CN109111344A - 一种乙醇催化转化制备甲基苯甲醇的方法及所用催化剂 - Google Patents

一种乙醇催化转化制备甲基苯甲醇的方法及所用催化剂 Download PDF

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CN109111344A
CN109111344A CN201811048385.3A CN201811048385A CN109111344A CN 109111344 A CN109111344 A CN 109111344A CN 201811048385 A CN201811048385 A CN 201811048385A CN 109111344 A CN109111344 A CN 109111344A
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metal
alcohol
transition metal
dehydrogenation
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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。本发明开发一条从绿色可持续的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采用的催化剂。与传统的石油基路线相比，该反应路径具有过程简单、环境友好、产物易分离等优点，是具有颠覆性的甲基苯甲醇生产路线。该路线的反应温度为150‑450℃，甲基苯甲醇的总选择性高达72％，具有良好的工业应用前景。本专利的创新为催化合成创新和反应路径的创新两个方面。

Description

一种乙醇催化转化制备甲基苯甲醇的方法及所用催化剂
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
甲基苯甲醇具有含氧功能化基团，是重要的有机化工中间体，主要由二甲苯在高压(0.4-3.0MPa)下氧化生成。二甲苯是通过石油产品萘酚的蒸汽裂解或催化重整生产。然而在苛刻的氧化条件下，所得目标产物进一步深度氧化，产生大量的酸和酯的衍生物，导致目标产物选择性低(～40％)，产品分离困难。此外，炼油厂目标转向汽油使全球芳烃原料短缺。因此，亟需开发一条从其它可替代资源出发直接合成甲基苯甲醇的路线。
生物质发酵法以及由合成气制乙醇工业化开发使得乙醇的可用性显著增加。2015年，我国乙醇产量高达1500万吨。乙醇作为一种可用的低碳含氧平台分子，通过脱氢、碳-碳偶联、环化脱氢反应转化为乙醛、高碳醇(C4-12)等含氧化学品。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，尤其是芳香含氧化学品。Resasco等人采用乙醛-乙醇混合物为反应物，在MgO和MgO改性的八面沸石上检测到仅少量的甲基苯甲醛生成[ChemSusChem 2016,9,736]。Flaherty等人采用乙醛-乙醇混合物共进料(乙醛/乙醇＝1:3)，在羟基磷灰石催化剂上检测到了有甲基苯甲醛和甲基苄醇生成，其选择性分别为30％和3％，乙醛转化率为55％[ACS Catal.2016,6,7278]。综上所述，由乙醇高效催化转化制备芳香含氧化合物极具挑战性。
因此，开发一条由乙醇直接催化转化制备甲基苯甲醇的路线既节能高效，又符合我国可持续发展的战略需求，可以替代或部分替代石油基路线，缓解我国芳烃的缺口，保障我国社会经济发展安全。
发明内容
本发明的目的在于开发一条从可持续的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采用的催化剂，特别强调低的反应温度和双床层催化剂反应体系。
其总反应式如下：
与传统的石油基路线相比，该反应路径具有过程简单、环境友好、产物易分离等优点，是具有颠覆性的甲基苯甲醇生产路线。该路线的反应温度为150-450℃，甲基苯甲醇的总选择性高达72％，远高于目前报道催化剂的水平，具有良好的工业应用前景。本专利的创新点包括催化合成创新和反应路径的创新两个方面。
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)脱氢催化剂的制备
(1.1)配制过渡金属盐水溶液和/或醇溶液；
(1.2)以步骤(1.1)配制的过渡金属盐水溶液和/或醇溶液等体积浸渍载体1～3次；浸渍完后室温静置0.1～2h；
(1.3)将步骤(1.2)静置后的混合物于50℃烘箱放置干燥0.1～20h；
(1.4)将步骤(1.3)干燥后的产物于100～150℃干燥0.5～2h，催化剂前驱体再依次于惰性、氢气氛围处理或直接于氢气氛围处理，即得到载体负载的过渡金属催化剂即为脱氢催化剂，记为过渡金属/载体；
所述的过渡金属选自Cu、Ni、Co、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合。
所述的载体为炭或炭/氧化物复合物时，所得催化剂前驱体于350～450℃惰性氛围下处理1～5h，随后在350～600℃经氢气氛围还原0.5-5h；
所述的载体为Al2O3、SiO2、ZrO2、ZnO、MgO时，所得催化剂前驱体于350～600℃直接经氢气气氛还原2～5h；
(2)芳构化催化剂的制备
(2.1)将金属A、B、C、D和E的硝酸盐加入到水中溶解，配制相应的水溶液；
(2.2)将磷酸氢二铵加入到水中溶解，配制相应的水溶液；
(2.3)将步骤(2.1)配制的硝酸盐溶液逐滴加入到步骤(2.2)中，并充分搅拌；其中，金属与磷的摩尔比为1.5～1.67；
(2.4)采用氨水调节步骤(2.3)所得浑浊液的pH值为8～12，然后在50～80℃搅拌24h；
(2.5)将步骤(2.4)所得的沉淀物在一定处理气氛下于25～200℃干燥1～10h，再于350～700℃热处理0.5～10h，即得到所述金属羟基磷酸盐即为芳构化催化剂；
所述的芳构化催化剂为金属羟基磷酸盐(AxByCzDmEn(OH)2(PO4)6，x+y+z+m+n＝9～10，9～10≥x,y,z,m,n≥0)和金属磷酸盐(AxByCzDmEn(PO4)2，x+y+z+m+n＝3，3≥x,y,z,m,n≥0)；
所述的金属A、B、C、D和E相同或不同，选自Mg、Ca、Sr、Ba、Pb、Cu、Ni、Co、Zn、Zr、Hf中的一种或两种以上组合；
当芳构化催化剂中包含过渡金属Cu、Ni、Co、Zn、Zr、Hf时，将步骤(2.4)所得沉淀物于350～550℃热处理；
(3)催化剂装填方式
(3.1)将上述步骤制备的脱氢催化剂和芳构化催化剂分别压片、成型、过筛到指定颗粒大小；
(3.2)将步骤(3.1)中成型的脱氢催化剂和芳构化催化剂依次装填到单根固定管中，二者之间用石英棉隔开；
(3.3)将步骤(3.2)中所得的双床层催化剂在氢气氛围下于350～750℃还原1～5h。
(4)在反应温度150～450℃，反应压力1-50atm条件下，将乙醇通入载有上述催化剂的反应器中，生产甲基苯甲醇。
步骤(1.1)中，所述的过渡金属盐的溶液为水溶液和/或醇溶液；所述的过渡金属盐水溶液浓度为0.075g/mL～0.75g/mL，过渡金属盐醇溶液浓度为0.075～0.225g/mL；过渡金属的可溶性盐选自氯化物、硝酸盐、乙酰丙酮盐、硫酸盐、醋酸盐中的一种或两种以上组合；醇溶剂选择甲醇和/或乙醇。
步骤(1.4)中，惰性氛围是He、Ar、N2中的一种或两种以上组合。
步骤(2.5)中，处理气氛是H2、He、Ar、N2、O2中一种或两种以上组合。
步骤(1.4)和步骤(3.3)中，氢还原浓度为5～20vol％H2/N2、H2/He、H2/Ar中的一种。
一种乙醇催化转化制备甲基苯甲醇的催化剂，所述的催化剂包括脱氢催化剂和芳构化催化剂两部分；两个催化剂装填在一个反应器中或各自独立的反应器中；以重量百分比计所包含的组分：
(1)脱氢催化剂，为过渡金属或其氧化物；过渡金属是单一或多元复合组分；采用过渡金属的氯化物、硝酸盐、乙酸丙酮盐、硫酸盐或醋酸盐为前驱体，通过焙烧和还原得到金属或其氧化物，或负载在载体上，担载量为载体重量的0.01～50wt％；
所述的过渡金属选自Cu、Ni、Co、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合；
(2)芳构化催化剂为金属羟基磷酸盐和/或金属磷酸盐，金属羟基磷酸盐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AxByCzDmEn(PO4)2，x+y+z+m+n＝3，3≥x,y,z,m,n≥0；磷酸盐化合物任选一种或两种以上的机械混合物。
所述的金属A、B、C、D和E相同或不同，选自Mg、Ca、Sr、Ba、Pb、Cu、Ni、Co、Zn、Zr、Hf中的一种或两种以上组合；
所述的脱氢催化剂中，过渡金属优选Cu，采用负载型催化剂，载体为Al2O3、SiO2、ZrO2、ZnO、MgO、炭、炭/氧化物复合物。优选炭载体，Cu的担载量为炭载体的0.01～50wt％，优选为0.1～5wt％。
所述的芳构化催化剂优选CaxCoy(OH)2(PO4)6、Ca10(OH)2(PO4)6、Sr10(OH)2(PO4)6。
此外优选固定床、常压反应器。采用单个反应器时，脱氢催化剂和芳构化催化剂可以为机械混合的单床层或者双床层结构。采用多反应器时，脱氢催化剂床层在前。
与现有技术相比，本发明提供了从来源广泛的乙醇出发直接生产甲基苯甲醇的路径及相应催化剂，在225℃的反应温度下，甲基苯甲醇的选择性高达72％。该反应路线生成大量的氢气，可直接用于燃料电池中。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。脂肪醇和甲基苯甲醇易于通过精馏分离，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1的10Cu/炭催化剂的XRD图谱；
图2是实施例2的10Cu/SiO2催化剂的XRD图谱；
图3是实施例6的不同的催化剂混料方式；
图4是实施例8的反应温度为225℃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。
脱氢催化剂用wMetal/载体表示，其中：
w＝Metal担载量占催化剂总重量的百分含量×100。
芳香化催化剂磷酸盐用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Mg、Ca、Sr、Ba、Pb、Cu、Ni、Co、Zn、Zr、Hf等中的一种或几种。
实施例1
炭负载Cu催化剂的制备过程：
(1)取炭载体，在120℃烘箱中干燥2h，除去表面物理吸附水；
(2)配制质量浓度分别为0.75g/mL的Cu(NO3)2·3H2O水溶液；
(3)在25℃下，取(2)中溶液等体积浸渍到炭上，静置0.1h；
(4)将步骤(3)静置后的混合物在50℃干燥0.5h，得到催化剂前驱体；
(5)将步骤(4)得到的前驱体在140℃干燥0.5h，于350℃惰性氛围处理1h，然后在450℃经氢气气氛处理2h，即得到炭负载的铜催化剂，记为10Cu/炭(表1中编号1)。
10Cu/炭催化剂的XRD图谱如图1所示。
表1实施例1的样品编号与制备条件的对应关系
实施例2
SiO2负载Cu催化剂的制备过程：
(1)取SiO2载体，在120℃烘箱中干燥2h，除去表面物理吸附水；
(2)配制质量浓度分别为0.75g/mL的Cu(NO3)2·3H2O水溶液；
(3)在25℃下，取(2)中溶液等体积浸渍到SiO2上，静置2h；
(4)将步骤(3)静置后的混合物在50℃干燥8h，得到催化剂前驱体；
(5)将步骤(4)得到的前驱体于450℃经氢气气氛处理2h，即得到SiO2负载的铜催化剂，记为10Cu/SiO2(表1中编号2)。
10Cu/SiO2催化剂的XRD图谱如图2所示。
其他氧化物担载金属催化剂的制备条件过程与实施例2相同。样品编号与制备条件的对应关系如表1所示。
实施例3
金属羟基磷酸盐Ca8Co2(OH)2(PO4)6的制备过程：
(1)将硝酸钙和硝酸钴加入水中溶解，配制成总摩尔分数为0.6M的水溶液；
(2)将磷酸氢二铵加入水中溶解，配制成摩尔分数为0.4M的水溶液，其中Ca+Co与P的摩尔比为1.67；
(3)将步骤(1)配制的硝酸钙和硝酸钴溶液逐滴(10mL/min)加入到(2)中，并充分搅拌60min；；
(4)在上述步骤(3)所得浑浊液中加入浓氨水(～25wt％)，调节整个体系的pH值大于11，然后在80℃搅拌24h；
(5)将步骤(4)所得的粉色沉淀物在特定气氛下于50℃干燥10h，再于550℃焙烧2h，即得到所述Ca8Co2(OH)2(PO4)6。
通过控制加入硝酸钙和硝酸钴的质量比值，可以调节Ca和Co的原子比例，其制备方法与实施例3相同。样品编号与制备条件的对应关系如表2所示。
通过控制所加入的硝酸盐，可以调节金属原子的种类和比例，其制备方法与实施例3相同。样品编号与制备条件的对应关系如表2所示。
表2实施例3的样品编号与制备条件的对应关系
实施例4
金属磷酸盐Ca2Co(PO4)2的制备过程：
(1)将氢氧化钙和氢氧化钴(Ca2+/Co2+＝2:1，摩尔比)固体分散到水中，配制成相应的固体悬浮液，搅拌；
(2)配制10wt％H3PO4溶液；
(3)将步骤(2)配制的磷酸溶液逐滴加入到(1)中，并充分搅拌，通过悬浮物的pH值控制加入磷酸的量，然后剧烈搅拌3h；
(4)将步骤(3)所得的白色沉淀物在特定气氛下于25～200℃干燥2h，再于600℃焙烧2h，即得到所述Ca2Co(PO4)2。
通过控制加入硝酸钙和硝酸钴的质量比值，可以调节Ca和Co的原子比例，其制备方法与实施例4相同。样品编号与制备条件的对应关系如表2所示。
通过控制所加入的硝酸盐，可以调节金属原子的种类和比例，其制备方法与实施例4相同。样品编号与制备条件的对应关系如表2所示。
实施例5
单反应器、双床层结构的脱氢和芳构化复合催化剂催化乙醇到甲基苯甲醇的活性
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225℃，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3所示。
表3实施例5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
实施例6
脱氢和芳构化复合催化剂混合方式对甲基苯甲醇选择性影响
以乙醇为原料，在固定床反应器内开展乙醇提质反应，脱氢催化剂为10Cu/炭，芳构化催化剂为HAP-8Ca2Co。反应条件如下：常压，反应温度225℃,乙醇液相流量为0.3mL/h，WHSV＝1.0h-1。采用三种催化剂混料方式：单反应器单床层(1)、单反应器双床层(2)、双反应器(3)。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。
催化剂混料方式如图3所示。
表4实施例6的脱氢和芳构化复合催化剂混合方式调变甲基苯甲醇选择性
实施例7
单反应器、双床层结构的脱氢和芳构化复合催化剂催化不同浓度乙醇转化的产物分布
以乙醇为原料，在固定床反应器内开展乙醇提质反应，脱氢催化剂为10Cu/炭，芳构化催化剂为HAP-8Ca2Co。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225℃,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5所示。
表5实施例7的乙醇浓度对甲基苯甲醇选择性的调变
流量(mL/h) 转化率/％ 选择性/％
0.05 34.8 50.1
0.1 27.5 58.9
0.15 21.0 62.3
0.2 18.6 67.1
0.27 16.1 72.5
0.32 13.4 72.1
2.7 2.2 28.9
实施例8
单反应器、双床层结构的脱氢和芳构化复合催化剂在不同温度下催化乙醇转化的产物分布
以乙醇为原料，在固定床反应器内开展乙醇提质反应，脱氢催化剂为10Cu/炭，芳构化催化剂为HAP-8Ca2Co。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6所示。
反应温度为225℃下的产物分布如图4所示。
表6实施例8的不同温度下催化乙醇转化的产物分布
温度 转化率/％ 选择性/％
150 1.2 42.7
175 3.9 61.1
200 8.9 68.3
225 16.1 72.5
250 20.4 67.2
275 28.7 65.0
300 37.7 65.3
325 36.7 54.0
350 45.8 43.1
400 75.1 22.0

Claims (9)

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)制备脱氢催化剂
(1.1)配制过渡金属盐水溶液和/或醇溶液；
(1.2)以步骤(1.1)配制的过渡金属盐水溶液和/或醇溶液等体积浸渍载体1～3次；浸渍完后室温静置0.1～2h；
(1.3)将步骤(1.2)静置后的混合物于50℃烘箱放置干燥0.1～20h；
(1.4)将步骤(1.3)干燥后的产物于100～150℃干燥0.5～2h，催化剂前驱体再依次于惰性、氢气氛围处理或直接于氢气氛围处理，即得到载体负载的过渡金属催化剂即为脱氢催化剂，记为过渡金属/载体；
所述的过渡金属选自Cu、Ni、Co、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合；
所述的载体为炭或炭/氧化物复合物时，所得催化剂前驱体于350～450℃惰性氛围下处理1～5h，随后在350～600℃经氢气氛围还原0.5-5h；
所述的载体为Al2O3、SiO2、ZrO2、ZnO或MgO时，所得催化剂前驱体于350～600℃直接经氢气气氛还原2～5h；
(2)制备芳构化催化剂
(2.1)将金属A、B、C、D和E的硝酸盐加入到水中溶解，配制相应的水溶液；
(2.2)将磷酸氢二铵加入到水中溶解，配制相应的水溶液；
(2.3)将步骤(2.1)配制的硝酸盐溶液逐滴加入到步骤(2.2)中，并充分搅拌；其中，金属与磷的摩尔比为1.5～1.67；
(2.4)采用氨水调节步骤(2.3)所得浑浊液的pH值为8～12，然后在50～80℃搅拌24h；
(2.5)将步骤(2.4)所得的沉淀物在一定处理气氛下于25～200℃干燥1～10h，再于350～700℃热处理0.5～10h，即得到所述金属羟基磷酸盐即为芳构化催化剂；
所述的芳构化催化剂为金属羟基磷酸盐(AxByCzDmEn(OH)2(PO4)6，x+y+z+m+n＝9～10，9～10≥x,y,z,m,n≥0)和金属磷酸盐(AxByCzDmEn(PO4)2，x+y+z+m+n＝3，3≥x,y,z,m,n≥0)；
所述的金属A、B、C、D和E相同或不同，选自Mg、Ca、Sr、Ba、Pb、Cu、Ni、Co、Zn、Zr、Hf中的一种或两种以上组合；
当芳构化催化剂中包含过渡金属Cu、Ni、Co、Zn、Zr、Hf时，将步骤(2.4)所得沉淀物于350～550℃热处理；
(3)催化剂装填方式
(3.1)将上述步骤制备的脱氢催化剂和芳构化催化剂分别压片、成型、过筛到指定颗粒大小；
(3.2)将步骤(3.1)中成型的脱氢催化剂和芳构化催化剂依次装填到单根固定管中，二者之间用石英棉隔开；
(3.3)将步骤(3.2)中所得的双床层催化剂在氢气氛围下于350～750℃还原1～5h；
(4)在反应温度150～450℃，反应压力1-50atm条件下，将乙醇通入载有上述催化剂的反应器中，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(1.1)中，所述的过渡金属盐的溶液为水溶液和/或醇溶液；所述的过渡金属盐水溶液浓度为0.075g/mL～0.75g/mL，过渡金属盐醇溶液浓度为0.075～0.225g/mL；过渡金属的可溶性盐选自氯化物、硝酸盐、乙酰丙酮盐、硫酸盐、醋酸盐中的一种或两种以上组合；醇溶剂选择甲醇和/或乙醇。
3.根据权利要求1或2所述的方法，其特征在于，步骤(1.4)中，惰性氛围是He、Ar、N2中的一种或两种以上组合。
4.根据权利要求3所述的方法，其特征在于，步骤(2.5)中，处理气氛是H2、He、Ar、N2、O2中一种或两种以上组合。
5.根据权利要求1、2或4所述的方法，其特征在于，步骤(1.4)和步骤(3.3)中，氢还原浓度为5～20vol％H2/N2、H2/He、H2/Ar中的一种。
6.根据权利要求3所述的方法，其特征在于，步骤(1.4)和步骤(3.3)中，氢还原浓度为5～20vol％H2/N2、H2/He、H2/Ar中的一种。
7.一种乙醇催化转化制备甲基苯甲醇的催化剂，其特征在于，所述的催化剂包括脱氢催化剂和芳构化催化剂两部分；两个催化剂装填在一个反应器中或各自独立的反应器中；以重量百分比计所包含的组分：
(1)脱氢催化剂，为过渡金属或其氧化物；过渡金属是单一或多元复合组分；采用过渡金属的氯化物、硝酸盐、乙酸丙酮盐、硫酸盐或醋酸盐为前驱体，通过焙烧和还原得到金属或其氧化物，或负载在载体上，担载量为载体重量的0.01～50wt％；
所述的过渡金属选自Cu、Ni、Co、Ag、Pd、Rh、Ru、Pt、Ir、Zn、Y中的一种或两种以上组合；
(2)芳构化催化剂为金属羟基磷酸盐和/或金属磷酸盐，金属羟基磷酸盐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AxByCzDmEn(PO4)2，x+y+z+m+n＝3，3≥x,y,z,m,n≥0；磷酸盐化合物任选一种或两种以上的机械混合物；
所述的金属A、B、C、D和E相同或不同，选自Mg、Ca、Sr、Ba、Pb、Cu、Ni、Co、Zn、Zr、Hf中的一种或两种以上组合。
8.根据权利要求7所述的脱氢催化剂，其特征在于，所述的过渡金属优选Cu，采用负载型催化剂，载体为Al2O3、SiO2、ZrO2、ZnO、MgO、炭、炭/氧化物复合物，所述的载体优选炭，Cu担载量为炭载体的0.01～50wt％。
9.根据权利要求7所述的芳构化催化剂，其特征在于，金属羟基磷酸盐优选CaxCoy(OH)2(PO4)6、Ca10(OH)2(PO4)6、Sr10(OH)2(PO4)6。
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