CN113549116B - 一种金属螯合咪唑催化剂的制备方法及应用 - Google Patents

一种金属螯合咪唑催化剂的制备方法及应用 Download PDF

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CN113549116B
CN113549116B CN202110947307.2A CN202110947307A CN113549116B CN 113549116 B CN113549116 B CN 113549116B CN 202110947307 A CN202110947307 A CN 202110947307A CN 113549116 B CN113549116 B CN 113549116B
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高子豪
王富民
张旭斌
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HEBEI MEIBANG ENGINEERING TECHNOLOGY CO LTD
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Abstract

该发明涉及高活性催化剂制备技术领域,具体关于一种金属螯合咪唑催化剂的制备方法及应用;该发明的一种金属螯合咪唑催化剂的制备方法及应用中本发明中催化剂有效地避免粘度高且搅拌易导致活性组分流失的缺点,催化稳定性得到提高;同时能够保证催化剂的高活性,保证催化效率。

Description

一种金属螯合咪唑催化剂的制备方法及应用
技术领域
该发明涉及高活性催化剂制备技术领域,尤其是一种金属螯合咪唑催化剂的制备方法及应用。
背景技术
氯乙烯又名乙烯基氯(Vinyl chloride)是一种应用于高分子化工的重要的单体,化学式是C2H3Cl,可由乙烯或乙炔制得,为无色、易液化气体。由于我国“煤多、油少、气贫”的特点,电石乙炔法是我国氯乙烯生产的主要工艺,即氯化汞催化乙炔和氯化氢反应生成氯乙烯,其产能约占总产能的80%左右。然而由于氯化汞所具有的高毒性、易挥发的弊端极大地污染了环境和危害人体健康。因此使催化剂向低汞化、无汞化方向发展,控制并逐步消除汞污染,寻找合成氯乙烯的清洁催化剂及工艺路线,是目前氯碱行业急需解决的难题。
CN105001040B报道了一种利用金属纳米粒子/离子液体体系催化乙炔氢氯化反应的方法,首先,制备金属纳米粒子/离子液体液相催化体系,该离子液体为表面活性离子液体;60~120℃下,先向金属纳米粒子/离子液体液相催化体系中通入氯化氢进行活化,再升温至140~220℃,通入乙炔和氯化氢进行反应,经后处理得到氯乙烯产品气。本发明采用特殊的表面活性离子液体与金属纳米粒子经原位反应或共混后得到金属纳米粒子/离子液体体系。
CN110743613B提供了一种负载型金属催化剂及其制备方法与应用;所述催化剂中,金属通过与离子液体配位的形式,稳定在催化剂的外表层,减少了传质的影响,同时提高了金属的分散度;离子液体是通过硅羟基稳定在载体表面,具有更高的稳定性,不易于从载体表面流失;本发明首次将外加静态电场引入到负载离子液体的金属基催化剂制备中,促进了金属活性中心在离子液体表层的富集;由于本发明催化剂金属活性中心分布在离子液体表层,减少了底物扩散的影响,在所评价的反应条件下,催化剂的诱导期消失。
然而,现有的应用于乙炔氢氯化合成氯乙烯的负载型非贵金属催化剂活性低、负载金等贵金属催化剂稳定性差和成本高、离子液体负载金等催化剂粘度高且搅拌易导致活性组分流失等缺点。
发明内容
本发明针对上述现有技术中存在的不足,公开了一种金属螯合咪唑催化剂的制备方法及应用,属于高活性催化剂制备技术领域。本发明使用的催化剂与常规离子液体为介质的气液相反应相比,金属螯合咪唑催化剂有效地避免粘度高且搅拌易导致活性组分流失的缺点,稳定性得到提高。
一种金属螯合咪唑催化剂的制备方法及应用:
S1:按重量份,在密闭高压反应釜中加入0.05-1份乙烯基咪唑,20-30份衣康酸,15-20份双(3-巯基丙酸)乙二醇,100-120份有机溶剂,加入1.5-3.2份的乙醇钠,升温搅拌,反应1-4h,蒸去溶剂,得到中间体1;
S2:在反应釜中,加入氢氧化钠2-7份,去离子水100-200份,10-15份中间体1,搅拌0.5-2h,再加入占催化剂总重量0.5-10wt%的非贵金属氯化物,占催化剂总重量0.01-1wt%贵金属氯化物,升温T1反应1-4h,随后加热去除水分,加入50-75份醋酸丁酯,升温T2搅拌反应1-4h,得到催化剂。
进一步的,所述S1中,有机溶剂为甲醇、乙醇、乙醚、丙酮、乙酸乙酯、苯、甲苯、三氯甲烷、四氯化碳或N,N-二甲基甲酰胺中的一种;
进一步的,所述S1中,有机溶剂更优选为乙醇、三氯甲烷、或N,N-二甲基甲酰胺中的一种;
进一步的,所述S1中,升温至60-75℃;搅拌为磁力搅拌,转速为200-250r/min;蒸去溶剂方法为油浴加热,加热温度为60-120℃;
进一步的,所述S2中,搅拌为磁力搅拌,转速为200-250r/min;T1温度为60-80℃;T2温度为50-60℃;
进一步的,所述S2中,非贵金属氯化物占催化剂总重量比例更优选为1.0-6.0wt%;
进一步的,所述S2中,贵金属氯化物占催化剂总重量比例更优选为0.05-0.6wt%;
进一步的,所述S2中,去除水分具体方法为油浴锅保温加热,温度为105-115℃,时间为4-6h;
进一步的,所述S2中,非贵金属氯化物含有选自钼、铁、钛、锌、镁、锰、铋、钨和铜的金属组分;贵金属氯化物含有选自锡、钯、铂、金、铋、汞或铑的氯化物的一种或几种为活性组分;
进一步的,利用上述金属螯合咪唑催化剂催化乙炔氢氯化反应制备氯乙烯,在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为120~240℃,反应压力为0.1~0.8MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1-1.5:1,,反应原料气体流速与催化剂的体积比=50-120h-1
进一步的,所述催化乙炔氢氯化反应制备氯乙烯的应用中,温度为160~200℃,压力为0.1~0.5MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.2-1.5:1,反应原料气体流速与催化剂的体积比=60-100h-1
反应机理为:
乙烯基咪唑,衣康酸,双(3-巯基丙酸)乙二醇,进行迈克尔加成反应,得到含有二羧基的咪唑化合物,进一步与氢氧化钠中和反应,再经过离子交换,将金属离子交换到催化剂中得到金属螯合咪唑催化剂。
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技术效果为:
1.与常规离子液体为介质的气液相反应相比,金属螯合咪唑催化剂采用乙烯基咪唑,衣康酸,双(3-巯基丙酸)乙二醇加成反应,得到含有二羧基的咪唑化合物,有效地避免粘度高且搅拌易导致活性组分流失的缺点,稳定性得到提高。
2.在本发明提出的金属螯合咪唑催化剂体系中,乙炔氢氯化反应的乙炔转化率大,可达98.6%,氯乙烯选择性均大于99.51%,且在测试的96h内本发明的催化活性未见下降,具有很好的稳定性。
附图说明
图1为实施例6制备的催化剂的乙炔转化率,氯乙烯选择性的趋势图。。
具体实施方式
催化剂制备实施例1
S1:按重量份,在密闭高压反应釜中加入0.05g 乙烯基咪唑,20g衣康酸,15g双(3-巯基丙酸)乙二醇,100g乙醇,加入1.5g乙醇钠;升温至60℃,开启磁力搅拌,转速为200r/min,反应2h;油浴加热,加热温度为80℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠2g,去离子水100g,10g中间体1;磁力搅拌1h,转速为200r/min;再加入占催化剂总重量0.5wt%的氯化钼,占催化剂总重量0.01wt%的氯化钯,升温至60℃,反应2h;随后油浴锅保温加热,温度为105℃,时间为4h,去除水分;加入50g醋酸丁酯,升温至50℃,磁力搅拌,转速为200r/min,反应2h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为120℃,反应压力为0.2MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.2:1,反应原料气体流速与催化剂的体积比=60h-1。反应96h后未见催化活下降,乙炔转化率为95.6%,氯乙烯选择性为99.51%。
催化剂制备实施例2
S1:按重量份,在密闭高压反应釜中加入0.2g 乙烯基咪唑,20g衣康酸,15g双(3-巯基丙酸)乙二醇,100g乙醇,加入1.8g乙醇钠;升温至65℃,开启磁力搅拌,转速为220r/min,反应2h;油浴加热,加热温度为80℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠3g,去离子水100g,10g中间体1;磁力搅拌1h,转速为220r/min;再加入占催化剂总重量2wt%的氯化钛,占催化剂总重量0.05wt%的氯化铂,升温至60℃,反应2h;随后油浴锅保温加热,温度为105℃,时间为4h,去除水分;加入50g醋酸丁酯,升温至50℃,磁力搅拌,转速为220r/min,反应2h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为140℃,反应压力为0.3MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.3:1,反应原料气体流速与催化剂的体积比=70h-1。反应96h后未见催化活下降,乙炔转化率为96.4%,氯乙烯选择性为99.56%。
催化剂制备实施例3
S1:按重量份,在密闭高压反应釜中加入0.4g 乙烯基咪唑,25g衣康酸,18g双(3-巯基丙酸)乙二醇,100g乙醇,加入2.0g乙醇钠;升温至65℃,开启磁力搅拌,转速为240r/min,反应3h;油浴加热,加热温度为80℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠4g,去离子水150g,12g中间体1;磁力搅拌1h,转速为240r/min;再加入占催化剂总重量4wt%的氯化钨,占催化剂总重量0.2wt%的氯化金,升温至70℃,反应3h;随后油浴锅保温加热,温度为110℃,时间为5h,去除水分;加入60g醋酸丁酯,升温至60℃,磁力搅拌,转速为240r/min,反应3h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为160℃,反应压力为0.4MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.4:1,反应原料气体流速与催化剂的体积比=80h-1。反应96h后未见催化活下降,乙炔转化率为97.7%,氯乙烯选择性为99.64%。
催化剂制备实施例4
S1:按重量份,在密闭高压反应釜中加入0.6g 乙烯基咪唑,25g衣康酸,18g双(3-巯基丙酸)乙二醇,100g乙醇,加入2.4g乙醇钠;升温至65℃,开启磁力搅拌,转速为240r/min,反应3h;油浴加热,加热温度为80℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠5g,去离子水150g,12g中间体1;磁力搅拌1h,转速为240r/min;再加入占催化剂总重量6wt%的氯化镁,占催化剂总重量0.4wt%的氯化钯,升温至70℃,反应3h;随后油浴锅保温加热,温度为110℃,时间为5h,去除水分;加入60g醋酸丁酯,升温至60℃,磁力搅拌,转速为240r/min,反应3h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为180℃,反应压力为0.5MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.3:1,反应原料气体流速与催化剂的体积比=90h-1。反应96h后未见催化活下降,乙炔转化率为97.4%,氯乙烯选择性为99.61%。
催化剂制备实施例5
S1:按重量份,在密闭高压反应釜中加入0.8g 乙烯基咪唑,30g衣康酸,20g双(3-巯基丙酸)乙二醇,120g乙醇,加入2.8g乙醇钠;升温至75℃,开启磁力搅拌,转速为250r/min,反应4h;油浴加热,加热温度为90℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠6g,去离子水200g,15g中间体1;磁力搅拌2h,转速为250r/min;再加入占催化剂总重量8wt%的氯化铜,占催化剂总重量0.6wt%的氯化铂,升温至80℃,反应4h;随后油浴锅保温加热,温度为110℃,时间为6h,去除水分;加入70g醋酸丁酯,升温至60℃,磁力搅拌,转速为250r/min,反应4h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为200℃,反应压力为0.7MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.4:1,反应原料气体流速与催化剂的体积比=100h-1。反应96h后未见催化活下降,乙炔转化率为98.6%,氯乙烯选择性为99.72%。
催化剂制备实施例6
S1:按重量份,在密闭高压反应釜中加入1g 乙烯基咪唑,30g衣康酸,20g双(3-巯基丙酸)乙二醇,120g乙醇,加入3.2g乙醇钠;升温至75℃,开启磁力搅拌,转速为250r/min,反应4h;油浴加热,加热温度为90℃,蒸去乙醇,得到中间体1;
S2:在反应釜中,加入氢氧化钠7g,去离子水200g,15g中间体1;磁力搅拌2h,转速为250r/min;再加入占催化剂总重量10wt%的氯化铋,占催化剂总重量0.8wt%的氯化锡,升温至80℃,反应4h;随后油浴锅保温加热,温度为110℃,时间为6h,去除水分;加入75g醋酸丁酯,升温至60℃,磁力搅拌,转速为250r/min,反应4h,得到催化剂。
催化剂性能评价
在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为220℃,反应压力为0.8MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.5:1,反应原料气体流速与催化剂的体积比=120h-1。反应96h后未见催化活下降,乙炔转化率为98.1%,氯乙烯选择性为99.68%。
对照例
在鼓泡反应器中,不加入任何催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为240℃,反应压力为0.8MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.5:1,反应原料气体流速与催化剂的体积比=120h-1。反应96h后,乙炔转化率为64.51%,氯乙烯选择性为80.14%。

Claims (10)

1.一种金属螯合咪唑催化剂的制备方法:
S1:按重量份,在密闭高压反应釜中加入0.05-1份乙烯基咪唑,20-30份衣康酸,15-20份双(3-巯基丙酸)乙二醇,100-120份有机溶剂,加入1.5-3.2份的乙醇钠,升温搅拌,反应1-4h,蒸去溶剂,得到中间体1;
S2:在反应釜中,加入氢氧化钠2-7份,去离子水100-200份,10-15份中间体1,搅拌0.5-2h,再加入占催化剂总重量0.5-10wt%的非贵金属氯化物,占催化剂总重量0.01-1wt%贵金属氯化物,升温T1反应1-4h,随后加热去除水分,加入50-75份醋酸丁酯,升温T2搅拌反应1-4h,得到催化剂;
所述非贵金属氯化物选自:氯化钼,氯化钛,氯化钨,氯化镁,氯化铋;
所述贵金属氯化物选自:氯化钯,氯化铂,氯化金。
2.根据权求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S1中,有机溶剂为甲醇、乙醇、乙醚、丙酮、乙酸乙酯、苯、甲苯、三氯甲烷、四氯化碳或N,N-二甲基甲酰胺中的一种。
3.根据权利要求2所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S1中,有机溶剂为乙醇、三氯甲烷、或N,N-二甲基甲酰胺中的一种。
4.根据权利要求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S1中,升温至60-75℃;搅拌为磁力搅拌,转速为200-250r/min;蒸去溶剂方法为油浴加热,加热温度为60-120℃。
5.根据权利要求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S2中,搅拌为磁力搅拌,转速为200-250r/min;T1温度为60-80℃;T2温度为50-60℃。
6.根据权利要求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S2中,非贵金属氯化物占催化剂总重量比例为1.0-6.0wt%。
7.根据权利要求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S2中,贵金属氯化物占催化剂总重量比例为0.05-0.6wt%。
8.根据权利要求1所述的一种金属螯合咪唑催化剂的制备方法,其特征在于:所述S2中,去除水分具体方法为油浴锅保温加热,温度为105-115℃,时间为4-6h。
9.根据权利要求1所述方法制备得到的金属螯合咪唑催化剂的应用,其特征在于:利用上述金属螯合咪唑催化剂催化乙炔氢氯化反应制备氯乙烯,在鼓泡反应器中,加入制备得到的催化剂,将反应原料气体乙炔和氯化氢混合后通入其中进行反应,反应温度为120~240℃,反应压力为0.1~0.8MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1-1.5:1,反应原料气体流速与催化剂的体积比=50-120h-1
10.根据权利要求9所述的金属螯合咪唑催化剂的应用,其特征在于:所述催化乙炔氢氯化反应制备氯乙烯的应用中,温度为160~200℃,压力为0.1~0.5MPa;反应原料气体比例为:氯化氢/乙炔的体积比=1.2-1.5:1,反应原料气体流速与催化剂的体积比=60-100h-1
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