CN109232401B - 一种三氯吡氧乙酸酯精馏残液资源化处理的方法 - Google Patents
一种三氯吡氧乙酸酯精馏残液资源化处理的方法 Download PDFInfo
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Abstract
本发明公开了一种三氯吡氧乙酸酯精馏过程产生的釜底残液进行资源化处理的方法，该方法将三氯吡氧乙酸酯精馏生产残液在碱性条件下水解，经过活性炭吸附、热过滤，冷却结晶，酸化，再过滤，最后干燥得到高纯度的三氯吡氧乙酸。结晶母液则经过多次套用，乙二醇丁醚的浓度累积高于一定含量，则进行蒸馏回收，再利用甲苯萃取，萃取相进行精馏回收乙二醇丁醚，萃余相当作水套用。通过本发明方法，三氯吡氧乙酸酯精馏残渣转化为有价值的乙二醇单丁醚及三氯吡氧乙酸，有效减轻残留液对企业及生态环境的影响，同时副产的乙二醇单丁醚可以用作原料继续进行三氯吡氧乙酸酯的生产，副产的三氯吡氧乙酸符合农药外售标准。
Description
技术领域
本发明属于生产废液资源化利用处理领域，重点涉及一种三氯吡氧乙酸酯精馏残液资源化处理的方法，通过该方法处理精馏残液，可以回收三氯吡氧乙酸及乙二醇丁醚。
背景技术
三氯吡氧乙酸丁氧基乙酯，商品名为绿草定-2-丁氧基乙酯，英文名称：Triclopy-butoxyethyl ester。三氯吡氧乙酸丁氧基乙酯纯品为无色透明液体，属内吸传导型选择性除草剂，可用于毛竹、核桃、板栗等经济林或果园杂草和灌木防治、造林前以及森林防火带的灭生性除草、培育松树以及树桩处理[17-18]。三氯吡氧乙酸也可用于禾本科草坪和牧场等非耕地除草。除此之外，也对公路、铁路、石油管道、电力线路两侧杂草和木本植物防治有较好的效果。
在工业上，三氯吡氧乙酸酯的合成以三氯吡啶醇钠和氯乙酸丁氧基乙酯为主要原料，在生产过程中，需要通过精馏对三氯吡氧乙酸酯进行提纯，大部分三氯吡氧乙酸酯蒸出，进入成品，少量的物料残留在釜底，其中三氯吡氧乙酸酯含量为50—80％，其中含有少量物料高温结焦产生的渣。目前对其处理方法还未见到相关的文献报道。
目前该精馏残液主要是作为危废委托有资质单位进行焚烧处置，不符合原子经济性的要求，同时对环境的影响较大。
发明内容
本发明旨在针对现有技术的技术缺陷，提供一种三氯吡氧乙酸酯精馏残液资源化处理的方法，以解决现有技术的有价值成分无法得到有效回收的技术问题。本发明要解决的另一技术问题是现有技术中三氯吡氧乙酸酯蒸馏方法的排放废液存在污染问题。本发明要解决的再一问题是现有技术中常规的三氯吡氧乙酸酯成本亟待降低。
为了达到上述目的，本发明提供的技术方案为：
所述三氯吡氧乙酸酯精馏残液资源化处理的方法包括如下步骤：
(1)以水作溶剂，将三氯吡氧乙酸酯精馏残液在碱性条件下进行水解反应，然后加入活性炭吸附有机杂质，经热过滤后得到三氯吡氧乙酸碱金属盐滤液；所述碱可以是氢氧化钾、氢氧化钠等无机碱的一种；
(2)将三氯吡氧乙酸碱金属盐滤液经冷却、结晶后过滤，得到三氯吡氧乙酸碱金属盐和结晶滤液；若结晶滤液中乙二醇丁醚的质量百分比含量小于20％，则将结晶滤液替代步骤(1)中的水作为下一批三氯吡氧乙酸酯精馏残液资源化处理的溶剂；若结晶滤液中乙二醇丁醚的质量百分比含量大于20％，则将结晶滤液进行蒸馏浓缩，在蒸出的乙二醇丁醚水溶液中加入萃取剂进行萃取，萃余水相与浓缩后的结晶滤液混合后替代步骤(1)中的水作为下一批三氯吡氧乙酸酯精馏残液资源化处理的溶剂；
(3)将三氯吡氧乙酸碱金属盐加入水中，滴加无机酸酸化，过滤，得到三氯吡氧乙酸湿品；
(4)将三氯吡氧乙酸湿品干燥后得到三氯吡氧乙酸。
优选地，所述三氯吡氧乙酸酯精馏残液中三氯吡氧乙酸酯的质量百分比含量为50—80％。
优选地，步骤(1)中所述三氯吡氧乙酸酯精馏残液与溶剂质量比为1:(2—10)。
优选地，步骤(1)中水解反应的温度为50—80℃，水解反应时间为1—5h。
优选地，步骤(1)活性炭的质量为三氯吡氧乙酸酯精馏残液质量的1—20％；所述活性炭平均粒径为100—200目，碘吸附值大于1000mg/g，比表面积大于500m2/g。
优选地，步骤(2)中结晶的温度0—20℃，结晶时间3—6h。
优选地，步骤(2)中所述萃取剂为甲苯、二甲苯、氯苯、三氯甲烷或二氯乙烷中，所述萃取剂与乙二醇丁醚水溶液的质量比为1:(0.2—1)。
优选地，步骤(2)所述萃余水相中乙二醇丁醚的质量百分比为0.5—2％。
优选地，步骤(3)所述酸化时的酸化试剂为质量百分比浓度为15％的盐酸、质量百分比浓度为35％的浓盐酸或质量百分比浓度为60—100％的硫酸；酸化时滴加酸到溶液pH值小于3，酸化温度小于60℃。
通过本发明方法，90％以上的三氯吡氧乙酸酯蒸馏残液可以转化成三氯吡氧乙酸，这不仅提高了原料的利用率，减少三废的产生，减轻了企业的环保压力，同时降低产品的生产成本。按照设计产能每年可节约生产成本1000多万。
附图说明
图1是本发明方法流程示意图。
具体实施方式
以下将对本发明的具体实施方式进行详细描述。为了避免过多不必要的细节，在以下实施例中对属于公知的结构或功能将不进行详细描述。以下实施例中所使用的近似性语言可用于定量表述，表明在不改变基本功能的情况下可允许数量有一定的变动。除有定义外，以下实施例中所用的技术和科学术语具有与本发明所属领域技术人员普遍理解的相同含义。
实施例1
取600.0kg三氯吡氧乙酸酯精馏残液(含量为61.01％)，3000kg水加入至水解罐，开启机械搅拌，控制水解罐温度在70—75℃，向其中加入固体碱氢氧化钾60kg，保温反应3h；加入15kg活性炭(型号为A)进行吸附处理1h，保温压滤，将滤液转至酸化釜，缓慢降温至20℃，搅拌结晶3小时，将溶剂抽出，滤渣为三氯吡氧乙酸钾盐；向其中加入自来水600.0kg，滴加浓盐酸进行酸化；直至pH值小于3，析出固体，过滤，烘干，得到三氯吡氧乙酸成品。
第2—4批次分别套用上批次水解母液，代替水进行水解，其他条件与上述一致，数据见下表1：
表1实施例1产出数据表
第4批次水解母液中，乙二醇丁醚浓度为21.9％。蒸馏浓缩出1500kg乙二醇丁醚水溶液，浓度为30.7％，加入甲苯600kg，搅拌1h，静置分层，甲苯相重量为1051.3kg，其中乙二醇丁醚的质量百分比为42.9％。
上述的乙二醇丁醚与甲苯混合物转至精馏塔精馏，回收甲苯馏分595kg，回收乙二醇丁醚469.3kg，纯度为98.1％，乙二醇丁醚的回收率为94.99％。
实施例2
取600.0kg三氯吡氧乙酸酯精馏残液(含量为61.01％)，3000kg水加入至水解罐，开启机械搅拌，控制水解罐温度在70—75℃，向其中加入固体碱氢氧化钾60kg，保温反应3h；加入15kg活性炭(型号为B)进行吸附处理1h，保温压滤，将滤液转至酸化釜，缓慢降温至0℃，搅拌结晶3小时，将溶剂抽出，滤渣为三氯吡氧乙酸钾盐；向其中加入自来水600.0kg，滴加浓盐酸进行酸化；直至pH值小于3，析出固体，过滤，烘干，得到三氯吡氧乙酸成品。
第2—4批次分别套用上批次水解母液，代替水进行水解，其他条件与上述一致，数据见下表2：
表2实施例2产出数据表
第4批次水解母液中，乙二醇丁醚浓度为20.2％。蒸馏浓缩出1500kg乙二醇丁醚水溶液，浓度为30.3％，加入氯苯600kg，搅拌1h，静置分层，氯苯相重量为1040.3kg，其中乙二醇丁醚的质量百分比为40.9％。
上述的乙二醇丁醚与氯苯混合物转至精馏塔精馏，回收氯苯馏分597kg，回收乙二醇丁醚430.5kg，纯度为97.5％，乙二醇丁醚的回收率为86.61％。
Claims (5)
1.一种三氯吡氧乙酸酯精馏残液资源化处理的方法，其特征在于，所述方法包括如下步骤：
（1）以水作溶剂，将三氯吡氧乙酸酯精馏残液在碱性条件下进行水解反应，然后加入活性炭吸附有机杂质，经热过滤后得到三氯吡氧乙酸碱金属盐滤液；所述三氯吡氧乙酸酯精馏残液中三氯吡氧乙酸酯的质量百分比含量为50—80%；所述活性炭的质量为三氯吡氧乙酸酯精馏残液质量的1—20%；所述活性炭平均粒径为100—200目，碘吸附值大于1000mg/g，比表面积大于500m2/g；
（2）将三氯吡氧乙酸碱金属盐滤液经冷却、结晶后过滤，得到三氯吡氧乙酸碱金属盐和结晶滤液；若结晶滤液中乙二醇丁醚的质量百分比含量小于20%，则将结晶滤液替代步骤（1）中的水作为下一批三氯吡氧乙酸酯精馏残液资源化处理的溶剂；若结晶滤液中乙二醇丁醚的质量百分比含量大于20%，则将结晶滤液进行蒸馏浓缩，在蒸出的乙二醇丁醚水溶液中加入萃取剂进行萃取，萃余水相与浓缩后的结晶滤液混合后替代步骤（1）中的水作为下一批三氯吡氧乙酸酯精馏残液资源化处理的溶剂；所述结晶的温度0—20℃，结晶时间3—6h， 所述萃取剂为甲苯、二甲苯、氯苯、三氯甲烷或二氯乙烷，所述萃取剂与乙二醇丁醚水溶液的质量比为1:（0.2—1）；
（3）将三氯吡氧乙酸碱金属盐加入水中，滴加无机酸酸化，过滤，得到三氯吡氧乙酸湿品；
（4）将三氯吡氧乙酸湿品干燥后得到三氯吡氧乙酸。
2.如权利要求1所述的方法，其特征在于，步骤（1）中所述三氯吡氧乙酸酯精馏残液与溶剂质量比为1:（2—10）。
3.如权利要求1所述的方法，其特征在于，步骤（1）中水解反应的温度为50—80℃，水解反应时间为1—5h。
4.如权利要求1所述的方法，其特征在于，步骤（2）所述萃余水相中乙二醇丁醚的质量百分比为0.5—2%。
5.如权利要求1所述的方法，其特征在于，步骤（3）所述酸化时的酸化试剂为质量百分比浓度为15%的盐酸、质量百分比浓度为35%的浓盐酸或质量百分比浓度为60—100%的硫酸；酸化时滴加酸到溶液pH值小于3，酸化温度小于60℃。
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