CN113210009A - 一种用于苯酚-甲醇合成苯甲醚的催化剂及其制备方法 - Google Patents
一种用于苯酚-甲醇合成苯甲醚的催化剂及其制备方法 Download PDFInfo
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- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 title claims abstract description 25
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 50
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
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- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
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- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
本发明公开了一种用于苯酚‑甲醇合成苯甲醚的催化剂及其制备方法。所述催化剂由分子筛载体和所负载的金属修饰组分组成，其中金属修饰组分为锡、铬、锆、钴、镁和铈中至少一种。所述催化剂的制备方法包括：（1）将分子筛加热搅拌分散在一定浓度的硝酸溶液中并烘干；（2）将金属活性组分分散负载到步骤（1）所得分子筛载体上，在特定气氛中焙烧得到金属‑分子筛催化剂。本发明所述催化剂在温和苯酚‑甲醇液相反应条件下，苯甲醚的收率大和选择性高。
Description
技术领域
本发明涉及苯酚-甲醇烷基化制备苯甲醚的技术领域，具体地说，涉及一种用于苯酚-甲醇甲基化合成苯甲醚的分子筛催化剂及其制备方法。
背景技术
甲醇是重要的基础化工原料，毒性较低、价格低廉，其高附加值化应用和研究一直是C1化工的研究热点之一。自二十世纪40年代首次报道苯酚气相烷基化反应以来，甲醇作为甲基化试剂逐渐应用于苯酚烷基化催化反应体系中，与苯酚反应合成C-烷基化产物（主要为邻、间、对甲酚）与O-烷基化产物（主要为苯甲醚），具有原料成本低、后处理简单的优势。
作为O-烷基化的产物，苯甲醚广泛应用于有机合成。苯甲醚的合成工艺主要为威廉姆逊合成法，所运用原料的经济成本和毒性较高。选用甲醇作为甲基化试剂，探索一种符合环保低毒、经济实用的制备方法，成为苯甲醚生产过程的革新方向。然而，甲醇作为弱的烷基化试剂，其活性不如硫酸二甲酯、溴甲烷等甲基化试剂。
目前应用于苯酚-甲醇反应较为成熟的是基于金属氧化物催化剂的高温气固相反应体系。虽然分子筛作为一种固体酸催化剂，利用其孔道限域作用，可有效提高苯甲醚的选择性，具有较好的发展前景，但其活性也很难实现在温和条件下高效制备苯甲醚。Chada等（Microporous and Mesoporous Materials, 300 (2020) 110144）报道了以磷酸镧负载在分子筛上作为催化剂进行苯酚与甲醇的气相反应，苯甲醚选择性在反应前16小时可保持在80%左右。高温气固非均相反应体系易产生选择性差、反应能耗较高和积碳等工艺问题，如何提高甲醇的反应活性及产物的选择性是本反应体系需要解决的关键问题。
针对上述苯酚-甲醇反应体系存在的甲醇活性不高、催化剂易积碳失活、产物选择性低等问题，本发明提供一种在液相温和条件下实现苯酚-甲醇甲基化高效反应合成苯甲醚的分子筛催化剂及其制备方法。
发明内容
本发明的目的在于提供一种用于苯酚-甲醇合成苯甲醚的催化剂及其制备方法。
上述的一种合成苯甲醚的催化剂由分子筛载体和所负载的金属修饰组分组成。以分子筛载体的重量为100%计，所负载的修饰金属的重量百分比为0.1%~10.0%。
上述的分子筛载体是指具有较高硅铝比的微孔分子筛，如Beta分子筛、ZSM-5分子筛、MCM-41分子筛、Y型分子筛等；金属修饰组分为锡、铬、锆、钴、镁和铈中至少一种。
上述金属修饰组分或该金属的氧化物或该金属任何一种离子的形式而不改变其催化作用。
上述一种用于苯酚-甲醇甲基化体系催化剂的制备方法包括如下步骤：（1）将分子筛载体搅拌分散在一定浓度的硝酸溶液中，搅拌蒸发、烘干；（2）加入金属修饰组分的前驱体盐溶液，搅拌蒸发、烘干、特定气氛中高温煅烧形成催化剂。
在上述制备方法中，步骤(1)中硝酸溶液浓度为0.1~5.0 mol/L、搅拌蒸发温度为40~90℃、烘干温度为80~120℃；步骤（2）所述的金属修饰组分的前驱体盐溶液为其金属硝酸盐或金属氯化盐溶液的一种，搅拌蒸发温度为40~90℃、烘干温度为80~120℃、煅烧气氛为氮气、空气或氢气中的至少一种、煅烧温度为300~800℃、焙烧时间为1~24 h。优选地，步骤（2）中煅烧气氛为空气、煅烧温度为500~700℃，煅烧时间为4~6 h。
与现有技术相比，本发明提供的用于苯酚-甲醇甲基化体系的分子筛催化剂制备方法简单、活性高、苯甲醚选择性高、催化稳定性好。
具体实施方式
下面结合具体实施例对本发明做出进一步地详细阐述，所述实施例只用于解释本发明，并非用于限定本发明的范围。
对比例1
直接将Beta分子筛在80℃下干燥得到催化剂。
对比例2
直接将ZSM-5分子筛在80℃下干燥得到催化剂。
实施例1
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由Beta分子筛和修饰金属Co组成，以分子筛载体的重量为100%计， Co的重量百分比含量为2.0%。制备过程为：将一定量Beta分子筛搅拌分散在3 mol/L的硝酸溶液中，60℃条件下搅拌蒸发、90℃烘干。然后，加入钴的硝酸盐溶液，80℃搅拌蒸发、120℃烘干、空气气氛400℃下煅烧5 h形成催化剂。
实施例2
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由MCM-41分子筛和修饰金属Ce组成，以分子筛载体的重量为100%计， Ce的重量百分比含量为0.5%。制备过程为：将一定量MCM-41分子筛搅拌分散在2 mol/L的硝酸溶液中，90℃条件下搅拌蒸发、110℃烘干。然后，加入铈的硝酸盐溶液，90℃条件下搅拌蒸发、100℃烘干、空气气氛500℃下煅烧4 h形成催化剂。
实施例3
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由Y型分子筛和修饰金属Cr组成，以分子筛载体的重量为100%计， Cr的重量百分比含量为3.0%。制备过程为：将一定量Y型分子筛搅拌分散在3 mol/L的硝酸溶液中，80℃条件下搅拌蒸发、100℃烘干。然后，加入铬的盐酸盐溶液，90℃条件下搅拌蒸发、120℃烘干、氮气气氛550℃下煅烧5 h形成催化剂。
实施例4
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由ZSM-5分子筛和修饰金属Zr组成，以分子筛载体的重量为100%计，Zr的重量百分比含量为6.0%。制备过程为：将一定量ZSM-5分子筛搅拌分散在4 mol/L的硝酸溶液中，70℃条件下搅拌蒸发、110℃烘干。然后，加入锆的硝酸盐溶液，90℃条件下搅拌蒸发、110℃烘干、氮气气氛600℃下煅烧6 h形成催化剂。
实施例5
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由Beta分子筛和修饰金属Sn组成，以分子筛载体的重量为100%计，Sn的重量百分比含量为8.0%。制备过程为：将一定量Beta分子筛搅拌分散在3 mol/L的硝酸溶液中，70℃条件下搅拌蒸发、90℃烘干。然后，加入锆的硝酸盐溶液，90℃条件下搅拌蒸发、110℃烘干、氮气气氛700℃下煅烧4 h形成催化剂。
实施例6
一种用于苯酚-甲醇合成苯甲醚的催化剂，所述催化剂由Beta分子筛和修饰金属Cr组成，以分子筛载体的重量为100%计，Cr的重量百分比含量为5.0%。制备过程为：将一定量Beta分子筛搅拌分散在5 mol/L的硝酸溶液中，60℃条件下搅拌蒸发、90 ℃烘干。然后，加入锆的硝酸盐溶液，80 ℃条件下搅拌蒸发、120 ℃烘干、氢气气氛500 ℃下煅烧15 h形成催化剂。
分别取0.2 g上述对比和实施案列所述催化剂，放置于高压平行反应釜中进行实验。实验条件如下：反应初始条件为氮气常压，釜内压力为溶液自生压力，苯酚与甲醇投料比为1:3.5，反应温度为192 ℃，反应时间19.5小时，反应釜搅拌速率800 r/min。活性评价结果如表1所示。
表1 催化剂活性评价结果
最后所应当说明的是，以上实施例仅用于说明本发明的技术方案而非对本发明保护范围的限制，对于本领域的普通技术人员来说，在上述说明及思路的基础上还可以做出其它不同形式的变化或变动，这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (5)
1.一种用于苯酚-甲醇合成苯甲醚的催化剂，其特征在于，催化剂由分子筛载体和所负载的金属修饰组分组成；以分子筛载体的重量为100%计，所负载的修饰金属的重量百分比为0.1%~10.0%。
2.如权利要求1所述的催化剂的制备方法，其特征在于包括如下步骤：S1.将分子筛载体搅拌分散在一定浓度的硝酸溶液中，搅拌蒸发、烘干；S2.将步骤S1所得分子筛载体加入金属修饰组分的前驱体盐溶液，搅拌蒸发、烘干、特定气氛中高温煅烧形成催化剂。
3.如权利要求2所述的制备方法，其特征在于：步骤S1中所述分子筛载体指具有高硅铝比的微孔分子筛，如Beta分子筛、ZSM-5分子筛、MCM-41分子筛、Y型分子筛等中的一种；步骤S2所述金属修饰组分为锡、铬、锆、钴、镁和铈中至少一种，所述的金属修饰组分的前驱体盐溶液为其金属硝酸盐或金属氯化盐溶液的一种。
4.如权利要求2所述的制备方法，其特征在于：步骤S1中硝酸溶液浓度为0.1~5.0 mol/L、搅拌蒸发温度为40~90℃、烘干温度为80~120 ℃；优选地，步骤S2中的搅拌蒸发温度为40~90℃、烘干温度为80~120℃、煅烧气氛为氮气、空气或氢气中的至少一种、煅烧温度为300~800℃、焙烧时间为1~24 h；步骤S2中煅烧气氛为空气、煅烧温度为500~700℃，煅烧时间为4~6 h。
5.权利要求1~4所述的金属-分子筛催化剂在苯酚-甲醇烷基化合成苯甲醚反应中的应用。
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