CN114539160A - 一种酸性光催化法合成多菌灵的生产工艺 - Google Patents
一种酸性光催化法合成多菌灵的生产工艺 Download PDFInfo
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- CN114539160A CN114539160A CN202210133777.XA CN202210133777A CN114539160A CN 114539160 A CN114539160 A CN 114539160A CN 202210133777 A CN202210133777 A CN 202210133777A CN 114539160 A CN114539160 A CN 114539160A
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- carbendazim
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Abstract
本发明公开了一种酸性光催化法合成多菌灵的生产工艺,属于多菌灵合成技术领域,包括以下步骤:第一步、将甲醇、邻硝基苯胺和Raney Ni催化剂混合,100‑120℃下反应2‑5h,过滤,回收催化剂,向一次滤液中加入去离子水和除杂粒子,搅拌后,过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏,得到邻苯二胺;第二步、向反应釜中加入氰胺基甲酸甲酯、邻苯二胺,升温至50‑60℃,滴加浓盐酸,将反应液转移至雾化器中处理2h,启动高压灯,将雾化好的底物喷雾进入合成釜内,100‑120℃下反应1‑2h,反应产物进行高温离心后保留固体,洗涤,干燥,得到多菌灵,本发明生产所得的多菌灵的收率较高、纯度较高。
Description
技术领域
本发明属于多菌灵合成技术领域,具体涉及一种酸性光催化法合成多菌灵的生产工艺。
背景技术
多菌灵是一种广谱性杀菌剂,对多种作物由真菌(如半知菌、多子囊菌)引起的病害有防治效果。可用于叶面喷雾、种子处理和土壤处理等。纯品为白色结晶固体,在碱性溶液中缓慢分解,随pH升高分解加快,随pH降低失去活性,以7作为基准。化学性质稳定,原药在阴凉、干燥处贮存2-3年,有效成分不变。
随着越来越严格的环境保护要求,对多菌灵的质量要求亦越来越高,尤其是多菌灵中含有的酚嗪类杂质2,3-二氨基酚嗪(DAP)和2-氨-3-羟基酚嗪(HAP),它们是强烈的致畸致癌物质,因此,要求多菌灵DAP+HAP≤3.5mg/kg,其中DAP和HAP的分子结构式分别如下:
经过研究测试发现,在多菌灵合成最后一步,中间体邻苯二胺和氰胺基甲酸甲酯在酸性条件下缩合成多多菌灵过程中,是不可能发生副反应而产生DAP和HAP的,而在中间体邻苯二胺合成过程中可能带入形成DAP和HAP的前体主要是邻硝基氯化苯,其在高温高压的氨化、碱性化水解条件下生成DAP和HAP,因此,严格控制生成过程中中间体邻苯二胺中DAP和HAP的含量,是保证多菌灵产品纯度的关键步骤,因此,本申请从如何提高中间体邻苯二胺的纯度出发,通过酸性光催化法合成高纯度多菌灵。
发明内容
本发明的目的在于提供一种酸性光催化法合成多菌灵的生产工艺,以解决背景技术中的问题。
一种酸性光催化法合成多菌灵的生产工艺,包括以下步骤:
第一步、将甲醇和邻硝基苯胺按照0.1-0.3kg:1mL加入反应釜中,反应釜内壁具有聚四氟乙烯涂层,搅拌桨具有聚四氟乙烯涂层;搅拌20-30min后,加入Raney Ni催化剂,催化剂用量为邻硝基苯胺质量的0.05-2%,通入氮气20min后通入氢气,氢气压力为0.5-3MPa,反应温度为100-120℃,反应时间为2-5h,反应完成后,过滤,回收催化剂,向一次滤液中加入去离子水和除杂粒子,搅拌20-60min后,过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏去除甲醇和去离子水,得到邻苯二胺;
第二步、向反应釜(同样具有聚四氟乙烯内衬和聚四氟乙烯涂层的搅拌桨)中加入氰胺基甲酸甲酯、邻苯二胺,升温至50-60℃,开始滴加摩尔浓度12mol/L的盐酸,滴加结束后,将反应液转移至雾化器中处理2h,然后启动高压灯,将雾化好的底物喷雾进入合成釜内,温度100-120℃下反应1-2h,反应结束后,通入氮气进行恒温赶气30-60min,赶出的气体直接导入碱液吸收,得到的反应产物进行高温离心后保留固体,用温度35-40℃温水进行洗涤,80℃下真空干燥至恒重,得到多菌灵;氰胺基甲酸甲酯、邻苯二胺和盐酸用量比为1-1.5mol:1mol:0.1L。
进一步地,所述高压灯设置为可见光高压灯、紫外线高压灯或红外线高压灯中的一种,高压灯设置4-8个且等距设置。
进一步地,所述除杂粒子由以下步骤制成:
步骤A1、室温条件下,将香草醛和吡啶置于三口烧瓶中,加入溶剂二氯甲烷并通过磁子搅拌溶解至澄清,氮气保护下,通过恒压滴液漏斗向三口烧瓶中滴加甲基丙烯酰氯二氯甲烷溶液,滴加结束后,回流反应3h,旋蒸去除二氯甲烷,旋蒸产物溶解于乙酸乙酯中,用饱和食盐水洗涤3次后,用饱和碳酸氢钠溶液洗涤3次,再用去离子水洗涤3次,最后有机层用无水硫酸镁干燥,旋蒸去除乙酸乙酯,得到香草醛衍生物;
其中,香草醛、吡啶、二氯甲烷和甲基丙烯酰氯二氯甲烷溶液的用量比为20mmol:1.7-1.9g:40-60mL:10mL,甲基丙烯酰氯二氯甲烷溶液由甲基丙烯酰氯和二氯甲烷按照21-24mmol:10mL混合而成;以吡啶为缚酸剂,使甲基丙烯酰氯和香草醛发生化学反应得到香草醛衍生物,反应过程如下:
步骤A2、将埃洛石纳米管加入质量分数30%的木质素磺酸钠水溶液中并超声分散形成悬浊液,然后于负压条件下静置2h,再以转速3000r/min条件下离心1.5h,沉淀于100℃下干燥至恒重后,转移至马弗炉中,在氮气气氛下,以5℃/min升温速度升温至500℃,保温2h,然后冷却至室温,用质量分数10%的HF溶液浸泡4-6h,然后过滤,滤饼用去离子水洗涤3-5次,置于60℃下干燥12h,得到多孔碳材;
其中,埃洛石纳米管和木质素磺酸钠水溶液的用量比为1.5-1.8g:20mL,以埃洛石纳米管为模板剂,木质素磺酸钠为碳源,制备出多孔碳材;
步骤A3、将多孔碳材和KOH按照质量比1:4置于研钵中,研磨20-40min后,将研磨产物置于管式炉中进行活化,在氮气保护下,由室温升温至850℃并维持1.0h,升温速度为5.0℃/min,然后用大量去离子水洗涤至中性,最后于100℃下干燥至恒重,得到多孔吸附基材;
步骤A4、将多孔吸附基材、无水乙醇和去离子水加入三口烧瓶中,频率40-50kHz下超声分散20min,然后加入偶联剂KH-590,搅拌反应6-8h,然后通入氮气,氮气保护下,向三口烧瓶中加入香草醛衍生物的乙醇溶液,升温至40℃,搅拌条件下加入催化剂三乙胺,然后升温至回流反应1-2h,反应结束后,转速1000-1500r/min条件下离心20min,沉淀用去离子水洗涤至洗涤液呈中性,在于100℃烘箱中干燥至恒重,得到除杂粒子;
其中,多孔吸附基材、无水乙醇、去离子水、KH-590、香草醛衍生物的乙醇溶液和三乙胺的用量比为3.8-4.5g:40-50mL:40-50mL:0.01mol:5mL:0.02mol,香草醛衍生物的乙醇溶液由香草醛衍生物和无水乙醇按照0.01mol:5mL混合而成;首先利用偶联剂KH-590对多孔吸附基材进行改性处理,使其表面接枝-SH键,然后在三乙胺的催化作用下,使-SH键与香草醛衍生物的不饱和双键发生化学反应,得到除杂粒子。
本发明的有益效果:
1.本发明多菌灵合成方法严格控制反应温度和pH,科学配比各种原料,在酸性条件下进行光催化反应,采用高压灯配合循环喷雾操作,使多菌灵产品纯度提高,品质提高,含量不低于98%,压制DAP和HAP杂质生成,并用热水多次清洗,进一步减少邻苯二胺残留,使多菌灵中的DAP、HAP残留得到控制。
2.针对多菌灵合成过程中杂质DAP和HAP主要来源于中间体邻苯二胺,本发明在邻苯二胺产物形成后,加入一种吸附颗粒,以埃洛石纳米管为模板剂,木质素磺酸钠为碳源,制备出多孔碳材,然后通过和KOH共磨焙烧活化得到除杂粒子,然后利用偶联剂KH-590对多孔吸附基材进行改性处理,使其表面接枝-SH键,然后在三乙胺的催化作用下,使-SH键与香草醛衍生物的不饱和双键发生化学反应,得到除杂粒子,除杂粒子同时具有大孔、介孔和微孔三种不同等级的孔道结构,具有优异的吸附性能,然后利用除杂离子表面接枝的香草衍生物的醛基与DAP和HAP发生缩合反应,进而通过物理和化学吸附实现去除DAP和HAP杂质,进而提高多菌灵的纯度。
附图说明
下面结合附图对本发明作进一步的说明。
图1是本发明一种酸性光催化法合成多菌灵的生产工艺的流程示意图。
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
本实施例提供一种除杂粒子,由以下步骤制成:
步骤A1、室温条件下,将20mmol香草醛和1.7g吡啶置于三口烧瓶中,加入溶剂40mL二氯甲烷并通过磁子搅拌溶解至澄清,氮气保护下,通过恒压滴液漏斗向三口烧瓶中滴加10mL甲基丙烯酰氯二氯甲烷溶液,滴加结束后,升温至回流反应3h,旋蒸去除二氯甲烷,旋蒸产物溶解于乙酸乙酯中,用饱和食盐水洗涤3次后,用饱和碳酸氢钠溶液洗涤3次,再用去离子水洗涤3次,最后有机层用无水硫酸镁干燥,旋蒸去除乙酸乙酯,得到香草醛衍生物,甲基丙烯酰氯二氯甲烷溶液由甲基丙烯酰氯和二氯甲烷按照21mmol:10mL混合而成;
步骤A2、将4.5g埃洛石纳米管加入60mL质量分数30%的木质素磺酸钠水溶液中并超声分散形成悬浊液,然后于负压条件下静置2h,再以转速3000r/min条件下离心1.5h,沉淀于100℃下干燥至恒重后,转移至马弗炉中,在氮气气氛下,以5℃/min升温速度升温至500℃,保温2h,然后冷却至室温,用质量分数10%的HF溶液浸泡4h,然后过滤,滤饼用去离子水洗涤3次,置于60℃下干燥12h,得到多孔碳材;
步骤A3、将多孔碳材和KOH按照质量比1:4置于研钵中,研磨20min后,将研磨产物置于管式炉中进行活化,在氮气保护下,由室温升温至850℃并维持1.0h,升温速度为5.0℃/min,然后用大量去离子水洗涤至中性,最后于100℃下干燥至恒重,得到多孔吸附基材;
步骤A4、将3.8g多孔吸附基材、40mL无水乙醇和40mL去离子水加入三口烧瓶中,频率40kHz下超声分散20min,然后加入0.01mol偶联剂KH-590,搅拌反应6h,然后通入氮气,氮气保护下,向三口烧瓶中加入5mL香草醛衍生物的乙醇溶液,升温至40℃,搅拌条件下加入催化剂0.02mol三乙胺,然后升温至回流反应1h,反应结束后,转速1000r/min条件下离心20min,沉淀用去离子水洗涤至洗涤液呈中性,在于100℃烘箱中干燥至恒重,得到除杂粒子,香草醛衍生物的乙醇溶液由香草醛衍生物和无水乙醇按照0.01mol:5mL混合而成。
实施例2
本实施例提供一种除杂粒子,由以下步骤制成:
步骤A1、室温条件下,将20mmol香草醛和1.8g吡啶置于三口烧瓶中,加入溶剂50mL二氯甲烷并通过磁子搅拌溶解至澄清,氮气保护下,通过恒压滴液漏斗向三口烧瓶中滴加10mL甲基丙烯酰氯二氯甲烷溶液,滴加结束后,升温至回流反应3h,旋蒸去除二氯甲烷,旋蒸产物溶解于乙酸乙酯中,用饱和食盐水洗涤3次后,用饱和碳酸氢钠溶液洗涤3次,再用去离子水洗涤3次,最后有机层用无水硫酸镁干燥,旋蒸去除乙酸乙酯,得到香草醛衍生物,甲基丙烯酰氯二氯甲烷溶液由甲基丙烯酰氯和二氯甲烷按照23mmol:10mL混合而成;
步骤A2、将4.8g埃洛石纳米管加入60mL质量分数30%的木质素磺酸钠水溶液中并超声分散形成悬浊液,然后于负压条件下静置2h,再以转速3000r/min条件下离心1.5h,沉淀于100℃下干燥至恒重后,转移至马弗炉中,在氮气气氛下,以5℃/min升温速度升温至500℃,保温2h,然后冷却至室温,用质量分数10%的HF溶液浸泡5h,然后过滤,滤饼用去离子水洗涤3次,置于60℃下干燥12h,得到多孔碳材;
步骤A3、将多孔碳材和KOH按照质量比1:4置于研钵中,研磨30min后,将研磨产物置于管式炉中进行活化,在氮气保护下,由室温升温至850℃并维持1.0h,升温速度为5.0℃/min,然后用大量去离子水洗涤至中性,最后于100℃下干燥至恒重,得到多孔吸附基材;
步骤A4、将4.2g多孔吸附基材、45mL无水乙醇和45mL去离子水加入三口烧瓶中,频率45kHz下超声分散20min,然后加入0.01mol偶联剂KH-590,搅拌反应7h,然后通入氮气,氮气保护下,向三口烧瓶中加入5mL香草醛衍生物的乙醇溶液,升温至40℃,搅拌条件下加入催化剂0.02mol三乙胺,然后升温至回流反应1.5h,反应结束后,转速1200r/min条件下离心20min,沉淀用去离子水洗涤至洗涤液呈中性,在于100℃烘箱中干燥至恒重,得到除杂粒子,香草醛衍生物的乙醇溶液由香草醛衍生物和无水乙醇按照0.01mol:5mL混合而成。
实施例3
本实施例提供一种除杂粒子,由以下步骤制成:
步骤A1、室温条件下,将20mmol香草醛和1.9g吡啶置于三口烧瓶中,加入溶剂60mL二氯甲烷并通过磁子搅拌溶解至澄清,氮气保护下,通过恒压滴液漏斗向三口烧瓶中滴加10mL甲基丙烯酰氯二氯甲烷溶液,滴加结束后,升温至回流反应3h,旋蒸去除二氯甲烷,旋蒸产物溶解于乙酸乙酯中,用饱和食盐水洗涤3次后,用饱和碳酸氢钠溶液洗涤3次,再用去离子水洗涤3次,最后有机层用无水硫酸镁干燥,旋蒸去除乙酸乙酯,得到香草醛衍生物,甲基丙烯酰氯二氯甲烷溶液由甲基丙烯酰氯和二氯甲烷按照24mmol:10mL混合而成;
步骤A2、将5.4g埃洛石纳米管加入60mL质量分数30%的木质素磺酸钠水溶液中并超声分散形成悬浊液,然后于负压条件下静置2h,再以转速3000r/min条件下离心1.5h,沉淀于100℃下干燥至恒重后,转移至马弗炉中,在氮气气氛下,以5℃/min升温速度升温至500℃,保温2h,然后冷却至室温,用质量分数10%的HF溶液浸泡6h,然后过滤,滤饼用去离子水洗涤5次,置于60℃下干燥12h,得到多孔碳材;
步骤A3、将多孔碳材和KOH按照质量比1:4置于研钵中,研磨40min后,将研磨产物置于管式炉中进行活化,在氮气保护下,由室温升温至850℃并维持1.0h,升温速度为5.0℃/min,然后用大量去离子水洗涤至中性,最后于100℃下干燥至恒重,得到多孔吸附基材;
步骤A4、将4.5g多孔吸附基材、50mL无水乙醇和50mL去离子水加入三口烧瓶中,频率50kHz下超声分散20min,然后加入0.01mol偶联剂KH-590,搅拌反应8h,然后通入氮气,氮气保护下,向三口烧瓶中加入5mL香草醛衍生物的乙醇溶液,升温至40℃,搅拌条件下加入催化剂0.02mol三乙胺,然后升温至回流反应2h,反应结束后,转速1500r/min条件下离心20min,沉淀用去离子水洗涤至洗涤液呈中性,在于100℃烘箱中干燥至恒重,得到除杂粒子,香草醛衍生物的乙醇溶液由香草醛衍生物和无水乙醇按照0.01mol:5mL混合而成。
实施例4
请参阅图1所示,一种酸性光催化法合成多菌灵的生产工艺,包括以下步骤:
第一步、将甲醇和邻硝基苯胺按照0.1kg:1mL加入反应釜中,反应釜内壁具有聚四氟乙烯涂层,搅拌桨具有聚四氟乙烯涂层;搅拌20min后,加入Raney Ni催化剂,催化剂用量为邻硝基苯胺质量的0.05%,通入氮气20min后通入氢气,氢气压力为0.5MPa,反应温度为100℃,反应时间为2h,反应完成后,过滤,回收催化剂,向一次滤液中加入去离子水和实施例1的除杂粒子,搅拌20min后,过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏去除甲醇和去离子水,得到邻苯二胺;
第二步、向反应釜(同样具有聚四氟乙烯内衬和聚四氟乙烯涂层的搅拌桨)中加入氰胺基甲酸甲酯、邻苯二胺,升温至50℃,开始滴加摩尔浓度12mol/L的盐酸,滴加结束后,将反应液转移至雾化器中处理2h,然后启动高压灯,将雾化好的底物喷雾进入合成釜内,温度100℃下反应1h,反应结束后,通入氮气进行恒温赶气30min,赶出的气体直接导入碱液吸收,得到的反应产物进行高温离心后保留固体,用温度35℃温水进行洗涤,80℃下真空干燥至恒重,得到多菌灵,氰胺基甲酸甲酯、邻苯二胺和盐酸的用量比为1mol:1mol:0.1L。
其中,所述高压灯设置为可见光高压灯、紫外线高压灯或红外线高压灯中的一种,高压灯设置4个且等距设置。
实施例5
一种酸性光催化法合成多菌灵的生产工艺,包括以下步骤:
第一步、将甲醇和邻硝基苯胺按照0.2kg:1mL加入反应釜中,反应釜内壁具有聚四氟乙烯涂层,搅拌桨具有聚四氟乙烯涂层;搅拌25min后,加入Raney Ni催化剂,催化剂用量为邻硝基苯胺质量的1%,通入氮气20min后通入氢气,氢气压力为2MPa,反应温度为100℃,反应时间为4h,反应完成后,过滤,回收催化剂,向一次滤液中加入去离子水和实施例2的除杂粒子,搅拌40min后,过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏去除甲醇和去离子水,得到邻苯二胺;
第二步、向反应釜(同样具有聚四氟乙烯内衬和聚四氟乙烯涂层的搅拌桨)中加入氰胺基甲酸甲酯、邻苯二胺,升温至55℃,开始滴加摩尔浓度12mol/L的盐酸,滴加结束后,将反应液转移至雾化器中处理2h,然后启动高压灯,将雾化好的底物喷雾进入合成釜内,温度110℃下反应1.5h,反应结束后,通入氮气进行恒温赶气40min,赶出的气体直接导入碱液吸收,得到的反应产物进行高温离心后保留固体,用温度38℃温水进行洗涤,80℃下真空干燥至恒重,得到多菌灵;氰胺基甲酸甲酯、邻苯二胺和盐酸的用量比为1.2mol:1mol:0.1L。
其中,所述高压灯设置为可见光高压灯、紫外线高压灯或红外线高压灯中的一种,高压灯设置6个且等距设置。
实施例6
一种酸性光催化法合成多菌灵的生产工艺,包括以下步骤:
第一步、将甲醇和邻硝基苯胺按照0.3kg:1mL加入反应釜中,反应釜内壁具有聚四氟乙烯涂层,搅拌桨具有聚四氟乙烯涂层;搅拌30min后,加入Raney Ni催化剂,催化剂用量为邻硝基苯胺质量的2%,通入氮气20min后通入氢气,氢气压力为3MPa,反应温度为120℃,反应时间为5h,反应完成后,过滤,回收催化剂,向一次滤液中加入去离子水和实施例3的除杂粒子,搅拌60min后,过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏去除甲醇和去离子水,得到邻苯二胺;
第二步、向反应釜(同样具有聚四氟乙烯内衬和聚四氟乙烯涂层的搅拌桨)中加入氰胺基甲酸甲酯、邻苯二胺,升温至60℃,开始滴加摩尔浓度12mol/L的盐酸,滴加结束后,将反应液转移至雾化器中处理2h,然后启动高压灯,将雾化好的底物喷雾进入合成釜内,温度120℃下反应2h,反应结束后,通入氮气进行恒温赶气60min,赶出的气体直接导入碱液吸收,得到的反应产物进行高温离心后保留固体,用温度40℃温水进行洗涤,80℃下真空干燥至恒重,得到多菌灵;氰胺基甲酸甲酯、邻苯二胺和盐酸的用量比为1.5mol:1mol:0.1L。
其中,所述高压灯设置为可见光高压灯、紫外线高压灯或红外线高压灯中的一种,高压灯设置8个且等距设置。
对比例1
将实施例4中的除杂粒子去除,其余原料及制备过程不变。
对比例2
将实施例5中的启动高压灯环节去除,其余原料及制备过程不变。
将实施例4-6生产工艺所得的多菌灵和对比例1-2所得的多菌灵进行收率测试和HPLC检测纯度;测试结果如下表所示:
项目 | 实施例4 | 实施例5 | 实施例6 | 对比例1 | 对比例2 |
收率(%) | 97.2 | 97.3 | 97.6 | 96.5 | 96.3 |
纯度(%) | 99.8 | 99.7 | 99.6 | 98.1 | 97.6 |
由上表可以看出,实施例4-6的生产所得的多菌灵纯度较高,得率较高。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (7)
1.一种酸性光催化法合成多菌灵的生产工艺,其特征在于,包括以下步骤:
第一步、将甲醇和邻硝基苯胺加入反应釜中,搅拌后加入Raney Ni催化剂,通入氮气20min后通入氢气,温度100-120℃下反应2-5h,反应完成后,过滤,回收催化剂,向一次滤液中加入去离子水和除杂粒子,搅拌后过滤去除滤饼,收集二次滤液,将二次滤液进行真空蒸馏,得到邻苯二胺;
第二步、向反应釜中加入氰胺基甲酸甲酯、邻苯二胺,升温至50-60℃,滴加盐酸,滴加结束后,将反应液转移至雾化器中处理2h,启动高压灯,将雾化好的底物喷雾进入合成釜内,100-120℃下反应1-2h,通入氮气赶气30-60min,反应产物离心后保留固体,洗涤,干燥,得到多菌灵。
2.根据权利要求1所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,第一步中Raney Ni催化剂用量为邻硝基苯胺质量的0.05-2%。
3.根据权利要求1所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,第二步中盐酸的浓度为12mol/L。
4.根据权利要求1所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,第二步中氰胺基甲酸甲酯、邻苯二胺和盐酸用量比为1-1.5mol:1mol:0.1L。
5.根据权利要求1所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,除杂粒子由以下步骤制成:
将多孔吸附基材、无水乙醇和去离子水超声分散,加入偶联剂KH-590,搅拌反应6-8h,然后通入氮气,加入香草醛衍生物的乙醇溶液,升温至40℃,搅拌条件下加入三乙胺,回流反应1-2h,离心,洗涤,干燥,得到除杂粒子。
6.根据权利要求5所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,香草醛衍生物由以下步骤制成:
室温条件下,将香草醛和吡啶置于三口烧瓶中,加入溶剂二氯甲烷并通过磁子搅拌,氮气保护下,滴加甲基丙烯酰氯二氯甲烷溶液,滴加结束后,回流反应3h,旋蒸,旋蒸产物溶解于乙酸乙酯中,洗涤,干燥,旋蒸,得到香草醛衍生物。
7.根据权利要求5所述的一种酸性光催化法合成多菌灵的生产工艺,其特征在于,多孔吸附基材由以下步骤制成:
步骤B1、将埃洛石纳米管加入木质素磺酸钠水溶液中并超声分散形成悬浊液,于负压条件下静置2h,离心后沉淀干燥,转移至马弗炉中,在氮气气氛下,500℃下保温2h,然后冷却,用HF溶液浸泡4-6h,过滤,洗涤,干燥,得到多孔碳材;
步骤B2、将多孔碳材和KOH置于研钵中,研磨20-40min后,将研磨产物置于管式炉中进行活化,在氮气保护下,升温至850℃并维持1.0h,洗涤,干燥,得到多孔吸附基材。
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