CN103694086B - 一种采用水解法分离回收含二腈萃余液中酚类的方法 - Google Patents
一种采用水解法分离回收含二腈萃余液中酚类的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 25
- 150000002989 phenols Chemical class 0.000 title claims abstract description 24
- 238000000926 separation method Methods 0.000 title claims abstract description 23
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 16
- 239000008346 aqueous phase Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000013517 stratification Methods 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 15
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000005669 hydrocyanation reaction Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 235000019605 sweet taste sensations Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
- C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/005—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from products, waste products or side-products of processes, not directed to the production of phenols, by conversion or working-up
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- Chemical & Material Sciences (AREA)
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Abstract
本发明公开了一种采用水解法分离回收含二腈萃余液中酚类的方法，包括以下步骤：1）往含二腈萃余液中加入水进行水解反应；2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将有机相转去精馏分离出酚类。本发明水解含二腈萃余液中存在的中毒镍催化剂和含磷配体，降低了其对后续分离己二腈的影响，并且回收水解产物酚类，例如甲基苯酚，酚类是合成催化剂的主要原料，大大降低了丁二烯法生产己二腈的催化剂成本。此外，此方法中的水相可循环套用，基本无三废产生。
Description
技术领域
本发明涉及己二腈的生产技术领域，涉及一种采用水解法分离回收含二腈萃余液中酚类的方法。
背景技术
己二腈分子式为CN（CH2）4CN，英文简写为ADN，是生产新型材料尼龙66的最主要原料之一，其性状为无色油状液体，稍带甜味，有毒性和腐蚀性，密度为962g/cm2，熔点1℃，沸点295℃（1atm）。此外，其在电子、轻工业及其它有机合成领域也有着广阔的应用。
己二腈的合成方法较多，目前生产己二腈的工艺路线主要有丙烯腈电解二聚法和丁二烯法二种。丁二烯法合成己二腈主要分一次氢氰化、异构化、二次氢氰化三个步骤，这三个步骤的反应方程式如下：
三步反应都可用零价镍作为催化剂进行均相催化反应。二次氢氰化后的含二腈反应液可利用萃取法分离回收其中的零价镍催化剂和含磷配体，轻相为分离回收的零价镍催化剂和含磷配体，重相为含二腈的萃余液。但是，萃取法分离回收零价镍催化剂和含磷配体后，含二腈的萃余液中还含有少量中毒的镍催化剂和含磷配体。中毒镍催化剂和含磷配体的存在会导致后续分离己二腈过程中形成高沸物结焦堵塞精馏塔，大大降低运行效率，并且含二腈萃余液在分离出己二腈后被视作有机废液处理，造成催化剂的浪费。
例如：公开号为CN103180290A的专利文献公开了一种用于制备腈的方法，其中公开了利用非极性溶剂萃取分离回收含己二腈反应产物中的催化剂，形成包含非极性溶剂和催化剂的非极性相和包含己二腈、促进剂和催化剂降解产物的极性相（萃余液），然后直接将萃余液送入己二腈提纯段3000，己二腈提纯段3000包括一系列的蒸馏塔，分离出己二腈产物、反应副产物以及催化剂降解产物（见其说明书第0086~0089段、第0096~0100段）。
发明内容
有鉴于此，本发明的目的在于提供一种采用水解法分离回收含二腈萃余液中酚类的方法，水解中毒的镍催化剂和含磷配体，并且回收合成催化剂的主要原料酚类，降低催化剂成本。
为达到上述目的，本发明提供如下技术方案：
本发明的采用水解法分离回收含二腈萃余液中酚类的方法，包括以下步骤：
1）往含二腈萃余液中加入水进行水解反应；
2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将有机相转去精馏分离出酚类。
进一步，所述步骤1）中，加入的水与含二腈萃余液的质量比为0.5~2:1。
进一步，所述步骤1）中，水解反应在搅拌状态下进行，水解温度为60～90℃，保温反应3~12小时。
进一步，所述步骤2）得到的水相返回步骤1）中循环套用。
本发明的有益效果在于：
本发明水解含二腈萃余液中存在的中毒镍催化剂和含磷配体，降低了其对后续分离己二腈的影响，并且回收水解产物酚类，例如甲基苯酚，酚类是合成催化剂的主要原料，大大降低了丁二烯法生产己二腈的催化剂成本。此外，此方法中的水相可循环套用，基本无三废产生。
具体实施方式
为了使本发明的目的、技术方案和有益效果更加清楚，下面将对本发明的优选实施例进行详细的描述。
实施例1
1）将200 g含二腈萃余液加入装有机械搅拌、温度计、冷凝器的三口瓶中，开动搅拌后，加入100 g去离子水，升温至80℃，保温反应5小时；
2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将水相返回步骤1）中循环套用，有机相转去精馏分离出甲基苯酚，经精馏回收得到的甲基苯酚含量大于99%，回收率为85%。
水解反应的主要方程式为：
实施例2
1）将200 g含二腈萃余液加入装有机械搅拌、温度计、冷凝器的三口瓶中，开动搅拌后，加入200 g去离子水，升温至90℃，保温反应10小时；
2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将水相返回步骤1）中循环套用，有机相转去精馏分离出甲基苯酚，经精馏回收得到的甲基苯酚含量大于99%，回收率为92%。
实施例3
1）将200 g含二腈萃余液加入装有机械搅拌、温度计、冷凝器的三口瓶中，开动搅拌后，加入400 g去离子水，升温至65℃，保温反应12小时；
2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将水相返回步骤1）中循环套用，有机相转去精馏分离出甲基苯酚，经精馏回收得到的甲基苯酚含量大于99%，回收率为93%。
最后说明的是，以上优选实施例仅用以说明本发明的技术方案而非限制，尽管通过上述优选实施例已经对本发明进行了详细的描述，但本领域技术人员应当理解，可以在形式上和细节上对其作出各种各样的改变，而不偏离本发明权利要求书所限定的范围。
Claims (4)
1.一种采用水解法分离回收含二腈萃余液中酚类的方法，其特征在于：包括以下步骤：
1）往含二腈萃余液中加入水进行水解反应；
2）将步骤1）得到的水解反应产物静置分层，轻相为包含酚类的有机相，重相为水相，将有机相转去精馏分离出酚类。
2.根据权利要求1所述的采用水解法分离回收含二腈萃余液中酚类的方法，其特征在于：所述步骤1）中，加入的水与含二腈萃余液的质量比为0.5~2:1。
3.根据权利要求1所述的采用水解法分离回收含二腈萃余液中酚类的方法，其特征在于：所述步骤1）中，水解反应在搅拌状态下进行，水解温度为60～90℃，保温反应3~12小时。
4.根据权利要求1、2或3所述的采用水解法分离回收含二腈萃余液中酚类的方法，其特征在于：所述步骤2）得到的水相返回步骤1）中循环套用。
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| CN103080075A (zh) * | 2010-07-07 | 2013-05-01 | 因温斯特技术公司 | 用于制备腈的方法 |
| CN103180290A (zh) * | 2010-07-07 | 2013-06-26 | 因温斯特技术公司 | 用于制备腈的方法 |
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