CN114904474B - 5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置及方法 - Google Patents
5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置及方法 Download PDFInfo
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Abstract
本发明公开了一种5‑溴甲基吡啶‑2,3‑二羧酸二乙酯反应装置及方法，属于甲氧咪草烟生产技术领域，其技术方案为：包括通过管路依次连接的预反应器、特制光反应器、活性炭过滤器和分离器；预反应器上设置有甲基PDE/催化剂一入口和溴素入口；特制光反应器包括引发段和光反应段，引发段涂覆有催化剂二，光反应段设置有紫外灯；活性炭过滤器内设置有活性炭层；分离器设置有水相出口和有机相出口。本发明反应时间短，反应更彻底，选择性好；甲基PDE转化率≥95%，反应过程中目标产物一溴PDE转化率高，溴PDE选择性≥98%；这不仅提高原料的利用率，减少副产杂质的产生，减轻了后续企业的环保压力，同时降低产品的生产成本。
Description
技术领域
本发明涉及甲氧咪草烟生产技术领域，具体涉及一种5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置及方法。
背景技术
甲氧咪草烟为咪唑啉酮类除草剂品种，通过叶片吸收、传导并积累于分生组织，抑制AHAS的活性，导致支链氨基酸—缬氨酸、亮氨酸与异亮氨酸生物合成停止，干扰DNA合成及细胞有丝分裂与植物生长，最终造成植株死亡，因其毒性小，效果好得到了广泛的应用，其制备方法也备受关注。
现阶段甲氧咪草烟中间体5-溴甲基吡啶-2,3-二羧酸二乙酯的制备主要采用釜式“一锅法”进行，即将5-甲基-2,3-吡啶二羧酸二甲酯（甲基PDE）、溶剂二氯乙烷、溴/氢氧化钠溶液还有催化剂偶氮二异丁腈同时加入，升温反应，该方法带来的结果就是，溴素利用率低，副产杂质5-二溴甲基吡啶-2,3-二羧酸二乙酯大量产生，导致废水有机物含量高、处理难度大易造成环境污染，同时生产成本高。
发明内容
本发明要解决的技术问题是：克服现有技术的不足，提供一种5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置及方法，采用预反应器和特制光反应器连续作用，通过复合催化实现甲基PDE的高转化率和溴PDE的高选择性。
本发明的技术方案为：
第一方面，公开了一种5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置，包括通过管路依次连接的预反应器、特制光反应器、活性炭过滤器和分离器；所述预反应器的外壁设置有夹套，外壁与夹套之间形成中空的夹层，预反应器的下部设置有与夹层相通的热水进口，预反应器的上部设置有与夹层相通的热水出口，预反应器上设置有甲基PDE/催化剂一入口和溴素入口；所述特制光反应器包括引发段和光反应段，引发段涂覆有催化剂二，光反应段设置有紫外灯；所述活性炭过滤器内设置有活性炭层；所述分离器设置有水相出口和有机相出口。
优选地，所述甲基PDE/催化剂一入口管路和溴素入口管路上分别设置有甲基PDE/催化剂一输送泵和溴素输送泵。
优选地，所述特制光反应器外壁依次设置有保温层和防护层。
优选地，所述特制光反应器上设置有视镜，便于观察特制光反应器内部情况。
优选地，特制光反应器外观为圆柱形，内置螺旋石英玻璃盘管；保温层为橡塑保温材料，防护层为合金不锈钢。
优选地，特制光光反应器，外径50-100cm，长度为2-3m，螺旋石英玻璃盘管直径8-11cm，催化剂二在螺旋石英玻璃盘管上的涂附长度为0.15-0.35m；紫外灯直径5-9cm，采用波长为300-400nm，保温层厚度为3-8cm，防护层厚度为0.2-0.35cm；催化剂二涂附厚度为0.5-1.5mm。。
第二方面，公开了制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，包括以下步骤：
1）按照比例将甲基PDE和催化剂一溶于二氯乙烷，形成溶液一，溴素加入氢氧化钠溶液稀释形成溶液二；
2）将溶液一和溶液二同时加入到预反应器中混合均匀并加热至70℃预处理，反应停留时间4-6min；
3）将预反应器中经预处理的溶液输送至特制光反应器，经过涂附催化剂二的引发段引发后进入紫外灯照射的光反应段反应，反应液输送至经活性炭过滤器；
4）活性炭过滤器处理之后的反应液进入分离器静置分层，上层水相送至厂区废水预处理车间统一处理回收副产溴化钠，下层有机相进入溴季铵盐合成工段进一步反应。
优选地，预反应器甲基PDE、溴素和催化剂一投料质量比为100：42~46：0.5~1.5，优选为208：92：2.08。
优选地，催化剂一为偶氮二异庚腈、偶氮二异丁腈、偶氮二异戊腈、偶氮二异辛腈以及偶氮二异己腈中的一种或多种，优选偶氮二异丁腈；催化剂二为复合催化剂，以Al2O3为载体，负载TiS2+CdO、TiS2+NiO、Fe2S3+CdO和Fe2S3+NiO中的一种，负载含量为8-11%+5-12%。
优选地，特制光反应器内温度为50~60℃，压力0.05~0.1MPa，反应停留时间为1.0~2.0min。
本发明与现有技术相比，具有以下有益效果：
本发明各反应原料和催化剂一首先经混合预热后，再经过催化剂二引发，后经紫外灯照射下反应段，缩短反应时间，反应更彻底，选择性好；甲基PDE转化率≥95%，反应过程中目标产物一溴PDE转化率高，溴PDE选择性≥98%；这不仅提高原料的利用率，减少副产杂质的产生，减轻了后续企业的环保压力，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超500万元。
附图说明
图1是本发明的结构示意图。
图2是本发明的特制光反应器结构示意图。
图3是本发明的特制光反应器光反应段截面结构示意图。
图中，1、甲基PDE/催化剂一输送泵；2、溴素输送泵；3、夹套；4、热水进口；5、预反应器；6、热水出口；7、特制光反应器；8、引发段；9、防护层；10、保温层；11、视镜；12、光反应段；13、紫外灯；14、活性炭过滤器；15、活性炭层；16、分离器；17、水相出口；18、有机相出口。
具体实施方式
实施例1
如图1-3所示，本实施例提供了一种5-溴甲基吡啶-2,3-二羧酸二乙酯反应装置，包括通过管路依次连接的预反应器5、特制光反应器7、活性炭过滤器14和分离器16；所述预反应器5的外壁设置有夹套3，外壁与夹套3之间形成中空的夹层，预反应器的下部设置有与夹层相通的热水进口4，预反应器的上部设置有与夹层相通的热水出口6，预反应器5上设置有甲基PDE/催化剂一入口和溴素入口；所述甲基PDE/催化剂一入口管路和溴素入口管路上分别设置有甲基PDE/催化剂一输送泵1和溴素输送泵2；特制光反应器外观为圆柱形，外径54cm，长度为2.5m，所述特制光反应器7包括引发段8和光反应段12，特制光反应器7内置螺旋石英玻璃盘管，螺旋石英玻璃管盘贯穿特制光反应器7内部，螺旋石英玻璃盘管直径10cm，引发段8涂覆有催化剂二，催化剂二在盘管上的涂附长度为0.25m，涂附厚度为0.5-1.5mm；光反应段12设置有紫外灯13，紫外灯13设置于螺旋石英玻璃盘管形成的空间内，紫外灯13直径8cm，采用波长为300-400nm；所述活性炭过滤器14内设置有活性炭层15；所述分离器16设置有水相出口17和有机相出口18。
制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，包括以下步骤：
将600kg甲基PDE和6kg偶氮二异丁腈溶于200kg二氯乙烷，264kg溴素与80kg 10%氢氧化钠溶液混合，分别通过输送泵打至预反应器5，搅拌下升温至70℃，反应停留5min，用转料泵将预反应液打入特制光反应器7，反应液首先经过涂附催化剂二（10%TiS2+10%CdO+Al2O3）的引发段8，之后进入光反应段12反应，将特制光反应器7控制压力0.08mPa、温度55℃条件下反应停留时间1.5min，然后反应液进入活性炭过滤器14处理，之后进入分离釜静置分层，分得上层水相由水相出口17输出送至厂区废水预处理车间统一处理回收副产溴化钠，分得下层有机相1004.6kg（其中溴PDE含量77.3%，甲基PDE含量2.69%，二氯乙烷17.3%，其他杂质2.71%），有机相由有机相出口18输出直接进入溴季铵盐合成工段进一步反应。反应工段反应时间6.5min，甲基PDE转化率95.5%，溴PDE选择性98.0%。
实施例2
在实施例1的基础上，所述特制光反应器7外壁依次设置有保温层10和防护层9，保温层10为橡塑保温材料，防护层9为合金不锈钢，保温层10厚度为5cm，防护层9厚度为0.3mm；保温层10的设置使特制光反应器7内的温度保持恒定，使引发和催化阶段更加稳定，效果更好，防护层9的设置能够延长特制光反应器7的使用寿命，减少生产成本。
对比例1
将600kg甲基PDE溶于200kg二氯乙烷，加70kg水，将混合液加入到反应釜中，向反应釜中加入6kg偶氮二异丁腈，搅拌均匀；将264kg溴素与80kg 10%氢氧化钠溶液混合后滴加到反应釜中，保持反应温度50℃，反应2h，然后反应液进入活性炭过滤器处理，之后进入分离釜静置分层，分得上层水相送至厂区废水预处理车间统一处理回收副产溴化钠。反应工段反应时间2h，甲基PDE转化率86.5%，溴PDE选择性83.2%。
利用实施例2的装置及制备方法制备5-溴甲基吡啶-2,3-二羧酸二乙酯，反应时间短，仅为6.5min，且甲基PDE转化率86.5%，溴PDE选择性83.2%，而对比例1的反应时间长达2h，溴素利用率低，甲基PDE转化率86.5%，溴PDE选择性83.2%，甲基PDE转化率和溴PDE选择性也远远低于实施例2，副产杂质5-二溴甲基吡啶-2,3-二羧酸二乙酯大量产生，导致废水有机物含量高、处理难度大易造成环境污染，同时生产成本高。
本发明各反应原料和催化剂一首先经混合预热后，再经过催化剂二引发，后经紫外灯13照射下反应段，缩短反应时间，反应更彻底，选择性好；甲基PDE转化率≥95%，反应过程中目标产物一溴PD和二溴转化率高，溴PDE选择性≥98%；这不仅提高原料的利用率，减少副产杂质的产生，减轻了后续企业的环保压力，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超500万元。
尽管通过参考附图并结合优选实施例的方式对本发明进行了详细描述，但本发明并不限于此。在不脱离本发明的精神和实质的前提下，本领域普通技术人员可以对本发明的实施例进行各种等效的修改或替换，而这些修改或替换都应在本发明的涵盖范围内/任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。
Claims (5)
1.一种制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，其特征在于，包括以下步骤：
1）按照比例将5-甲基-2,3-吡啶二羧酸二甲酯和催化剂一溶于二氯乙烷，形成溶液一，溴素加入氢氧化钠溶液稀释形成溶液二；
2）将溶液一和溶液二同时加入到预反应器(5)中混合均匀并加热至70℃预处理，反应停留时间4-6min；
3）将预反应器(5)中经预处理的溶液输送至特制光反应器（7），经过涂附催化剂二的引发段(8)引发后进入紫外灯(13)照射的光反应段（12）反应，反应液输送至经活性炭过滤器(14)；
4）活性炭过滤器(14)处理之后的反应液进入分离器(16)静置分层，上层水相送至厂区废水预处理车间统一处理回收副产溴化钠，下层有机相进入溴季铵盐合成工段进一步反应；
催化剂一为偶氮二异庚腈、偶氮二异丁腈、偶氮二异戊腈、偶氮二异辛腈以及偶氮二异己腈中的一或多种；催化剂二为复合催化剂，以Al2O3为载体，负载TiS2+CdO、TiS2+NiO、Fe2S3+CdO和Fe2S3+NiO中的一种，TiS2或Fe2S3的负载量为8-11%，CdO或NiO的负载量为5-12%。
2.如权利要求1所述的制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，其特征在于：预反应器(5)中5-甲基-2,3-吡啶二羧酸二甲酯、溴素和催化剂一投料质量比为100：42-46：0.5-1.5。
3.如权利要求1所述的制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，其特征在于：预反应器(5)中5-甲基-2,3-吡啶二羧酸二甲酯、溴素和催化剂一投料质量比为208：92：2.08。
4.如权利要求3所述的制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，其特征在于：催化剂一为偶氮二异丁腈。
5.如权利要求1所述的制备5-溴甲基吡啶-2,3-二羧酸二乙酯的方法，其特征在于：特制光反应器（7）内温度为50-60℃，压力0.05-0.1MPa，反应停留时间为1.0-2.0min。
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