的负载量为载体质量的5-15％。
3.如权利要求1所述的催化剂，其特征在于，组分之二氧化镍的负载量为载体质量的5-15％。
4.如权利要求1所述的催化剂，其特征在于，组分之三氧化磷、氧化硼、氧化铜、氧化锌或氧化镁负载量为载体质量的1-5％。
5.权利要求1所述的合成吡啶的负载型催化剂的制备方法，其特征在于包括以下过程：
1)将质量比为0.9-1.1:1的蒸馏水和拟薄水铝石混合为面团状，挤压成圆柱状，在干燥箱中90-130℃干燥4-6h，置于马弗炉中以8-10℃/min升温速率升温至400-600℃焙烧4-6小时，得到载体γ-Al2O3；
2)将钼酸铵和硝酸镍溶解于蒸馏水中配制成溶液，再将磷酸二氢铵、硼酸、硝酸铜、硝酸锌、硝酸镁其中之一加入溶液；将步骤1)中的载体γ-Al2O3浸渍在上述溶液中，室温浸渍10-24h，得到湿的改性催化剂；
3)将步骤2)所得的湿的改性催化剂在温度90-130℃下，干燥6-12h,然后在500-600℃焙烧4-6h，冷却至室温，得到用于生产吡啶的催化剂。
CN201610173757.XA 2016-03-24 2016-03-24 四氢糠醇气固相催化合成吡啶的负载型催化剂及其制备方法 Pending CN105618091A (zh)

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