CN105801474B - 一种精制3,6‑二氯吡啶甲酸的方法 - Google Patents

一种精制3,6‑二氯吡啶甲酸的方法 Download PDF

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CN105801474B
CN105801474B CN201610357994.1A CN201610357994A CN105801474B CN 105801474 B CN105801474 B CN 105801474B CN 201610357994 A CN201610357994 A CN 201610357994A CN 105801474 B CN105801474 B CN 105801474B
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王琪宇
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Shandong Zhongxin Kenong Life Technology Co.,Ltd.
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation

Abstract

发明名称：一种精制3,6‑二氯吡啶甲酸的方法摘要：本发明涉及一种精制3,6‑二氯吡啶甲酸的方法，首先制备吸附剂，3,6‑二氯吡啶甲酸粗品和水混合使用吸附剂进行吸附，可得到质量3,6‑二氯吡啶甲酸纯化产品。

Description

一种精制3,6-二氯吡啶甲酸的方法
技术领域
本发明涉及一种精制方法，尤其是一种精制3,6-二氯吡啶甲酸的方法。
背景技术
目前对电化学还原法得到的二氯吡啶酸溶液后处理方法是在溶液中加酸使二氯吡啶酸结晶析出，然后通过过滤、真空蒸发的方法分离提取二氯吡啶酸和氯化钠盐。真空蒸发的缺点是能量消耗高、运行费用较高。所以，人们需要探寻一种既高效又经济环保的新型分离技术，经过长时间的探究，扩散渗析法膜分离技术成为研究者们关注的焦点。
CN102351788A涉及一种提取精制二氯吡啶酸的方法,利用膜浓缩分离技术对用电化学合成法制得的二氯吡啶酸溶液进行浓缩处理,通过微滤和超滤作预处理,再采用多级膜法浓缩工艺提纯得到二氯吡啶酸精品。本发明得到的二氯吡啶酸具有纯度高、品质好的特点,HPLC含量达97%以上,本发明通过对传统工艺进行技术改造,可减低能耗,减少废水废气的排放,经过处理的废水可直接回用或达标排放,对环境保护更加有利,同时提高了二氯吡啶酸的收率。
CN 104447529 A涉及3,6-二氯吡啶甲酸的提取纯化方法。本发明要解决的技术问题是现有方法的收率低，操作复杂，成本高，不适合工业化生产。本发明解决上述技术问题的方案是通过在不同温度和pH值条件下3,6-二氯吡啶甲酸与杂质溶解度的不同，对产品进行分离纯化。本发明操作简便，装置简单，不需要增加其他昂贵的分离试剂和材料，成本低，适合工业化生产。
US4334074 涉及3,6-二氯吡啶甲酸，高活性的植物生长调节剂中，从基本的，水溶液用HCl在絮凝剂的存在下回收通过酸化物，分离出沉淀的杂质，在母液中用汽提从溶剂中萃取酸与碱性含水进料溶液。公开了利用树脂吸附提高提取纯化收率的方法。
现有技术中的3,6-二氯吡啶甲酸提纯技术由于反应液中杂质较多，得到的产品纯度往往不高，还需要二次结晶，这无疑会降低产品收率、增加生产成本。
发明内容
本发明目的在于解决现有技术中存在的上述技术问题，提供一种精制3,6-二氯吡啶甲酸的方法。。其特征在于制备步骤包括：
步骤1.吸附剂的制备：
在反应釜中按重量份计加入100份螯合高流速琼脂糖微球、1-10份3,7-二甲基-2,6-辛二烯醛，0.01-0.1份1-乙烯基-3-乙基咪唑四氟硼酸盐，500-1000份水，1-4份羟丙基甲基纤维素，0.5-2份过氧化苯甲酰，在80℃反应6h后升温至85℃反应2h，再升温至95℃反应6h，过滤，烘干后得到吸附剂；
步骤2. 吸附提纯3,6-二氯吡啶甲酸：
按重量份计，100份3,6-二氯吡啶甲酸粗品，300-1000份水混合1-5h,在50～100℃条件下, 经过装有吸附剂的层析柱中进行吸附，流速1-5BV/h,可得到质量3,6-二氯吡啶甲酸纯化产品。
所述的螯合高流速琼脂糖微球为市售产品，如西安蓝晓科技新材料股份有限公司生产的产品；3,7-二甲基-2,6-辛二烯醛为市售产品，如上海抚生生物科技有限公司生产的产品； 1-乙烯基-3-乙基咪唑四氟硼酸盐为市售产品，如中科院兰州化学物理研究所生产的产品。
所述的3,6-二氯吡啶甲酸为市售产品。3,6-二氯吡啶甲酸粗品为提纯前的3,6-二氯吡啶甲酸，也可以是含3,6-二氯吡啶甲酸的混合物。
所述的知的脱盐，脱水技术，包括结晶，过滤，萃取，膜分离，精馏技术中的一种或多种。
与现有技术相比，本发明的催化剂及其制备方法，具有以下有益效果：
螯合高流速琼脂糖微球具有微孔结构，在其表面引入3,7-二甲基-2,6-辛二烯醛，1-乙烯基-3-乙基咪唑四氟硼酸盐的醛基功能团，提高了对3,6-二氯吡啶甲酸粗品中醛类杂质的吸附能力，可得到质量百分含量最高99.9%的3,6-二氯吡啶甲酸产品。
具体实施方式
以下实例仅仅是进一步说明本发明，并不是限制本发明保护的范围。
实施例中3,6-二氯吡啶甲酸粗品为按重量份计，将100份质量百分比含量99.9%的3,6-二氯吡啶甲酸和5份甲醛混合,配置成3,6-二氯吡啶甲酸粗品。
实施例1:
步骤1.
吸附剂的制备：在1000L反应釜中加入100KgAmbermite XAD16HP螯合高流速琼脂糖微球、5Kg3,7-二甲基-2,6-辛二烯醛，0.05Kg1-乙烯基-3-乙基咪唑四氟硼酸盐，800Kg水，2Kg羟丙基甲基纤维素，1Kg过氧化苯甲酰，在80℃反应6h后升温至85℃反应2h，再升温至95℃反应6h，过滤，烘干后得到吸附剂；
步骤2. 吸附提纯3,6-二氯吡啶甲酸：
将100Kg3,6-二氯吡啶甲酸粗品，10Kg氢氧化钠，600Kg份水混合3h,在75℃条件下, 经过装有吸附剂的层析柱中进行吸附，流速3BV/h,得到提纯的3,6-二氯吡啶甲酸钠盐，再加入盐酸中和至PH=7，再经公知的脱盐，脱水技术得到3,6-二氯吡啶甲酸纯化产品。3,6-二氯吡啶甲酸质量百分含量见表1，编号为M-1。
实施例2:
步骤1.吸附剂的制备：
在1000L反应釜中加入100KgAmbermite XAD16HP螯合高流速琼脂糖微球、1Kg3,7-二甲基-2,6-辛二烯醛，0.01Kg1-乙烯基-3-乙基咪唑四氟硼酸盐，500Kg水，1Kg羟丙基甲基纤维素，0.5Kg过氧化苯甲酰，在80℃反应6h后升温至85℃反应2h，再升温至95℃反应6h，过滤，烘干后得到吸附剂；
步骤2. 吸附提纯3,6-二氯吡啶甲酸：
将100Kg3,6-二氯吡啶甲酸粗品，5Kg氢氧化钠，300Kg份水混合1h,在50℃条件下,经过装有吸附剂的层析柱中进行吸附，流速1BV/h,得到提纯的3,6-二氯吡啶甲酸钠盐，再加入盐酸中和至PH=7，再经公知的脱盐，脱水技术，得到3,6-二氯吡啶甲酸纯化产品。3,6-二氯吡啶甲酸质量百分含量见表1，编号为M-2。
实施例3
步骤1.吸附剂的制备：
在1000L反应釜中加入100KgAmbermite XAD1180螯合高流速琼脂糖微球、10Kg3,7-二甲基-2,6-辛二烯醛，0.1Kg1-乙烯基-3-乙基咪唑四氟硼酸盐，1000Kg水，4Kg羟丙基甲基纤维素，2Kg过氧化苯甲酰，在80℃反应6h后升温至85℃反应2h，再升温至95℃反应6h，过滤，烘干后得到吸附剂；
步骤2. 吸附提纯3,6-二氯吡啶甲酸：
将100Kg3,6-二氯吡啶甲酸粗品，20Kg氢氧化钠，1000Kg份水混合5h,在100℃条件下, 经过装有吸附剂的层析柱中进行吸附，流速5BV/h,得到提纯的3,6-二氯吡啶甲酸钠盐，再加入盐酸中和至PH=7，再经公知的脱盐，脱水技术，得到3,6-二氯吡啶甲酸纯化产品。3,6-二氯吡啶甲酸质量百分含量见表1，编号为M-3。
对比例1
不加入3,7-二甲基-2,6-辛二烯醛，其它同实施例1。3,6-二氯吡啶甲酸质量百分含量见表1，编号为M-4。
对比例2
不加入1-乙烯基-3-乙基咪唑四氟硼酸盐，其它同实施例1。3,6-二氯吡啶甲酸质量百分含量见表1,编号为M-5。
对比例3
去掉步骤1，吸附剂使用XAD-1吸附树脂，其它同实施例1，3,6-二氯吡啶甲酸质量百分含量见表1,编号为M-6。
经过气相色谱检测，实施例1-3以及对比例1-3提纯后3,6-二氯吡啶甲酸质量百分含量的比较见表1：
表1：不同工艺做出的试验样品吸附后3,6-二氯吡啶甲酸质量百分含量的比较
编号 3,6-二氯吡啶甲酸质量百分含量%
M-1 99.9
M-2 99.9
M-3 99.9
M-4 99.1
M-5 99.4
M-6 97.5
以上仅为本发明的具体实施例，但本发明的技术特征并不局限于此。任何以本发明为基础，为解决基本相同的技术问题，实现基本相同的技术效果，所作出的简单变化、等同替换或者修饰等，皆涵盖于本发明的保护范围之中。

Claims (1)

1.一种精制3,6-二氯吡啶甲酸的方法，其特征在于包括以下步骤：
步骤1.吸附剂的制备：
在反应釜中按重量份计加入100份螯合高流速琼脂糖微球、1-10份3,7-二甲基-2,6-辛二烯醛，0.01-0.1份1-乙烯基-3-乙基咪唑四氟硼酸盐，500-1000份水，1-4份羟丙基甲基纤维素，0.5-2份过氧化苯甲酰，在80℃反应6h后升温至85℃反应2h，再升温至95℃反应6h，过滤，烘干后得到吸附剂；
步骤2.吸附提纯3,6-二氯吡啶甲酸：
按重量份计，将100份3,6-二氯吡啶甲酸粗品，10-20份氢氧化钠，300-1000份水混合1-5h,,在50～100℃条件下,经过装有吸附剂的层析柱中进行吸附，流速1-5BV/h，得到提纯的3,6-二氯吡啶甲酸钠盐，再加入盐酸中和至PH=7，再经公知的脱盐，脱水技术，得到3,6-二氯吡啶甲酸纯化产品。
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