CN107266290A - 一种甲基丙烯酸甲酯联产甲基烯丙醇的方法 - Google Patents

一种甲基丙烯酸甲酯联产甲基烯丙醇的方法 Download PDF

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CN107266290A
CN107266290A CN201710595561.4A CN201710595561A CN107266290A CN 107266290 A CN107266290 A CN 107266290A CN 201710595561 A CN201710595561 A CN 201710595561A CN 107266290 A CN107266290 A CN 107266290A
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methyl methacrylate
coproducing
alcohol
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allyl alcohol
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李善龙
刘士华
陈新建
汪青海
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Heze HOLLEY New Material Co Ltd
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SHANDONG YIDALI CHEMICAL Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein

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Abstract

本发明涉及联产工艺技术领域，特别涉及一种甲基丙烯酸甲酯联产甲基烯丙醇的方法。本发明采用叔丁醇/异丁烯为原料氧化生成甲基丙烯酸，甲基丙烯酸被氧化酯化生产甲基丙烯酸甲酯；而甲基丙烯醛作为原料进行选择还原加氢得到甲基烯丙醇，由此，实现了甲基丙烯酸甲酯联产甲基烯丙醇工艺。本发明工艺简单，产品规划合理，生产成本低，原子利用率高且清洁，绿色环保，实现了甲基丙烯酸甲酯联产甲基烯丙醇先进工艺的开发。

Description

一种甲基丙烯酸甲酯联产甲基烯丙醇的方法
（一）技术领域
本发明涉及联产工艺技术领域，特别涉及一种甲基丙烯酸甲酯联产甲基烯丙醇的方法。
（二）背景技术
甲基丙烯酸甲酯（MMA）是重要的有机化工原料，主要用于生产有机玻璃（PMMA），并且广泛用于塑料、涂料、树脂、粘合剂及多种工业助剂的生产。而甲基烯丙醇是一种重要的有机中间体，主要用于合成聚羧酸系高性能减水剂的关键原料、香料、树脂等。
国内生产甲基丙烯酸甲酯主要有丙酮氰醇法和碳四氧化法，丙酮氰醇法主要原料氢氰酸主要来自丙烯腈装置的副产品，该方法合成路线复杂，工艺流程长，多步反应后产率低，成本高且其生产过程中使用剧毒的氢氰酸和强腐蚀性的原料，产生硫酸铵等很多有害的副产品和对环境有危害的废水。而近几年由混合C4经水合得到异丁烯，通过直接氧化法来合成甲基丙烯酸甲酯，使得C4资源得到高价值的利用，是一条新工艺，可以避免丙酮氰醇法的弊端，能够节约资源，降低生产成本，并且无废水产生。
国内生产甲基烯丙醇的主要工艺有异丁烯氯化水解法和碳四氧化和加氢法，目前异丁烯氯化水解工艺以异丁烯为主要原料，先通过氯气发生取代反应，合成甲基烯丙基氯，同时副产氯化氢（HCl）；甲基烯丙基氯经过提纯后再进行取代水解，副产大量的含NaCl的废水。该工艺虽然投资较少，但使用氯气作为原料，副产大量的氯化氢和含盐废水，原子经济利用率低，无论是从经济上还是环保上，都是没有进一步发展和推广的工艺路线。碳四氧化加氢法是采用叔丁醇脱水得到的异丁烯直接氧化法制取MAL（叔丁醇→甲基丙烯醛），然后在催化剂的条件下加氢反应得到甲基烯丙醇。
（三）发明内容
本发明为了弥补现有技术的不足，提供了一种绿色环保、产品规划合理、生产成本低、原子利用率高的甲基丙烯酸甲酯联产甲基烯丙醇的方法。
本发明是通过如下技术方案实现的：
一种甲基丙烯酸甲酯联产甲基丙烯醇的方法，以叔丁醇或异丁烯为原料，包括如下步骤：
（1）将原料叔丁醇或异丁烯在反应器内与空气混合均匀，氧化生产甲基丙烯醛和甲基丙烯酸混合气体，经过后系统的吸收和精馏分离得到含量为60-92%的粗甲基丙烯醛和10-40%的粗甲基丙烯酸中间产品；
（2）粗甲基丙烯酸中间产品经过萃取、酯化反应及精馏，得到纯度大于99.9%行业标准的甲基丙烯酸甲酯产品；
（3）粗甲基丙烯醛经过萃取、共沸精馏操作，得到纯度大于99%以上的甲基丙烯醛产品；
（4）甲基丙烯醛产品在加氢反应器经过催化剂的催化进行选择性加氢，得到甲基烯丙醇混合物，在经过蒸发、精馏得到99.5%以上的甲基烯丙醇产品。
本发明采用叔丁醇/异丁烯为原料氧化生成甲基丙烯酸，甲基丙烯酸被氧化酯化生产甲基丙烯酸甲酯；而甲基丙烯醛作为原料进行选择还原加氢得到甲基烯丙醇，由此，实现了甲基丙烯酸甲酯联产甲基烯丙醇工艺。
本发明的更优技术方案为：
步骤（1）中，反应器内的反应压力为20-70KPaG，温度为320-430℃。
步骤（4）中，加氢反应器内的反应温度为40-120℃，压力为50-400KPaG。
本发明整体模式为一个头两个尾巴，首先将甲基丙烯酸甲酯先进生产工艺路线取代传统工艺路线，将生产过程中得到的中间产品甲基丙烯醛充分利用，再在低温、低压的条件下还原加氢生产甲基烯丙醇，提高了异丁烯的利用率，减少了废水的排放。
本发明工艺简单，产品规划合理，生产成本低，原子利用率高且清洁，绿色环保，实现了甲基丙烯酸甲酯联产甲基烯丙醇先进工艺的开发。
（四）附图说明
下面结合附图对本发明作进一步的说明。
图1为本发明的工艺流程示意图。
（五）具体实施方式
实施例：甲基丙烯酸甲酯和甲基烯丙醇的联合生产方法，包括以下步骤：
（1）叔丁醇/异丁烯与空气混合均匀后，在压力20-70KPaG、温度320-430℃的反应器内，原料叔丁醇/异丁烯与空气氧化生产甲基丙烯醛和甲基丙烯酸混合气体，经过后系统的吸收和精馏得到需要的含量为60-92%粗甲基丙烯醛和10-40%粗甲基丙烯酸中间产品；
（2）粗甲基丙烯酸中间产品经过萃取、酯化反应及精馏，得到纯度大于99.9%行业标准的甲基丙烯酸甲酯产品；
（3）粗甲基丙烯醛经过萃取、共沸精馏等化工单元操作，最终得到纯度大于99%以上的甲基丙烯醛产品；
（4）纯度大于99%的甲基丙烯醛产品在加氢反应器经过催化剂的催化温度40-120℃，压力50-400KPaG下进行选择性加氢得到甲基烯丙醇混合物，再经过蒸发、精馏等单元操作得到99.5%以上的甲基烯丙醇产品；
至此，实现甲基丙烯酸甲酯联产甲基烯丙醇清洁生产工艺。

Claims (3)

1.一种甲基丙烯酸甲酯联产甲基烯丙醇的方法，以叔丁醇或异丁烯为原料，其特征为，包括如下步骤：（1）将原料叔丁醇或异丁烯在反应器内与空气混合均匀，氧化生产甲基丙烯醛和甲基丙烯酸混合气体，经过后系统的吸收和精馏分离得到含量为60-92%的粗甲基丙烯醛和10-40%的粗甲基丙烯酸中间产品；（2）粗甲基丙烯酸中间产品经过萃取、酯化反应及精馏，得到纯度大于99.9%行业标准的甲基丙烯酸甲酯产品；（3）粗甲基丙烯醛经过萃取、共沸精馏操作，得到纯度大于99%以上的甲基丙烯醛产品；（4）甲基丙烯醛产品在加氢反应器经过催化剂的催化进行选择性加氢，得到甲基烯丙醇混合物，在经过蒸发、精馏得到99.5%以上的甲基烯丙醇产品。
2.根据权利要求1所述的甲基丙烯酸甲酯联产甲基烯丙醇的方法，其特征在于：步骤（1）中，反应器内的反应压力为20-70 KPaG，温度为320-430℃。
3.根据权利要求1所述的甲基丙烯酸甲酯联产甲基烯丙醇的方法，其特征在于：步骤（4）中，加氢反应器内的反应温度为40-120℃，压力为50-400KPaG。
CN201710595561.4A 2017-07-20 2017-07-20 一种甲基丙烯酸甲酯联产甲基烯丙醇的方法 Pending CN107266290A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004116A (zh) * 2019-12-19 2020-04-14 湖北美和科技有限公司 一种用于制备结焦抑制剂组份的甲基丙烯酸酯单体
CN113694860A (zh) * 2021-08-25 2021-11-26 宁波昊德化学工业股份有限公司 一种甲基烯丙醇的生产工艺及设备

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CN103755523A (zh) * 2013-12-02 2014-04-30 江苏苏博特新材料股份有限公司 一种2-甲基烯丙醇的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111004116A (zh) * 2019-12-19 2020-04-14 湖北美和科技有限公司 一种用于制备结焦抑制剂组份的甲基丙烯酸酯单体
CN113694860A (zh) * 2021-08-25 2021-11-26 宁波昊德化学工业股份有限公司 一种甲基烯丙醇的生产工艺及设备

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