CN102658162A - 一种用于合成乙撑胺的催化剂及制备乙撑胺的方法 - Google Patents
一种用于合成乙撑胺的催化剂及制备乙撑胺的方法 Download PDFInfo
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- CN102658162A CN102658162A CN2012101087431A CN201210108743A CN102658162A CN 102658162 A CN102658162 A CN 102658162A CN 2012101087431 A CN2012101087431 A CN 2012101087431A CN 201210108743 A CN201210108743 A CN 201210108743A CN 102658162 A CN102658162 A CN 102658162A
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Abstract
本发明涉及一种用于合成乙撑胺的催化剂及制备乙撑胺的方法。催化剂是由主活性组分、助剂和氨化处理过的载体三部分组成,主活性组分为Ni或Co,助剂为Fe、Cu、Ru、Re、K、Zn、B等金属或氧化物中的一种或几种;氨化处理过的载体选用经过氨化处理的SiO2或Al2O3。在催化剂总重量中主活性组分占1~40%,助剂占0.1~20%。本发明催化剂的特点是是所采用的载体需要经过氨化特殊处理。使用本发明的催化剂进行乙醇胺氨化反应,在临氢条件下合成乙撑胺产品,表现出高活性、高选择性和稳定性。
Description
技术领域
本发明涉及一种用于合成乙撑胺的催化剂及其应用。更详细地,涉及一种用于临氢条件下乙醇胺(MEA)和氨转化为乙二胺(EDA)、二乙烯三胺(DETA)、羟乙基乙二胺(AEEA)、哌嗪(PIP)、羟乙基哌嗪(HEP)、氨乙基哌嗪(AEP)等乙撑胺的催化剂及制备乙撑胺的方法。
背景技术
乙撑胺产品是重要的化工原料和精细化工中间体,其主要包括乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺、哌嗪等产品,可用作环氧树脂固化剂、乳化剂、抗冻剂、有机溶剂和化学分析试剂;用于生产农药杀菌剂、杀虫剂、除草剂、燃料、医药、表面活性剂、金属络合剂等多种化学助剂;也可用于生产螯合剂、防蚀剂、土壤改良剂、润滑剂、润滑油添加剂和橡胶促进剂以及纺织、造纸、涂料和粘合剂等行业,用途十分广泛。
目前工业上合成乙撑胺的方法主要是二氯乙烷工艺和乙醇胺工艺。
二氯乙烷工艺对设备的腐蚀性严重、能耗大并且会造成严重的环境污染,从而造成生产成本高,因而该工艺路线正逐渐被淘汰。
乙醇胺工艺路线投资低,并且环境污染小。乙醇胺工艺又分为还原工艺和缩合工艺,其中还原工艺需要在高压临氢条件下反应,产品大部分为乙二胺;而缩合工艺无需临氢,反应产物以环胺为主。
国外对工业乙撑胺的合成工艺开发较早,其中BASF首先开发成功乙醇胺工艺,并于上世纪60年代实现了工业化,其后较多欧美公司采用。BASF所开发的乙醇胺工艺采用Ni、Co、Cu等金属催化剂,反应温度为150~230℃,压力为20.0~30.0MPa,其产品主要是乙二胺、二乙烯三胺、羟乙基乙二胺、哌嗪、氨乙基哌嗪、羟乙基哌嗪等。而国内由于生产技术和生产能力与国外差距很大,目前工业乙撑胺产品绝大部分依靠进口。
乙醇胺与氨在催化剂存在下胺化生成乙二胺,由于中间产物亚胺比氨具有更高的反应活性,因此反应不可避免的产生复杂的多亚烷基多胺副产物,使得乙二胺的收率降低并导致产物分离困难。常用的方法能提高产物的选择性,但是转化率降低,影响了乙二胺的产能。因此,需要一种催化剂不仅能提高目标产物的选择性,并且保持良好的胺化转化率。
US5068330采用不同的镍基金属催化剂,添加Ir、Pt、Ru等贵金属,在120~300℃,乙醇胺转化率为20%~45%,并且生成的乙二胺的选择性为15%~55%,且二乙烯三胺的选择性为10%~20%。该催化剂的乙醇胺转化率和乙二胺选择性均难达到要求,而且在制备过程中反复连续加入贵金属,增加了工艺操作的复杂性和生产成本。
US4642303报道了在Ni-Cu-Cr催化剂的作用下,乙醇胺氨化反应温度在低温下有利于乙二胺的生成。
US4209424报道了镍负载量对催化剂活性的影响,其中发现随着镍负载量的增加,原料乙醇胺的转化率不断提高,但是反应对环胺(如哌嗪)具有更高的选择性。
US4123462指出催化剂活性与载体材料有密切的关系,其中改变载体的表面积、孔尺寸、孔体积和载体形状等表面性能,将在一定范围内影响催化剂的活性。
但是,上述现有技术的催化剂以及制备乙撑胺的方法在活性、选择性和稳定性等一个或多个方面需要进一步提高。
发明内容
本发明的目的是提供一种用于合成乙撑胺的催化剂及制备乙撑胺的方法,所述催化剂及制备乙撑胺的方法可以实现以下中的一项或多项:(1)使乙醇胺临氢胺化生产乙撑胺可以在较低的反应压力下实现,(2)调变反应条件可以灵活调变乙撑胺的组成,(3)降低生产装置一次性投资和生产成本,(4)实现易操作,(5)提高催化剂的活性,(6)提高对产物的选择性,(7)提高原料的转化率,和(8)提高方法的稳定性。
本发明的发明人发现:载体材料和催化剂活性有密切的关系,将催化剂采用的载体进行氨化处理,由于载体SiO2或Al2O3的表面上存在大量的羟基使载体表面呈酸性环境,有利于中间产物亚胺聚合,而载体表面被氨化以后,表面大量的羟基转化为胺基,因而载体为碱性环境,这就降低了亚胺聚合的可能性,提高了催化剂的活性、选择性和稳定性;由此可以实现上述目的中的一个或多个。
因此,在一个方面,本发明提供一种用于合成乙撑胺的催化剂,所述催化剂是由主活性组分、助剂和氨化处理过的载体三部分组成,其中所述主活性组分选自由Ni和Co组成的组中的一种或多种,所述助剂选自由Fe、Cu、Ru、Re、K、Zn和B以及它们各自的氧化物组成的组中的一种或多种;所述氨化处理过的载体由选自由SiO2和Al2O3组成的组中的一种或多种载体经过氨化处理而得到,所述氨化处理包括:将载体与氨源在200至400℃的温度接触0.5至24小时。
在一个优选的实施方案中,所述载体的比表面积为150~350m2/g,并且平均孔径为8-80nm。
在另一个优选的实施方案中,所述氨源选自由氨气、液氨、氨水和尿素组成的组中的一种或多种。
在另一个优选的实施方案中,所述主活性组分在所述催化剂的总重量中占1~40%,优选5~30%。
在另一个优选的实施方案中,所述助剂在所述催化剂的总重量中占0.1~20%,优选0.1~15%。
在另一个方面,本发明提供一种用于由乙醇胺和氨制备乙撑胺的方法,所述方法包括:在上面所述的催化剂存在下,在临氢条件下将乙醇胺和氨转化为乙撑胺。
在一个优选的实施方案中,所述方法在温度为135~200℃,压力为6.0~22.0MPa并且乙醇胺的液体空速为0.3~1.5h-1的条件下进行。
在另一个优选的实施方案中,所述催化剂在使用之前在氢气气氛中并且在压力为常压,温度为150~400℃并且氢气空速为500~4000h-1的条件下还原活化。
具体实施方式
更具体而言,本发明提供一种用于合成乙撑胺产品的负载型催化剂,是由主活性组分、助剂和氨化处理过的载体组成,主活性组分为Ni和/或Co,助剂为Fe、Cu、Ru、Re、K、Zn和B以及它们各自的氧化物组成的组中的一种或多种;载体选用SiO2和/或Al2O3,并且载体已经经过氨化特殊处理。其中,催化剂通过浸渍法制备,其中用Ni和/或Co的可溶性盐的溶液浸渍载体,所述可溶性盐是Ni和/或Co的硝酸盐、氯化盐、乙酸盐、草酸盐、硫酸盐、柠檬酸盐或其他可溶性盐。主活性组分在催化剂总重量中占1~40%;助剂在催化剂总重量中占0.1~20%;载体SiO2或Al2O3的比表面积为150~350m2/g,平均孔径为8-80nm。载体SiO2和/或Al2O3采用氨气、液氨、氨水或者尿素来进行氨化处理。
本发明的催化剂在应用前在氢气气氛中还原活化:压力为常压,温度为150~400℃,氢气空速为500~4000h-1。在临氢条件下将乙醇胺和氨转化为乙撑胺产品的反应条件:温度为135~200℃,压力为6.0~22.0MPa,乙醇胺的液体空速为0.3~1.5h-1。
本发明的反应器可以采用固定床反应器、浆态床反应器或滴流床反应器。其中优选滴流床反应器。
本发明的反应体系中,可直接将液态的乙醇胺和氨混合物泵入到预热器中与氢气混合后预热至135~200℃后进入到滴流床反应器中。
本催化剂应用于临氢条件下乙醇胺和氨的反应中,表现出了优异的活性、选择性和稳定性,生成的乙撑胺产品包括乙二胺、二乙烯三胺、羟乙基乙二胺、哌嗪、氨乙基哌嗪、羟乙基哌嗪等乙撑胺。
本发明中,临氢条件是指有氢气存在的条件下。
本发明与现有技术相比,其显著的效果是:本发明的催化剂的载体SiO2或Al2O3采用氨气、液氨、氨水或者尿素来进行氨化处理。由于载体SiO2或Al2O3的表面上存在大量的羟基使载体表面呈酸性环境,有利于中间产物亚胺聚合而产生大量的副产物,从而降低了乙二胺的选择性。而载体表面被氨化以后,表面大量的羟基转化为胺基而呈碱性,这就降低了亚胺聚合的可能性,提高了选择性和稳定性。处理后的载体负载主活性组分和助剂以后,将其应用于临氢条件下乙醇胺和氨的反应中,表现出了优异的活性、选择性和稳定性,优化了反应条件,实现了乙撑胺产品的灵活调变,为工业生产适应市场波动提供了可能性。其反应操作工艺条件的温度、压力明显低于现有技术。生产工艺条件优化会降低对反应设备的压力要求,降低反应装置的一次性投资和生产成本,同时减小操作难度。
实施例
下面结合实施例对本发明的方法做进一步说明,并不是对本发明的限定。除非另外指出,本申请中的份、百分比以及含量按重量计。
实施例1:
5%Ni-15%Re-1.2%B/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时,然后引入10%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将2.477克Ni(NO3)2·6H2O,2.161克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。用此水溶液的一半浸渍上述氨化处理过的SiO2载体,自然晾干,随后120℃干燥4小时,接着500℃焙烧4小时。然后,用上述剩余的另一半水溶液第二次浸渍上述氨化处理过的SiO2载体,接着自然晾干,120℃干燥4小时,500℃焙烧4小时。催化剂使用前,在375℃氢气流中(常压,2000h-1)还原4小时。反应器内温度自然降温到160℃时,升压至8MPa,系统稳定后,将NH3/乙醇胺=10的液体流经泵打入反应器中,调节乙醇胺的液体空速为0.5h-1,H2/NH3/乙醇胺=0.25∶10∶1(摩尔比),进行反应,反应时间50小时,取样分析。SE-30毛细管色谱柱,FID检测器,N,N-二甲基甲酰胺为内标进行定量分析,反应结果见表1。
实施例2:
15%Ni-3.6%Re-1.2%B/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.432克Ni(NO3)2·6H2O,0.518克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例3:
30%Ni-0.2%Re-15%K/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时,然后引入50%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将14.864克Ni(NO3)2·6H2O,0.029克NH4ReO4和3.879克KNO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例4:
15%Ni-3.6%Cu-1.2%B/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.432克Ni(NO3)2·6H2O,1.369克Cu(NO3)2·3H2O和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例5:
15%Co-3.6%Re-1.2%B/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.408克Co(NO3)2·H2O,0.518克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例6:
5%Ni-8%Re-1.2%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入10%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将2.477克NiCl2·6H2O,1.152克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例7:
15%Ni-2%Re-1.2%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.432克Ni(NO3)2·6H2O,0.288克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例8:
30%Ni-2%Re-1.2%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入50%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将12.712克Ni(CH3COO)2·6H2O,0.288克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例9:
15%Ni-0.2%Re-10%Zn/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为200℃,氨化时间5小时。将6.356克Ni(CH3COO)2·6H2O,0.029克NH4ReO4和4.549克Zn(NO3)2·6H2O溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例10:
15%Ni-3.6%Re-0.2%Zn/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.432克Ni(NO3)2·6H2O,0.518克NH4ReO4和0.091克Zn(NO3)2·6H2O溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例11:
30%Ni-2%Re/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入50%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将14.864克Ni(NO3)2·6H2O和0.288克NH4ReO4溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例12:
15%Ni-2%Re-12%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.432克Ni(NO3)2·6H2O,0.288克NH4ReO4和6.86克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例13:
5%Co-15%Cu-1.2%K/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入10%氨气-氢气混合气(摩尔含量),氨化温度为200℃,氨化时间5小时。将2.469克Co(NO3)2·H2O,5.703克Cu(NO3)2·3H2O和0.310克KNO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例14:
15%Co-3.6%Re-1.2%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入20%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将7.408克Co(NO3)2·H2O,0.518克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例15:
30%Co-2%Re-1.2%B/Al2O3催化剂的制备及应用
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时,然后引入50%氨气-氢气混合气(摩尔含量),氨化温度为300℃,氨化时间5小时。将14.816克Co(NO3)2·H2O,0.288克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。其余制备步骤和催化剂评价方案参见实施例1。反应结果见表1。
实施例16:
催化剂的稳定性试验,按实施例7中的催化剂制备方法制备的催化剂在固定床反应器中,反应条件:温度为160℃,压力为8MPa,乙醇胺的液体空速为0.5h-1,H2/NH3/乙醇胺=0.25∶10∶1(摩尔比),进行反应,每隔反应24小时取样分析。SE-30毛细管色谱柱,FID检测器,N,N-二甲基甲酰胺为内标进行定量分析,1000小时的反应结果表明催化剂的活性和选择性基本相同。
对比例1:
载体未经氨化处理的15%Ni-3.6%Re-1.2%B/SiO2催化剂的制备及应用
称取10克载体SiO2(20-40目),将载体SiO2装于石英管中,惰性气氛下,200℃干燥5小时。将7.432克Ni(NO3)2·6H2O,0.518克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。用此水溶液的一半浸渍上述SiO2载体,自然晾干,随后120℃干燥4小时,接着500℃焙烧4小时。然后,用上述剩余的另一半水溶液第二次浸渍上述载有金属的SiO2载体,接着自然晾干,120℃干燥4小时,500℃焙烧4小时。催化剂评价方案参见实施例1。
对比例2:
载体未经氨化处理的15%Co-3.6%Re-1.2%B/Al2O3催化剂的制备及应用。
称取10克载体Al2O3(20-40目),将载体Al2O3装于石英管中,惰性气氛下,200℃干燥5小时。将7.408克Co(NO3)2·H2O,0.518克NH4ReO4和0.686克H3BO3溶解在12ml去离子水中。用此水溶液的一半浸渍上述Al2O3载体,自然晾干,随后120℃干燥4小时,接着500℃焙烧4小时。然后,用上述剩余的另一半水溶液第二次浸渍上述载有金属的Al2O3载体,接着自然晾干,120℃干燥4小时,500℃焙烧4小时。催化剂评价方案参见实施例1,反应结果见表1。
乙醇胺的摩尔转化率和产品摩尔选择性如下计算:
乙醇胺的转化率:Conv.(%)=(1-NEDA×CEDA/(NEDA×CEDA+∑Ni×Ci))×100%产品的选择性:Si=(Ni×Ci/∑Ni×Ci)×100%
其中:
NEDA:产品中乙醇胺的摩尔数;
CEDA:乙醇胺的碳原子数;
Ni:产物中产品i的摩尔数;
Ci:产物中产品i的碳原子数。
实施例2和对照例1的催化剂组分相同,不同的是实施例2的载体经过氨化处理,对照例1的载体没有经过氨化处理,比较结果,不难发现,乙醇胺的转化率提高了31%,乙二胺的选择性提高了32%。
实施例14和对照例2的催化剂组分相同,不同的是实施例14的载体经过氨化处理,对照例2的载体没有经过氨化处理,比较结果,不难发现,乙醇胺的转化率提高了34%,乙二胺的选择性提高了27%。
综合上面的比较分析结果可以认定,催化剂载体采用氨化处理后,可以在所述催化剂及制备乙撑胺的方法中实现以下中的一项或多项:(1)在较低的反应压力下实现,(2)调变反应条件可以灵活调变乙撑胺的组成,(3)降低生产装置一次性投资和生产成本,(4)实现易操作,(5)提高催化剂的活性,(6)提高对产物的选择性,(7)提供原料的转化率,和(8)提高方法的稳定。
Claims (10)
1.一种用于合成乙撑胺的催化剂,所述催化剂是由主活性组分、助剂和氨化处理过的载体三部分组成,其中所述主活性组分选自由Ni和Co组成的组中的一种或多种,所述助剂选自由Fe、Cu、Ru、Re、K、Zn和B以及它们各自的氧化物组成的组中的一种或多种;所述氨化处理过的载体由选自由SiO2和Al2O3组成的组中的一种或多种载体经过氨化处理而得到,所述氨化处理包括:将载体与氨源在150至400℃的温度接触0.5至15小时。
2.按照权利要求1所述的催化剂,其中所述载体的比表面积为150~350m2/g,并且平均孔径为8-80nm。
3.按照权利要求1所述的催化剂,其中所述氨源选自由氨气、液氨、氨水和尿素组成的组中的一种或多种。
4.按照权利要求1所述的催化剂,其中所述主活性组分在所述催化剂的总重量中占1~40%。
5.按照权利要求1所述的催化剂,其中所述主活性组分在所述催化剂的总重量中占5~30%。
6.按照权利要求1所述的催化剂,其中所述助剂在所述催化剂的总重量中占0.1~20%。
7.按照权利要求1所述的催化剂,其中所述助剂在所述催化剂的总重量中占0.1~15%。
8.一种用于由乙醇胺和氨制备乙撑胺的方法,所述方法包括:在权利要求1所述的催化剂存在下,在临氢条件下将乙醇胺和氨转化为乙撑胺。
9.按照权利要求8所述的的方法,其中所述方法在温度为135~200℃,压力为6.0~22.0MPa并且乙醇胺的液体空速为0.3~1.5h-1的条件下进行。
10.按照权利要求8所述的方法,其中所述催化剂在使用之前在氢气气氛中并且在压力为常压,温度为150~400℃并且氢气空速为500~4000h-1的条件下还原活化。
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