CN115448872B - 一种均相催化氧化紫晶制备百草枯的工艺 - Google Patents
一种均相催化氧化紫晶制备百草枯的工艺 Download PDFInfo
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- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 title claims abstract description 30
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 30
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010009 beating Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
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- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 claims abstract description 3
- IARCGBCZSPZLGK-UHFFFAOYSA-N 1-methyl-1,2-dihydropyridin-1-ium;chloride Chemical compound Cl.CN1CC=CC=C1 IARCGBCZSPZLGK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 3
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- 229940050176 methyl chloride Drugs 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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Abstract
本发明涉及一种均相催化氧化紫晶制备百草枯的工艺,属于农药合成技术领域,包括如下步骤:将吡啶和甲醇混合,然后滴加氯甲烷,经过吡啶烷基化反应生成N‑甲基吡啶氯化物,经过二聚反应生成1,1‑二甲基‑4,4‑二氢联吡啶,经过水洗除杂后,加入打浆水、酸溶液和均相催化剂,通入液氯,搅拌反应,反应结束后,过滤分离出均相催化剂,得到百草枯溶液。本发明中的反应条件温和,产品的收率高,成本低,操作方便,催化剂和母液可以多次循环利用,能够满足工业化生产的需要,大大降低了生产成本,减少了物能耗,清洁生产,减少环境污染,该工艺符合节能环保的要求,具有很好的经济社会和环保效益。
Description
技术领域
本发明属于农药合成技术领域,具体地,涉及一种均相催化氧化紫晶制备百草枯的工艺。
背景技术
百草枯,化学名称是1,1-二甲基-4,4-联吡啶阳离子盐,是一种快速灭生性除草剂,具有良好的内吸、传导性能,能迅速被植物绿色组织吸收使其枯死。有触杀和传导性作用,与土壤接触后很快失效,因而是一种对土壤及植物根部没有伤害的除草剂。目前国内氨氰法生产工艺取得重大突破,其工艺有很多优点,市场竞争力也很强,但在氧化工段中,紫晶(1,1-二甲基-4,4'-联吡啶阳离子)打浆后通氯气氧化,反应前期生成的百草枯在碱性环境中易分解,但反应前期反应剧烈,通常控制通氯速度减慢,不利于紫晶氧化,正常通氯时间过长。
发明内容
为了解决背景技术中提到的技术问题,本发明提供一种均相催化氧化紫晶制备百草枯的工艺。
本发明的目的可以通过以下技术方案实现:
一种均相催化氧化紫晶制备百草枯的工艺,包括如下步骤:
将吡啶和甲醇混合,然后滴加氯甲烷,经过吡啶烷基化反应生成N-甲基吡啶氯化物,经过二聚反应生成1,1-二甲基-4,4-二氢联吡啶即紫晶,经过水洗除杂后,加入打浆水、酸溶液和催化剂,在搅拌速度为600-1000r/min条件下,通入液氯,搅拌反应,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应结束后,在打料时,过滤分离出催化剂,得到百草枯溶液。
进一步地,搅拌反应时反应温度为40~68℃,反应压力-0.05~0.05MPa,反应时间为2~5h。
进一步地,吡啶、甲醇、氯甲烷、打浆水、酸溶液、催化剂的用量质量比为400:40:270:548:100:20~40。
进一步地,所述酸溶液为盐酸、硫酸中的一种,酸溶液的质量分数10~20%。
进一步地,所述酸溶液还包括母液。
进一步地,所述催化剂的粒径为30~60μm。
进一步地,所述催化剂通过如下步骤制备:
将碳材料和蒸馏水混合,设置温度为80℃,加热分散得到分散液,将MeC l 2用蒸馏水中溶解,然后加入乙酸调节pH值为5~6,加入分散液中,搅拌分散55-60min,抽滤,将得到的滤饼,在80℃条件下干燥,待其干燥后,取出冷却,用研钵将研磨好的样品放入陶瓷坩埚中,于400℃马弗炉中煅烧3h,得到催化剂。
进一步地,碳材料、MeC l 2的质量比为100:1,碳材料和蒸馏水的用量比为1g:10mL。
进一步地,Me为金属Mn、Fe、Cu中的一种。
进一步地,碳材料为碳纳米管、氧化石墨烯和活性炭中的一种。
本发明的有益效果:
本发明为解决草枯合成氧化工段中存在的问题,将负载过渡金属或其盐的碳材料催化加入反应中,打浆后加酸调pH至弱酸性再通氯,本发明中催化剂的催化活性高,且易于回收,再利用和再生反应结束后,溶液中的金属离子重新吸附到碳材料表面,以多相催化剂形式回收,该过程无需添加任何辅助化学试剂。反应条件温和,产品的收率高,成本低,操作方便,催化剂和母液可以多次循环利用,能够满足工业化生产的需要,大大降低了生产成本,减少了物能耗,清洁生产,减少环境污染,该工艺符合节能环保的要求,具有很好的经济社会和环保效益,是一条有竞争力的新的安全生产工艺路线。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
制备催化剂:
将碳纳米管和蒸馏水混合,设置温度为80℃,加热分散得到分散液,将MnC l 2用蒸馏水中溶解,然后加入乙酸调节pH值为5,加入分散液中,搅拌分散55min,抽滤,将得到的滤饼,在80℃条件下干燥,待其干燥后,取出冷却,用研钵将研磨好的样品放入陶瓷坩埚中,于400℃马弗炉中煅烧3h,得到催化剂。
其中,碳纳米管、MnC l 2的质量比为100:1,碳纳米管和蒸馏水的用量比为1g:10mL。
实施例2
制备催化剂:
将氧化石墨烯和蒸馏水混合,设置温度为80℃,加热分散得到分散液,将FeC l 2用蒸馏水中溶解,然后加入乙酸调节pH值为6,加入分散液中,搅拌分散60min,抽滤,将得到的滤饼,在80℃条件下干燥,待其干燥后,取出冷却,用研钵将研磨好的样品放入陶瓷坩埚中,于400℃马弗炉中煅烧3h,得到催化剂。
其中,氧化石墨烯、FeC l 2的质量比为100:1,氧化石墨烯和蒸馏水的用量比为1g:10mL。
实施例3
制备催化剂:
将活性炭和蒸馏水混合,设置温度为80℃,加热分散得到分散液,将CuC l 2用蒸馏水中溶解,然后加入乙酸调节pH值为6,加入分散液中,搅拌分散60min,抽滤,将得到的滤饼,在80℃条件下干燥,待其干燥后,取出冷却,用研钵将研磨好的样品放入陶瓷坩埚中,于400℃马弗炉中煅烧3h,得到催化剂。
其中,活性炭、CuC l 2的质量比为100:1,活性炭和蒸馏水的用量比为1g:10mL。
实施例4
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数20%的盐酸,20g粒径为40μm的实施例2制备的催化剂于反应釜中,在搅拌速度为1000r/min时,通入液氯。反应温度为40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应3h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量36.8%,收率96.1%。
实施例5
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数15%的硫酸,25g粒径为60μm实施例1制备的催化剂于反应釜中,在搅拌速度为800r/min时,通入液氯。反应温度为40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应5h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量38.2%,收率97.1%。
实施例6
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数10%的盐酸,30g粒径为30μm实施例1制备的催化剂于反应釜中,在搅拌速度为700r/min时,通入液氯。反应温度为40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应2h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量38.2%,收率96.9%。
实施例7
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数20%的盐酸,35g粒径为60μm实施例1制备的催化剂于反应釜中,在搅拌速度为600r/min时,通入液氯。反应温度40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应5h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量38%,收率97.7%。
实施例8
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数15%的盐酸,30g粒径为50μm实施例1制备的催化剂于反应釜中,在搅拌速度为600r/min时,通入液氯。反应温度为40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应3h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量39.6%,收率97.8%。
实施例9
分别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、100g质量分数20%的盐酸,40g粒径为35μm实施例1制备的催化剂于反应釜中,在搅拌速度为900r/min时,通入液氯。反应温度为40~68℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应4h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量38.4%,收率96.8%。
实施例10
别将400g吡啶、40g甲醇加入反应釜,滴加270g氯甲烷完成百草枯合成的MPC、MV、水洗阶段。加入548g打浆水、150g实施例8中的母液(指合成出来的百草枯溶液)和实施例1制备催化剂(已重复使用5次)于反应釜中,在搅拌速度为600r/min时,通入液氯。反应温度为60℃,反应压力-0.05~0.05MPa,待反应釜温度二次降温后测料,反应液紫黑色变红棕色透光时结束,反应3h。反应结束后,打料时,过滤分离出催化剂,得到百草枯溶液。含量41.2%,收率98.6%。
在说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (3)
1.一种催化氧化紫晶制备百草枯的工艺,其特征在于,包括如下步骤:
将吡啶和甲醇混合,然后滴加氯甲烷,经过吡啶烷基化反应生成N-甲基吡啶氯化物,经过二聚反应生成1,1-二甲基-4,4-二氢联吡啶,经过水洗除杂后,加入打浆水、酸溶液和催化剂,在搅拌速度为600-1000r/min条件下,通入液氯,搅拌反应,反应结束后,在打料时,过滤分离出催化剂,得到百草枯溶液;吡啶、甲醇、氯甲烷、打浆水、酸溶液、催化剂的用量质量比为400:40:270:548:100:20~40;所述酸溶液为盐酸、硫酸中的一种,酸溶液的质量分数10~20%;
所述催化剂通过如下步骤制备:
将碳材料和蒸馏水混合,设置温度为80℃,加热分散得到分散液,将MeCl2用蒸馏水中溶解,然后加入乙酸调节pH值为5~6,加入分散液中,搅拌分散55-60min,抽滤,将得到的滤饼,在80℃条件下干燥,待其干燥后,取出冷却,用研钵将研磨好的样品放入陶瓷坩埚中,于400℃马弗炉中煅烧3h,得到催化剂;所述碳材料、MeCl2的质量比为100:1;所述Me为金属Mn、Fe中的一种;所述催化剂的粒径为30~50μm。
2.根据权利要求1所述的一种催化氧化紫晶制备百草枯的工艺,其特征在于,搅拌反应时反应温度为40~68℃,反应压力-0.05~0.05MPa,反应时间为2~4h。
3.根据权利要求1所述的一种催化氧化紫晶制备百草枯的工艺,其特征在于,所述碳材料为碳纳米管、氧化石墨烯和活性炭中的一种。
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