CN110357762A - 一种连续生产α-苯乙醇的制备方法 - Google Patents
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- DBIVJHXZCKUNSO-UHFFFAOYSA-N cobalt ethylbenzene Chemical compound [Co].C(C)C1=CC=CC=C1 DBIVJHXZCKUNSO-UHFFFAOYSA-N 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C07C29/143—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 ketones
- C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
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- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
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Abstract
本发明公开了一种连续生产α‑苯乙醇的制备方法,该方法以乙苯为原料,经过氧化工段得到苯乙酮苯乙醇的混合溶液,经过酯化工段除酸的过程,在加氢工段得到苯乙醇的混合溶液,通过精馏的方式得到纯度99.0%以上的苯乙醇产品。该方法以α‑苯乙醇为目标产品,通过引入酯化除酸工段,将乙苯氧化的过程与苯乙酮加氢制备苯乙醇过程耦合在一起,缩减了传统的工艺流程,仅需一步精馏过程即可得到较高纯度的α‑苯乙醇,具有能耗低,收率高的优点。
Description
技术领域
本发明涉及化学化工领域,具体地说是一种连续生产α-苯乙醇的制备方法。
背景技术
α-苯乙醇又叫1-苯乙醇,是重要的化工原料之一,在香料和医药行业应用广泛。例如其在香料制造业中被广泛的应用于香气调和,并作为玫瑰花香的主要成分,用于各种玫瑰油、精油的合成。在很多药物中α-苯乙醇也有重要的应用,例如在镇定药物的合成中,α-苯乙醇是重要的原材料。
目前制取α-苯乙醇的方法主要是天然提取、微生物发酵、化学合成等多种方法。天然提取法原料有限,成本高;发酵法同时会产生乳酸等副产物,分离成本高。目前化学合成的方法成为了现在的主流的α-苯乙醇的合成方法。目前主要的合成路线为乙苯氧化得到苯乙酮和苯乙醇的混合溶液,二者分离后,苯乙酮再加氢得到苯乙醇。例如专利CN1305981A中公开了一种利用苯乙酮加氢的方法制备苯乙醇的路线。但是该专利中对于苯乙酮原料中的有机酸的浓度要求在1umol/L以下,因此对于加氢的原料要求较高。而乙苯的氧化液中具有苯甲酸等有机酸,不适宜直接加氢制备苯乙醇。传统的路线中,需要将苯乙酮与苯乙醇分离,继而对苯乙酮加氢。但是苯乙酮与苯乙醇二者的沸点分别为203.5℃、202℃二者分离困难,分离成本较高。例如专利CN 104447267 A公布了一种利用分子蒸馏与精馏的结合的方式来分离苯乙酮与苯乙醇的方法,该方法分离效果较好,但是涉及多步分离,能耗高,损失大。因此发展新的路线或者催化剂实现乙苯氧化液的直接加氢得到苯乙醇的方法,是目前苯乙醇生产的趋势。
发明内容
为了更加高效得到α-苯乙醇,解决乙苯氧化液无法直接加氢的难题,本方法旨在提供一种利用乙苯氧化液加氢的方法。
按照本发明,其特征在于:该方法以乙苯为原料,经过氧化工段得到苯乙酮苯乙醇的混合溶液,经过酯化工段除酸的过程,在加氢工段得到苯乙醇的混合溶液,通过精馏的方式得到苯乙醇产品。
按照本发明,其特征在于:所述的氧化工段为乙苯的无溶剂氧化过程。
按照本发明,其特征在于:所述的氧化温度为60-250℃,优选为80-120℃,压力为0.05-2.0MPa,优选为0.3-0.6MPa,停留时间为1-10h,优选为3-5h。
按照本发明,其特征在于:所述的催化剂为异辛酸钴、氯化钴、硬脂酸钴、乙酰丙酮钴、环烷酸钴中的一种或两种以上,催化剂的加入量为乙苯的0.01-5%,优选为0.05-0.1%。
按照本发明,其特征在于:在氧化反应液中加入甲醇,高温无催化酯化降低氧化液酸值的过程。
按照本发明,其特征在于:所加入的甲醇质量为氧化液质量的1-20倍,优选为2-5倍;所述的酯化温度为60-250℃,优选为180-220℃,压力为0.05-2.0MPa,优选为1-1.5MPa,停留时间为1-10h,优选为3-5h。
按照本发明,其特征在于:加氢工段为酯化液混合加氢的过程。
按照本发明,其特征在于:所述的加氢温度为60-250℃,优选为80-120℃,压力为0.05-2.0MPa,优选为1.0-1.2MPa,时间为1-10h,优选为1-2h。
按照本发明,其特征在于:所述的加氢工段的催化剂为Ru/C,RaneyNi,Pd/C中的一种或者两种以上,催化剂的加入量为酯化液的0.1-10%。
按照本发明,其特征在于:包括加氢后的对混合液的精馏分离得到α-苯乙醇的过程。
本发明的有益效果:
该方法以α-苯乙醇为目标产品,与传统的工艺路线相比较,流程短,分离步骤少,仅需一步精馏过程即可得到较高纯度的α-苯乙醇,具有能耗低,收率高的优点。
附图说明
图1乙苯连续直接氧化制备苯乙醇流程图。
图2实施例1连续实验苯乙醇结果。
具体实施方式
下面结合附图和实施例对本发明提供的方法进行详述,但不以任何形式限制本发明。
实施例1
如图1所示,含有质量分数为0.1%异辛酸钴乙苯溶液进入到氧化工段中,氧化温度为120℃,氧气压力为0.3MPa,停留时间为2h,氧化后的反应液经过泵输送到酯化工段,酯化工段加入甲醇质量为氧化反应液质量的4倍,酯化温度为220℃,压力为1.5MPa,停留时间为1h,酯化完成后的酯化反应液经过泵输送至加氢工段,加氢催化剂为酯化液质量1%的Ru/C(Ru质量含量5%wt),所述的加氢温度为110℃,压力为1.0MPa,停留时间为2h,最后经泵进入精馏工段,分离出纯度大于98%的苯乙醇,分离出的甲醇与未反应完全的乙苯可以继续返回使用。图2为实施例1连续实验苯乙醇结果。
实施例2-5
重复实施例1的反应过程和反应条件,不同的是部分反应条件不同,不同之处如下表。各实施例的具体原料反应条件和结果列于表1中。
表1
该方法以α-苯乙醇为目标产品,通过引入酯化除酸工段,将乙苯氧化的过程与苯乙酮加氢制备苯乙醇过程耦合在一起,缩减了传统的工艺流程,仅需一步精馏过程即可得到较高纯度的α-苯乙醇,具有能耗低,收率高的优点。
Claims (9)
1.一种连续生产α-苯乙醇的制备方法,其特征在于:该方法以乙苯为原料,经过氧化工段得到苯乙酮和苯乙醇的混合溶液,经过酯化工段除酸的过程,然后在加氢工段得到苯乙醇的混合溶液,通过精馏的方式得到苯乙醇产品。
2.按照权利要求1所述的制备方法,其特征在于:所述的氧化工段为乙苯的无溶剂氧化过程。
3.按照权利要求1或2所述的制备方法,其特征在于:所述氧化工段过程,所述的氧化温度为60-250℃,优选为80-120℃,压力为0.05-2.0MPa,优选为0.3-0.6MPa,反应时间或停留时间为1-10h,优选为3-5h。
4.按照权利要求1、2或3所述的制备方法,其特征在于:所述氧化工段过程,所采用的催化剂为异辛酸钴、氯化钴、硬脂酸钴、乙酰丙酮钴、环烷酸钴中的一种或两种以上,催化剂的加入量为乙苯质量的0.01-5%,优选为0.05-0.1%。
5.按照权利要求1所述的制备方法,其特征在于:所述酯化工段是,在氧化工段后产生的氧化反应液中加入甲醇,是一种高温无催化酯化降低氧化液酸值的过程,得酯化液。
6.按照权利要求5所述的制备方法,其特征在于:所加入的甲醇质量为氧化反应液质量的1-20倍,优选为2-5倍;所述的酯化温度为60-250℃,优选为180-220℃,压力为0.05-2.0MPa,优选为1-1.5MPa,反应时间或停留时间为1-10h,优选为3-5h。
7.按照权利要求1所述的制备方法,其特征在于:所述加氢工段是一种酯化液混合加氢的过程;
所述的加氢温度为60-250℃,优选为80-120℃,压力为0.05-2.0MPa,优选为1.0-1.2MPa,停留时间为1-10h,优选为1-2h。
8.按照权利要求1或7所述的制备方法,其特征在于:所述的加氢工段采用的催化剂为Ru质量负载量为Ru/C(0.5-10wt%),Raney Ni,Pd质量负载量为Pd/C(0.5-10wt%)中的一种或者两种以上,催化剂的加入量为酯化液质量的0.1-10%。
9.按照权利要求1所述的制备方法,其特征在于:包括加氢后的对混合液的精馏分离得到α-苯乙醇的过程。
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