CN114602545B - 一种多级孔复合分子筛催化剂的制备及其应用 - Google Patents
一种多级孔复合分子筛催化剂的制备及其应用 Download PDFInfo
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Abstract
本发明公开了一种多级孔复合分子筛催化剂的制备及其应用,包括以下步骤,将ZSM‑5/MOR共结晶分子筛与氧化铝粘结剂混捏、挤条、干燥、焙烧和水热处理,制得所述催化剂,其中ZSM‑5占ZSM‑5/MOR的重量百分比为30~95%,ZSM‑5/MOR分子筛的介孔孔容>0.3ml/g,外比表面>60m2/g。本发明采用上述结构的一种多级孔复合分子筛催化剂的制备及其应用,与现有技术相比,本发明制备的ZSM‑5/MOR催化剂用于甘油、丙醛和氨气反应制备吡啶碱过程,3‑甲基吡啶收率高,并可促进生物基甘油的高值化转化利用。
Description
技术领域
本发明涉及精细化工技术领域,特别是涉及一种多级孔复合分子筛催化剂的制备及其应用。
背景技术
3-甲基吡啶是制备烟酸和烟酸氨的主要原料,还可以用来制备维生素,又是合成吡啶类香料和新型杀虫剂的重要中间体,目前呈现供不应求的局面。3-甲基吡啶最先是从煤焦化分馏副产品中回收,但由于焦化副产品中吡啶组份多、产品复杂、分离困难,且产量较少,目前主要采用醛氨合成法生产。
目前合成3-甲基吡啶的方法,主要是在乙醛和氨气合成2-甲基吡啶和4-甲基吡啶的基础上,通过往原料中添加大量甲醛来制备吡啶和3-甲基吡啶。英国专利USP3946020、4089863、5395940报道了采用乙醛和氨气合成2-甲基吡啶和4-甲基吡啶的方法,在温度为440℃左右,空速为800h-1,通入丙烯醛/氨气/水蒸气/氮气=1/1/4/2的混合气体,得到88%左右的吡啶碱,其中采Ag-Pb-Si-Al-O和Ag-Ca-Si-Al-O催化剂,得到吡啶13%,2-甲基吡啶38%,4-甲基吡啶37%。而在需要得到3-甲基吡啶时,只需将原料换成乙醛和甲醛的混合物即可,由于该方法成熟,工艺操作简单,目前工业上制备3-甲基吡啶都是采用此方法。
美国专利US3946020报道在H-SiO2-Al2O3催化剂上,甲醛/乙醛/氨气=12/12/26.4,420℃左右,空速为1160h-1条件下,得到吡啶收率为38.1%,3-甲基吡啶为25.9%。中国专利1506353、1506354、1566093也报道了采用甲醛乙醛法合成吡啶和3-甲基吡啶的方法。其中CN1566093报道采用甲醛/乙醛/氨气=1/2/4.5,在以Co-Pb-ZSM5为催化剂,450℃左右,空速为1000h-1条件下,得到了吡啶碱收率为83%,其中吡啶收率为68%,2-甲基吡啶为4%,3-甲基吡啶为4.5%,4-甲基吡啶为6.5%。当甲醛/乙醛/氨气=1/1/4.5时,吡啶碱收率为81.5%,其中,吡啶收率为56%,3-甲基吡啶收率达到24.5%,基本不产生2-甲基吡啶和4-甲基吡啶。由此可见通过增加甲醛的量,可以提高3-甲基吡啶的收率,但是难以完全避免4-甲基吡啶的生成。众所周知,3-甲基吡啶和4-甲基吡啶难以分离,这样难以得到高纯度3-甲基吡啶。而且,通过甲醛/乙醛/氨气法生产吡啶碱时,3-甲基吡啶是吡啶的联产品,其产量的多少受制于吡啶的产量,同时,该法得到的3-甲基吡啶产率较低。
为了以3-甲基吡啶为目标产品、且避免4-甲基吡啶的生成,就需要在原料中避免使用乙醛,因而,大量研究采用丙烯醛为原料来制备3-甲基吡啶。英国专利1020857、1187347、1208291、1222971报道了使用丙烯醛和氨气气相合成吡啶和3-甲基吡啶的方法,而且产物不含4-甲基吡啶。其中BP1020857报道了采用丙烯醛/氨气/水=1/5/1,以B-P/SiO2-Al2O3为催化剂,温度为350℃左右,接触时间为5秒,得到吡啶碱收率为60%,其中吡啶收率为25%,3-甲基吡啶为35%。由于采用丙烯醛和氨气气相反应生成3-甲基吡啶产物有大量吡啶生成,应该是丙烯醛高温裂解产生或者3-甲基吡啶裂解脱甲基产生。同时由于丙烯醛比较活泼,容易自聚。
目前,国内外大多采用ZSM-5和ZSM-11分子筛开展甘油、丙醛和氨气反应制3-甲基吡啶的研究,但是目前仍然存在3-甲基吡啶收率不高的问题。
发明内容
本发明的目的是提供一种多级孔复合分子筛催化剂的制备及其应用,以解决上述分子筛催化剂应用于甘油、丙醛和氨气反应生产3-甲基吡啶过程得到的3-甲基吡啶产率不高的问题。
为实现上述目的,本发明提供了一种多级孔复合分子筛催化剂的制备,包括以下步骤,将ZSM-5/MOR共结晶分子筛与氧化铝粘结剂混捏、挤条、干燥、焙烧和水热处理,制得所述催化剂,其中ZSM-5占ZSM-5/MOR的重量百分比为30~95%,ZSM-5/MOR分子筛的介孔孔容>0.3ml/g,外比表面>60m2/g。
优选的,氧化铝粘接剂为硝酸铝、薄水铝石或硫酸铝中至少一种。
优选的,氧化铝粘接剂占ZSM-5/MOR催化剂的重量百分比为10~40%。
优选的,干燥温度为100~120℃,干燥时间为3~5小时。
优选的,焙烧温度为450~550℃,焙烧时间2~4小时。
优选的,水热处理温度为490~600℃,处理时间1.5~5小时。
一种多级孔复合分子筛催化剂的应用,制备的ZSM-5/MOR催化剂应用于甘油、丙醛和氨气反应生成吡啶碱的化学反应过程。
优选的,化学反应的反应条件:压力为0.05~0.30MPa,温度360~560℃,丙烯醛重量空速0.05~1.5h-1,丙醛与甘油的摩尔比1:5~1:2,氨气与甘油的摩尔比6:1~2:1。
因此,本发明采用上述结构的一种多级孔复合分子筛催化剂的制备及其应用,多级孔ZSM-5/MOR共结晶分子筛催化剂用于甘油、丙醛和氨气反应制备吡啶碱的过程,与单一的ZSM-5或MOR分子筛催化剂相比,多级孔ZSM-5/MOR共结晶分子筛催化剂由于其不同晶相间的协同作用、独特的酸性分布和多级孔结构,有利于原料和产物分子的扩散传质(对于体积较大的分子更为有利,包括形成更大的反应中间体)、以及分子筛酸性活性位的利用率提高,使得3-甲基吡啶的收率更高,与现有技术相比,本发明制备的ZSM-5/MOR催化剂用于甘油、丙醛和氨气反应制备吡啶碱过程,3-甲基吡啶收率高,并可促进生物基甘油的高值化转化利用。
下面通过实施例,对本发明的技术方案做进一步的详细描述。
具体实施方式
以下将对本发明进行进一步的描述,需要说明的是,本实施例以本技术方案为前提,给出了详细的实施方式和具体的操作过程,但本发明并不限于本实施例。
对比例1
将85g ZSM-5分子筛与19.5g薄水铝石(干基77%)混捏,挤条,120℃下干燥4小时,在540℃下焙烧3小时,500℃下水处理2小时,破碎成20-40目的颗粒,制得催化剂记为Cat-I(样品中,ZSM-5分子筛占催化剂的重量比为85%)。将催化剂Cat-I装入固定床反应器中进行反应,反应前催化剂在N2(60ml/min)气氛升到450℃,恒温活化2小时,然后在0.1MPa,425℃,甘油重量空速0.3h-1,甘油与丙醛的摩尔比为2:1,氨气与甘油的摩尔比为4:1,N2:40-50ml/min条件下反应5小时,反应器出口接冷凝器,出口接接收瓶,尾气用三级洗涤吸收。气相色谱进行原料和产物分析,归一化按碳平衡进行计算,结果3-甲基吡啶收率为19.0%,吡啶收率为28.0%。
对比例2
其它与对比例1相同,不同的是将所用ZSM-5分子筛替换为MOR分子筛。所制备的成品催化剂记为Cat-II。在与对比例1相同的反应条件下进行反应,反应结果为3-甲基吡啶收率为7.2%,吡啶收率为18.5%。
实施例1
其它与对比例1相同,不同的是所用ZSM-5分子筛替换为多级孔ZSM-5/MOR共结晶分子筛催化剂,其中ZSM-5与MOR晶相比例为70%:30%,介孔孔容为0.36ml/g,外比表面>85m2/g。所制备的成品催化剂记为Cat-III。在与对比例1相同的反应条件下进行反应,反应结果为3-甲基吡啶收率为53.5%,吡啶收率为27.1%。
实施例2
其它与比较例1相同,不同的是所用ZSM-5分子筛替换为多级孔ZSM-5/MOR共结晶分子筛催化剂,其ZSM-5与MOR晶相比例为85%:15%,介孔孔容为0.32ml/g,外比表面>73m2/g。所制备的成品催化剂记为Cat-IV。在0.1MPa,450℃,甘油重量空速0.2h-1,甘油与丙醛的摩尔比为4/1,氨气与甘油的摩尔比为6:1的反应条件下进行反应,反应结果为3-甲基吡啶收率为56.5%,吡啶收率为23.7%。
注:3-甲基吡啶选择性为3-甲基吡啶收率与吡啶收率的比值。
从上表中可以看出实施例1-2制成的催化剂不仅可以大大提高吡啶和3-甲基吡啶的总收率,而且可以大大提高3-甲基吡啶的收率,增加3-甲基吡啶的选择性,便于后续直接分离吡啶和3-甲基吡啶的混合物,直接得到3-甲基吡啶。本发明中的混捏、挤条、干燥、焙烧步骤为催化剂提供了成型条件,水热处理主要为了增加分子筛上的酸性活性位和增加多级孔结构,多级孔结构在催化甘油、丙醛和氨气反应生成吡啶碱过程中有利于原料、产物分子和反应中间体的扩散,进而进一步提高酸性活性位的利用率。
因此,本发明采用上述结构的一种多级孔复合分子筛催化剂的制备及其应用,与现有技术相比,本发明制备的ZSM-5/MOR催化剂用于甘油、丙醛和氨气反应制备吡啶碱过程,3-甲基吡啶收率高,并可促进生物基甘油的高值化转化利用。
最后应说明的是:以上实施例仅用以说明本发明的技术方案而非对其进行限制,尽管参照较佳实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对本发明的技术方案进行修改或者等同替换,而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的精神和范围。
Claims (4)
1.一种多级孔复合分子筛催化剂的应用,其特征在于:多级孔复合分子筛催化剂应用于甘油、丙醛和氨气反应生成吡啶碱的化学反应过程;
所述多级孔复合分子筛催化剂的制备包括以下步骤,将ZSM-5/MOR共结晶分子筛与氧化铝粘结剂混捏、挤条、干燥、焙烧和水热处理,制得所述催化剂,其中ZSM-5占ZSM-5/MOR的重量百分比为30~95%,ZSM-5/MOR的介孔孔容>0.3ml/g,外比表面>60m2/g;
氧化铝粘结剂为硝酸铝、薄水铝石或硫酸铝中至少一种;
干燥温度为100~120℃,干燥时间为3~5小时;
焙烧温度为450~550℃,焙烧时间3小时。
2.根据权利要求1所述的一种多级孔复合分子筛催化剂的应用,其特征在于:所述多级孔复合分子筛催化剂的制备步骤中氧化铝粘接剂占ZSM-5/MOR催化剂的重量百分比为10~40%。
3.根据权利要求1所述的一种多级孔复合分子筛催化剂的应用,其特征在于:所述多级孔复合分子筛催化剂的制备步骤中水热处理温度为490~600℃,处理时间1.5~5小时。
4.根据权利要求1所述的一种多级孔复合分子筛催化剂的应用,其特征在于,化学反应的反应条件:压力为0.05~0.30MPa,温度360~560℃,丙烯醛重量空速0.05~1.5h-1,丙醛与甘油的摩尔比1:5~1:2,氨气与甘油的摩尔比6:1~2:1。
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