CN111004127A - 一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法 - Google Patents
一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法 Download PDFInfo
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Abstract
本发明涉及一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,以二甲醚(DME)、合成气(H2+CO)和氨气(NH3)为反应原料,经过新型多床层分步式进料固定床反应器内进行接触反应,一步制得乙胺、甲胺。本发明设计科学合理、工艺高效,结合一种新型分步式进料固定床反应器,甲催化路线不使用贵金属催化剂,反应条件温和,二甲醚的转化率由18%提高到23%,乙胺选择性由25%提高到38%,甲胺选择性由26%提高到45%,提供了一种具有良好的工业应用前景且极具潜力的乙胺合成新路径,适用于大力推广使用。
Description
技术领域
本发明属于化工技术领域,涉及合成技术,尤其是一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法。
背景技术
乙胺(EA)是重要的有机化工原料。目前工业以乙醇催化胺化法制备乙胺,原料丰富,收率较高,副产物生成水,易于实现清洁化生产。然而,所用原料乙醇,主要由糖质、淀粉原料发酵获得,或乙烯水合法制得。第一个途径由于糖类发酵可能会加剧食品危机,面临产品分离能耗高、成本高的问题;第二个途径中所用原料乙烯,主要来源于石油裂解气,易受原油价格波动影响。
甲胺也是一类重要的有机化工原料,广泛用于制造染料、农药、医药、***、表面活性剂、防腐剂等。包括一甲胺(MMA)、二甲胺(DMA)与三甲胺(TMA)。工业上采用甲醇胺化法,以甲醇和氨为原料,在高温、高压、硅铝酸盐催化剂存在下合成一甲胺、二甲胺和三甲胺粗产物,然后经分离纯化,得到纯相产物。
综上,选择一种甲胺选择性较高,催化路线不使用贵金属催化剂,反应条件温和,具有良好的工业应用前景且极具潜力的乙胺合成新路径具有重要的研发意义,本发明在实际研发过程中,创新了一种新型多床层分步式进料固定床反应器,结合催化合成方法,使用高效便捷。
发明内容
本发明的目的在于克服现有技术的不足之处,以现有合成气制乙醇技术为基础,发展一种DME、合成气和NH3一步法选择性制乙胺并联产甲胺的方法,该技术在分段进料式固定床反应器中实现,DME与CO发生羰基化反应生成MA,然后MA加氢生成乙醇与甲醇,最后乙醇和甲醇与氨气反应生成乙胺、甲胺。
本发明解决其技术问题是采取以下技术方案实现的:
一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,以二甲醚(DME)、合成气(H2+CO)和氨气(NH3)为反应原料,经过新型多床层分步式进料固定床反应器内进行接触反应,一步制得乙胺、甲胺,具体的方法步骤如下:
⑴取MOR、FER分子筛中的一种,在空气中550℃下煅烧3h,造粒至20-40目,用石英棉将其限定在固定床反应器的顶部第一催化床层中;
⑵取20-40目Cu基催化剂用石英棉将其限定在固定床反应器的中部第二催化床层中;
⑶取20-40目酸性分子筛用石英棉将其限定在固定床反应器的底部第三催化床层中;
⑷在反应之前,将Cu基催化剂在纯氢气流中250-350℃下原位还原5-10h;
⑸随后通入二甲醚、合成气和氨气混合气体,进行反应。
而且,所述的新型多床层分步式进料固定床反应器包括空腔壳体,该空腔壳体的上部开设有第一气体入口,第一气体入口的一侧开设有第二气体入口,在所述空腔壳体内,与所述的第一气体入口连接处,同轴可拆卸插装有不锈钢制气管,所述的空腔壳体内由上至下依次设置有第一催化床层、第二催化床层和第三催化床层,所述的不锈钢制气管依次穿装过第一催化床层、第二催化床层和第三催化床层。
而且,在所述不锈钢制气管的末端均布开设有若干个出气孔,该出气孔通入所述的第三催化床层中。
而且,所述空腔壳体的下部开设有产物出口。
而且,在第二催化床层和第三催化床层之间设置有石英棉。
而且,原料摩尔比为DME/H2/CO/NH3=1~5:40~50:40~50:1~5,反应温度为200-500℃、反应压强为0.5-10MPa。
而且,MOR分子筛为H型MOR,FER分子筛为H型FER。
而且,所述的第三层催化剂酸性分子筛为H-MOR、H-Y、H-Beta、H-ZSM-5中的一种或多种。
而且,所述的Cu基催化剂为Cu-Zn-Al2O3催化剂。
而且,Cu-Zn-Al2O3催化剂采用共沉淀法制备,具体为将含有硝酸铜、硝酸锌、硝酸铝的混合溶液加入尿素水溶液中,不断搅拌,然后将混合物加热至90℃并在此温度下保持2h,直到混合物完全沉淀,将所得浆液在室温下老化过夜,然后过滤并用去离子水洗涤,所得滤饼在120℃干燥,350℃煅烧2h。
本发明的优点和积极效果是:
1、目前工业上乙胺由乙醇催化胺化法得到,乙醇主要来源于粮食或石油路线,容易受粮食安全或石油价格波动影响。本发明以非粮食生物质或煤炭资源得到的合成气、二甲醚为原料,在同一反应器中发生二甲醚羰基化、乙酸甲酯加氢和乙醇胺化三个反应,得到乙胺,并联产甲胺。
2、本发明的催化剂装填在一种新型多床层分步式进料固定床反应器内,通过原料气的分步进入,实现反应过程强化。传统固定床反应器中,二甲醚、合成气和氨气均由反应器入口直接通入催化剂床层。在二甲醚羰基化、乙酸甲酯加氢反应床层,氨气的混入不仅降低了二甲醚与合成气分压,还会引发其他副反应,造成主反应选择性降低。本发明的新型分步式进料固定床反应器,通过内置的配有均匀孔分步的不锈钢管,将氨气直接通入乙醇胺化催化剂床层。由于固定床层存在反应压降,因此通入的氨气不会混入上层催化剂床层,由此实现二甲醚、合成气和氨气的分步进料。该新型反应器通过调节气体的进料方式,可以提高二甲醚羰基化、乙酸甲酯加氢反应的转化效率,减少副产物生成,实现二甲醚、合成气和氨气一步高选择性生成乙胺,并联产甲胺。
3、本发明的三步反应催化剂分别对应三种催化材料,第一步反应为二甲醚羰基化反应,催化剂为MOR、FER型分子筛中的一种,第二步反应为中间产物乙酸甲酯加氢成醇,催化剂为Cu基催化剂,第三步反应为醇胺化生成乙胺、甲胺,催化剂为酸性分子筛H-MOR、H-Y、H-Beta、H-ZSM-5中的一种。二甲醚转化率高,乙胺选择性高。进一步通过各催化剂组分比例的精确调控,可高选择生成目标产物。
4、本发明构建了一种组合式催化剂,分别由二甲醚羰基化反应催化剂、乙酸甲酯加氢成醇催化剂以及醇胺化生成乙胺、甲胺催化剂组成,通过反应工艺条件的优化,二甲醚、合成气和氨气一步高选择性生成乙胺,并联产甲胺。不同于目前的乙醇合成与乙醇胺化两步法制乙胺路径,一步法路线简洁,生产成本更低。此外,该路径实现了以煤或非粮食生物质为能源的乙胺合成路线。
5、本发明设计了一种新型分步式进料固定床反应器,通过内置气体入口,将原料精确通入特定催化剂床层,不仅提高了二甲醚羰基化、乙酸甲酯加氢反应的转化效率,同时减少了副产物生成、提高了乙胺的选择性。相比于传统固定床反应器,在新型床反应器中二甲醚的转化率由18%提高到23%,乙胺选择性由25%提高到38%,甲胺选择性由26%提高到45%。
6、本发明设计科学合理、工艺高效,结合一种新型分步式进料固定床反应器,甲催化路线不使用贵金属催化剂,反应条件温和,二甲醚的转化率由18%提高到23%,乙胺选择性由 25%提高到38%,甲胺选择性由26%提高到45%,提供了一种具有良好的工业应用前景且极具潜力的乙胺合成新路径,适用于大力推广使用。
附图说明
图1为本发明的结构示意图(局部剖)。
具体实施方式
下面结合附图并通过具体实施例对本发明作进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。
一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,以二甲醚(DME)、合成气(H2+CO)和氨气(NH3)为反应原料,经过新型多床层分步式进料固定床反应器内进行接触反应,一步制得乙胺、甲胺,具体的方法步骤如下:
⑴取MOR、FER分子筛中的一种,在空气中550℃下煅烧3h,造粒至20-40目,用石英棉将其限定在固定床反应器的顶部第一催化床层中;
⑵取20-40目Cu基催化剂用石英棉将其限定在固定床反应器的中部第二催化床层中;
⑶取20-40目酸性分子筛用石英棉将其限定在固定床反应器的底部第三催化床层中;
⑷在反应之前,将Cu基催化剂在纯氢气流中250-350℃下原位还原5-10h;
⑸随后通入二甲醚、合成气和氨气混合气体,进行反应。
具体的,原料摩尔比为DME/H2/CO/NH3=1~5:40~50:40~50:1~5,反应温度为200-500℃、反应压强为0.5-10MPa。
具体的,MOR分子筛为H型MOR,FER分子筛为H型FER。
具体的,第三层催化剂酸性分子筛为H-MOR、H-Y、H-Beta、H-ZSM-5中的一种或多种。
具体的,Cu基催化剂为Cu-Zn-Al2O3催化剂。
具体的,Cu-Zn-Al2O3催化剂采用共沉淀法制备,具体为将含有硝酸铜、硝酸锌、硝酸铝的混合溶液加入尿素水溶液中,不断搅拌,然后将混合物加热至90℃并在此温度下保持2h,直到混合物完全沉淀,将所得浆液在室温下老化过夜,然后过滤并用去离子水洗涤,所得滤饼在120℃干燥,350℃煅烧2h。
本发明采用的固定床反应器为一种新型多床层分步式进料固定床反应器,如图1所示,包括空腔壳体10,该空腔壳体的上部开设有第一气体入口1,第一气体入口的一侧开设有第二气体入口2,该空腔壳体的下部开设有产物出口9,在所述空腔壳体内,与所述的第一气体入口连接处,同轴可拆卸插装有不锈钢制气管3,在该不锈钢制气管的末端均布开设有若干个出气孔7。
所述的空腔壳体内由上至下依次设置有第一催化床层4、第二催化床层5和第三催化床层8,所述的不锈钢制气管依次穿装过第一催化床层、第二催化床层和第三催化床层,不锈钢制气管的出气孔通入所述的第三催化室中,在第二催化室和第三催化室之间设置有石英棉 6。
以二甲醚、合成气和氨气一步法制乙胺并联产甲胺为例,具体操作如下:
二甲醚(DME)、合成气(H2+CO)和氨气(NH3)为反应原料,经过新型多床层分步式进料固定床反应器内进行接触反应,一步制得乙胺、甲胺,第一催化剂床层的催化剂为MOR 或FER分子筛,第二催化剂床层的层催化剂为Cu基催化剂,第三催化床层的催化剂为酸性分子筛。
二甲醚与合成气混合后由固定床反应器的第二气体入口通入第一、第二催化剂床层,氨气经过固定床反应器的第一气体入口进入不锈钢制气管,从该不锈钢制气管末端均布开设的若干个出气孔中直接引入至第三催化床层,最终产物由空腔壳体的下部开设有产物出口得到。
尽管为说明目的公开了本发明的实施例和附图,但是本领域的技术人员可以理解:在不脱离本发明及所附权利要求的精神和范围内,各种替换、变化和修改都是可能的,因此,本发明的范围不局限于实施例和附图所公开的内容。
Claims (10)
1.一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:以二甲醚(DME)、合成气(H2+CO)和氨气(NH3)为反应原料,经过新型多床层分步式进料固定床反应器内进行接触反应,一步制得乙胺、甲胺,具体的方法步骤如下:
⑴取MOR、FER分子筛中的一种,在空气中550℃下煅烧3h,造粒至20-40目,用石英棉将其限定在固定床反应器的顶部第一催化床层中;
⑵取20-40目Cu基催化剂用石英棉将其限定在固定床反应器的中部第二催化床层中;
⑶取20-40目酸性分子筛用石英棉将其限定在固定床反应器的底部第三催化床层中;
⑷在反应之前,将Cu基催化剂在纯氢气流中250-350℃下原位还原5-10h;
⑸随后通入二甲醚、合成气和氨气混合气体,进行反应。
2.一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:所述的新型多床层分步式进料固定床反应器包括空腔壳体,该空腔壳体的上部开设有第一气体入口,第一气体入口的一侧开设有第二气体入口,在所述空腔壳体内,与所述的第一气体入口连接处,同轴可拆卸插装有不锈钢制气管,所述的空腔壳体内由上至下依次设置有第一催化床层、第二催化床层和第三催化床层,所述的不锈钢制气管依次穿装过第一催化床层、第二催化床层和第三催化床层。
3.根据权利要求1所述的一种新型多床层分步式进料固定床反应器,其特征在于:在所述不锈钢制气管的末端均布开设有若干个出气孔,该出气孔通入所述的第三催化床层中。
4.根据权利要求1所述的一种新型多床层分步式进料固定床反应器,其特征在于:所述空腔壳体的下部开设有产物出口。
5.根据权利要求1所述的一种新型多床层分步式进料固定床反应器,其特征在于:在第二催化床层和第三催化床层之间设置有石英棉。
6.根据权利要求1所述的一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:原料摩尔比为DME/H2/CO/NH3=1~5:40~50:40~50:1~5,反应温度为200-500℃、反应压强为0.5-10MPa。
7.根据权利要求1所述的一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:MOR分子筛为H型MOR,FER分子筛为H型FER。
8.根据权利要求1所述的一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:所述的第三层催化剂酸性分子筛为H-MOR、H-Y、H-Beta、H-ZSM-5中的一种或多种。
9.根据权利要求1所述的一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:所述的Cu基催化剂为Cu-Zn-Al2O3催化剂。
10.根据权利要求9所述的一种二甲醚、合成气和氨气一步法制乙胺并联产甲胺的方法,其特征在于:Cu-Zn-Al2O3催化剂采用共沉淀法制备,具体为将含有硝酸铜、硝酸锌、硝酸铝的混合溶液加入尿素水溶液中,不断搅拌,然后将混合物加热至90℃并在此温度下保持2h,直到混合物完全沉淀,将所得浆液在室温下老化过夜,然后过滤并用去离子水洗涤,所得滤饼在120℃干燥,350℃煅烧2h。
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