CN109111345B - 一种乙醇催化转化制备甲基苯甲醇的方法 - Google Patents

一种乙醇催化转化制备甲基苯甲醇的方法 Download PDF

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CN109111345B
CN109111345B CN201811048420.1A CN201811048420A CN109111345B CN 109111345 B CN109111345 B CN 109111345B CN 201811048420 A CN201811048420 A CN 201811048420A CN 109111345 B CN109111345 B CN 109111345B
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transition metal
phosphate
ethanol
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benzyl alcohol
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CN109111345A (zh
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陆安慧
王庆楠
李文翠
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Qingdao Sanli Bennuo New Materials Ltd By Share Ltd
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Dalian University of Technology
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Abstract

本发明提供了一种乙醇催化转化制备甲基苯甲醇的方法及所用催化剂，属于化工催化技术领域。本发明的目的在于开发一条从乙醇出发制备甲基苯甲醇的路线，并提供该催化转化路线所需催化剂，特别强调采用工艺简单地单床层催化剂实现该催化反应过程，期望能成为芳烃含氧化合物增产的重要替代路线。本发明提供了从乙醇出发通过催化转化直接生产甲基苯甲醇的路径及相应催化剂，甲基苯甲醇的选择性高达60％，同时所制备的催化剂具有优异的稳定性。该反应路线生成大量的氢气，且不含有CO等气体，可直接用于化学反应和燃料电池中。此外该路线还生成了高碳链醇，其可作为燃料或油品添加剂，部分替代石油产品，减少我国对原油的依赖。

Description

一种乙醇催化转化制备甲基苯甲醇的方法
技术领域
本发明涉及一种乙醇催化转化制备甲基苯甲醇的方法及所用催化剂，属于化工催化技术领域。
背景技术
与芳烃相比，甲基苯甲醇具有含氧功能化基团，在氧化、聚合等反应中表现出高的反应活性，可用于生产医药，也可以直接替代二甲苯作为生产邻苯二甲酸和邻苯二甲酸酐的前体，具有重要的医药和工业应用价值。目前其生产方法主要有二甲苯空气氧化法、甲苯羰基化法等[Catal.Rev.,1991,33,319]。二甲苯和甲苯是通过石油产品萘酚的蒸汽裂解或催化重整生产。此外，炼油厂目标转向汽油导致全球芳烃原料短缺[Science 2014,344,616；Angew.Chem.Int.Ed. 2013,52,11980]。因此，亟需开发一条从其它可替代资源出发，通过催化转化直接合成甲基苯甲醇的路线。
乙醇来源广泛，通过生物质和陈粮发酵的全球产量高达1亿吨(2015年)。此外，以生活废弃物、生物质、化石资源等为原料，通过部分氧化可以制备大量的合成气；由合成气制乙醇工业化的开发使得乙醇的可用性进一步增加[US Patent US2016/0311740 A1]。乙醇作为一种可用的低碳含氧平台分子，通过碳- 碳偶联反应可转化为高碳数的含氧化学品。然而，由于乙醇链增长过程中存在复杂的竞争反应，目前报道的催化剂对于高碳数产物的选择性都较低，尤其是甲基苯甲醇(<3％)。开发一条由乙醇直接催化转化制备甲基苯甲醇的路线符合我国能源可持续发展的战略需求，可以替代或部分替代石油基路线，缓解我国芳烃资源的短缺，保证我国经济社会发展的安全和稳定。
发明内容
本发明的目的在于开发一条从乙醇出发制备甲基苯甲醇的路线，并提供该催化转化路线所需催化剂，特别强调采用工艺简单地单床层催化剂实现该催化反应过程，期望能成为芳烃含氧化合物增产的重要替代路线。
其反应式如下：
Figure GDA0002505768500000021
与传统的石油基路线相比，该反应路径具有原子经济性高、环境友好、气液易于分离等优点，是具有颠覆性的甲基苯甲醇生产路线。该反应路线的反应温度为150-450℃，甲基苯甲醇的总选择性高达60％，具有良好的工业应用前景。所以本专利的创新包括反应路径创新和催化剂合成创新两个方面。
本发明的技术方案：
一种乙醇催化转化制备甲基苯甲醇的方法，步骤如下：
(1)配制一定浓度的过渡金属盐水溶液和/或过渡金属盐醇溶液；
(2)以步骤(1)配制的过渡金属盐水溶液和/或过渡金属盐醇溶液，等体积浸渍磷酸盐；浸渍完后室温静置0.5～2h；
(3)将步骤(2)静置后的混合物于50℃烘箱放置干燥8～20h；
(4)将步骤(3)干燥后的产物于350～450℃经氧气气氛氧化1～5h，然后在300～700℃氢气还原0.5～2h，即得到过渡金属修饰的磷酸盐催化剂；
(5)在反应温度100～450℃，反应压力1-50atm条件下，将乙醇通入载有过渡金属修饰的磷酸盐催化剂的反应器中，一步法生产甲基苯甲醇。
步骤(1)中，所述的过渡金属盐水溶液浓度为0.08g/mL～1.0g/mL，过渡金属盐醇溶液浓度为0.08～0.3g/mL；过渡金属的可溶性盐选自氯化物、硝酸盐、乙酰丙盐、硫酸盐、醋酸盐中的一种或两种以上混合；醇溶剂选择甲醇和/或乙醇。
步骤(4)中，氧气氧化的浓度为0.01～20vol％O2/N2、O2/He、O2/Ar中的一种；氢还原浓度为5～20vol％H2/N2、H2/He、H2/Ar中的一种。
所用催化剂为过渡金属修饰的磷酸盐，以重量百分比计所包含的组分：
(1)过渡金属选自Co、Ni、Cu、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合；过渡金属是氧化态或金属态；采用过渡金属的硝酸盐、氯化物、乙酸丙酮盐、硫酸盐或醋酸盐为前驱体，修饰量为磷酸盐重量的0.01～50 wt％；
(2)磷酸盐为羟基金属磷酸盐(AxByCzDmEn(OH)2(PO4)6，x+y+z+m+n＝9～ 10，9～10≥x,y,z,m,n≥0)和/或金属磷酸盐(AxByCzDmEn(PO4)2，x+y+z+m+n＝3, 3≥x,y,z,m,n≥0)，其中A、B、C、D和E相同或不同，选自Mg、Ca、Sr、Ba、 Pb中的一种或两种以上组合；磷酸盐是一种或两种以上的机械混合物。
所述的过渡金属，优选Co，其修饰量为磷酸盐的0.01～50wt％，优选范围为0.1～5wt％。
所述的磷酸盐优选Ca10(OH)2(PO4)6。此外优选固定床、常压反应器。
与现有技术相比，本发明提供了从乙醇出发通过催化转化直接生产甲基苯甲醇的路径及相应催化剂，甲基苯甲醇的选择性高达60％，同时所制备的催化剂具有优异的稳定性。该反应路线生成大量的氢气，且不含有CO等气体，可直接用于化学反应和燃料电池中。此外该路线还生成了高碳链(C4-12)醇，其可作为燃料或油品添加剂，部分替代石油产品，减少我国对原油的依赖。此外，甲基苯甲醇和高碳链脂肪醇的极性、水溶性、分馏温度等物性参数相差较大，易于通过精馏分离，后期操作成本低，所以本发明所提供的反应路径具有极大地工业化应用前景。
附图说明
图1是实施例4的反应温度为325℃下具体的产物分布的图谱。
具体实施方式
以下通过一些实施例对本发明做出详细表述，但本发明并不局限于这些实施例。
磷酸盐用HAP-M和PO-M表示，其中：
HAP表示羟基金属磷酸盐，PO表示金属磷酸盐，M指代金属，是Ca、Mg、Ba、 Sr、Pb等中的一种或几种。
催化剂用xMetal-HAP-M和xMetal-PO-M载体表示，其中：
x＝Metal修饰量占催化剂总重量的百分含量×100。
实施例1
Co物种修饰HAP-Ca催化剂的制备过程：
(1)取HAP-Ca，在120℃气流烘箱中干燥2h，除去表面物理吸附水；
(2)在25℃下，取按表1中编号5配制的Co(NO3)2·6H2O水溶液等体积浸渍步骤(1)干燥得到的HAP-Ca上，静置2h；
(3)将步骤(2)静置后的混合物，在50℃干燥10h，得到催化剂前驱体；
(4)将步骤(3)获得的催化剂前驱体于350℃经氧气气氛氧化2h，随后在400℃氢还原2h(10vol％H2/N2)，即得Co修饰的HAP-Ca催化剂，记为 Co-HAP-Ca(表1中编号5)催化剂。
(5)通过控制金属盐溶液的浓度和浸渍的次数可以控制Co的修饰量，制备方法与上述步骤相同，对应表1中编号2、3、5、7、8和9。
其他催化剂的制备条件过程与实施例1相同。样品编号与制备条件的对应关系如表1所示。
表1实施例1的样品编号与制备条件的对应关系
Figure GDA0002505768500000051
Figure GDA0002505768500000061
实施例2
Co和Ni双金属物种修饰HAP-Ca催化剂的制备过程：
(1)取HAP-Ca，在120℃气流烘箱中干燥2h，除去表面物理吸附水；
(2)在25℃下，取按表1中编号5配制的Co(NO3)2·6H2O水溶液和编号 19配制的Ni(NO3)2·6H2O水溶液等体积混合，然后等体积浸渍步骤(1)干燥得到的HAP-Ca上，静置2h；
(3)将步骤(2)静置后的混合物，在50℃干燥10h，得到催化剂前驱体；
(4)将步骤(3)获得的催化剂前驱体于350℃经氧气气氛氧化2h，随后在400℃氢还原2h(10vol％H2/N2)，即得Ni和Co修饰的HAP-Ca催化剂，记为CoNi-HAP-Ca(表1中编号24)催化剂。
实施例3
不同过渡金属修饰磷酸盐催化乙醇制甲基苯甲醇。
以乙醇为原料，在固定床反应器内开展乙醇提质反应。反应条件如下：在内径为8mm的固定床反应器内装填催化剂，常压，反应温度325℃，乙醇液相流量为0.3mL/h。反应稳定后，反应原料及产物利用在线色谱分析。样品编号与乙醇提质活性的对应关系如表2所示。
表2实施例3的样品编号与乙醇转化率和甲基苯甲醇选择性的对应关系
Figure GDA0002505768500000062
Figure GDA0002505768500000071
实施例4
在不同温度下Co-HAP-Ca催化乙醇制甲基苯甲醇。
以乙醇为原料，在固定床反应器内开展乙醇提质反应。反应条件如下：在内径为8mm的固定床反应器内装填催化剂，常压，反应温度100～450℃,乙醇液相流量为0.3mL/h，WHSV＝1.0h-1。反应稳定后，反应原料及产物利用在线色谱分析。反应结果如表3所示。
反应温度为325℃下的产物分布如图1所示。
表3实施例4的反应温度与Co-HAP-Ca催化乙醇制甲基苯甲醇活性的对应关系
温度 转化率/％ 选择性/％
100 0.5 0.5
250 6.9 12.8
275 11.4 34.7
300 19.2 49.2
325 34.9 60.1
350 53.1 65.1
400 85.1 65.8
450 >99 50.5
实施例5
在325℃下，乙醇液相流量对甲基苯甲醇选择性的调控。
以乙醇为原料，在固定床反应器内开展乙醇提质反应。反应条件如下：在内径为8mm的固定床反应器内装填催化剂，常压，反应温度325℃,乙醇液相流量为0.05-2.7mL/h。反应稳定后，反应原料及产物利用在线色谱分析。反应结果如表4所示。
表4实施例5的乙醇液相流量对甲基苯甲醇选择性的调控
流量(mL/h) 转化率/％ 选择性/％
0.05 69.7 42.1
0.1 55 47.8
0.15 41.2 52.1
0.2 37.3 54.2
0.27 33.5 57.4
0.32 25.8 58.0
2.7 5.2 18.9

Claims (6)

1.一种乙醇催化转化制备甲基苯甲醇的方法，其特征在于，步骤如下：
(1)配制过渡金属盐水溶液和/或过渡金属盐醇溶液；
(2)以步骤(1)配制的过渡金属盐水溶液和/或过渡金属盐醇溶液，等体积浸渍磷酸盐；浸渍完后室温静置0.5～2h；
(3)将步骤(2)静置后的混合物于50℃烘箱放置干燥8～20h；
(4)将步骤(3)干燥后的产物于350～450℃经氧气气氛氧化1～5h，然后在300～700℃氢气还原0.5～2h，即得到过渡金属修饰的磷酸盐催化剂；
所述的过渡金属修饰的磷酸盐催化剂包括两部分：过渡金属和磷酸盐，过渡金属修饰量为磷酸盐重量的0.01～50wt％；过渡金属修饰的磷酸盐催化剂以重量百分比计所包含的组分：
1)过渡金属为Co、Ni、Cu、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合；过渡金属是氧化态或金属态；采用过渡金属的硝酸盐、氯化物、乙酸丙酮盐、硫酸盐或醋酸盐为前驱体，修饰量为磷酸盐重量的0.1～50wt％；
2)磷酸盐为羟基金属磷酸盐和/或金属磷酸盐，其中，羟基金属磷酸盐为AxByCzDmEn(OH)2(PO4)6，x+y+z+m+n＝9～10，9～10≥x,y,z,m,n≥0；金属磷酸盐为AxByCzDmEn(PO4)2，x+y+z+m+n＝3,3≥x,y,z,m,n≥0；其中A、B、C、D、E相同或不同，选自Mg、Ca、Sr、Ba、Pb中的一种或两种以上组合；磷酸盐是一种或两种以上的机械混合物；
(5)在反应温度300～450℃，反应压力1-50atm条件下，将乙醇通入载有过渡金属修饰的磷酸盐催化剂的反应器中，乙醇的液相流量为0.05～0.32mL/h，一步法生产甲基苯甲醇。
2.根据权利要求1所述的方法，其特征在于，步骤(1)中，所述的过渡金属盐水溶液的浓度为0.08g/mL～1.0g/mL，过渡金属盐醇溶液的浓度为0.08～0.3g/mL。
3.根据权利要求1或2所述的方法，其特征在于，所述的过渡金属对应的可溶性盐为氯化物、硝酸盐、乙酰丙盐、硫酸盐、醋酸盐中的一种或两种以上混合；醇溶剂选择甲醇和/或乙醇。
4.根据权利要求1或2所述的方法，其特征在于，步骤(4)中，氧气氧化的浓度为0.01～20vol％O2/N2、0.01～20vol％O2/He、0.01～20vol％O2/Ar中的一种；氢还原浓度为5～20vol％H2/N2、5～20vol％H2/He、5～20vol％H2/Ar中的一种。
5.根据权利要求3所述的方法，其特征在于，步骤(4)中，氧气氧化的浓度为0.01～20vol％O2/N2、0.01～20vol％O2/He、0.01～20vol％O2/Ar中的一种；氢还原浓度为5～20vol％H2/N2、5～20vol％H2/He、5～20vol％H2/Ar中的一种。
6.根据权利要求1所述的方法，其特征在于，所述的过渡金属修饰的磷酸盐催化剂中的过渡金属为Co，其修饰量为磷酸盐的0.01～50wt％。
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