CN106582700A - 一种合成气制低碳混合醇的石墨烯负载催化剂及制法和应用 - Google Patents
一种合成气制低碳混合醇的石墨烯负载催化剂及制法和应用 Download PDFInfo
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Abstract
一种合成气制低碳混合醇的石墨烯负载催化剂的重量百分比组成为:石墨烯:5‑25%,Cu:20‑40%,Fe:10‑30%,Mn:5‑15%,Zn:5‑15%,Zr:5‑10%,Co:1‑4%,M:0.1‑5%;其中M为碱金属或碱土金属一种,其中碱金属为Na、K、Li或Cs;碱土金属为Mg或Ba。本发明具有稳定性好,成本低,寿命长,在温和反应条件下高选择性的优点。
Description
技术领域
本发明属于一种合成气制低碳混合醇的石墨烯负载催化剂及制法和应用。
背景技术
低碳混合醇可作为优良的洁净车用燃料,由于醇本身含有氧,具有燃烧充分、效率高且CO、NOx及烃类排放量少等优点。其本身也是一种良好的洁净燃料,加之近年来经济价格较高的高级醇类的市场需求增加也使得低碳醇的研究受到关注。因此,CO加氢催化合成低碳混合醇反应是C1化学领域中具有重要应用前景。
由合成气直接合成低碳醇的研究较为广泛,所形成的催化剂体系主要有以下四种:
(1)改性甲醇合成催化剂(Cu/ZnO/Al2O3,ZnO/Cr2O3):此催化剂由甲醇合成催化剂加入适量的碱金属或碱土金属化合物改性而得,较典型的专利有EP-0034338-A2(C.E.Hofstadt等人)及美国专利4513100(Snam公司资助,发明人为Fattore等人)。此类催化剂虽然活性较高,产物中异丁醇含量高,但缺点是反应条件苛刻(压力为14-20MPa,温度为350-450℃),高级醇选择性低(一般小于35%),产物中含水量高(一般为30-50%);(2)Rh基催化剂(如US 4014913及4096164):负载型Rh催化剂中加入一到两种过渡金属或金属氧化物助剂后,对低碳醇合成有较高的活性和选择性,特别是对C2 +醇的选择性较高,产物以乙醇为主。但Rh化合物价格昂贵,催化剂易被CO2毒化,其活性和选择性一般达不到工业生产的要求。(3)抗硫MoS2催化剂:最值得一提是美国DOW公司开发的钼系硫化物催化剂(主要专利见Stevens等人的US patent4882360),该催化体系不仅具有抗硫性,产物含水少,而且高级醇含量较高,达30-70%,其中主要是乙醇和正丙醇。此催化剂存在的主要问题是其中的助剂元素极易与一氧化碳之间形成羰基化合物,造成助剂元素的流失,影响催化剂的活性及选择性,致使催化剂稳定性和寿命受到限制。(4)Cu-Co催化剂:法国石油研究所(IFP)首先开发了Cu-Co共沉淀低碳醇催化剂,仅1985前就获得了四个催化剂专利(US Patent4122110,4291126及GB Patent 2118061,2158730),此催化剂合成的产物主要为C1-C6直链正构醇,副产物主要为C1-C6脂肪烃,反应条件温和(与低压甲醇合成催化剂相似)。该催化剂的缺点是稳定性较差。
石墨烯为“单层石墨”,是碳原子,以SP2混成轨域呈蜂巢晶格排列构成的单层二维晶体,具有非凡的物理及电学性质,如高比表面积、高导电性、高机械强度、易于修饰及大规模生产等。石墨烯是由单层碳原子平面结构石墨烯堆垛而成,厚度为纳米尺度的两维石墨纳米材料,其极端情况是单层石墨烯,它的一个重要特征是有一条一维尖锐的刀口状边缘,电场增强系数大,是很好的电子场发射材料,再加之导热、导电好,化学性质稳定,力学强度高由于其独特而完美的结构使得石墨烯具有优异的电学、力学、热学和光学等特性。石墨烯的这些特性为其成为金属催化剂的优良载体提供了可能。石墨烯用于金属催化剂的负载,研究新型高性能的负载型金属催化剂。因此石墨烯尤其适合作为催化剂载体。石墨烯良好的化学稳定性,有利于保持催化剂结构的稳定,从而延长催化剂寿命;良好的导热导电性能,有利于催化剂在反应过程中的热传递以及催化剂活性组分与载体间的电子传递。目前,国内外对于由合成气制低碳混合醇的以石墨烯为基体的催化剂研究还相对较少。中国专利CN2013104161493A报道一种氧化石墨烯负载席夫碱钯催化剂及制备方法,该催化剂可在C-C偶合反应中具有较好的防止钯聚集和流失。但催化剂活性组分为钯,价格昂贵,致使催化剂的工业应用受到限制。
发明内容
本发明的目的是提供一种稳定性好,成本低,寿命长,在温和反应条件下高选择性的由合成气制低碳混合醇的催化剂及其制备方法和应用。
本发明的目的是这样实现的,运用沉淀法将FeCu催化剂负载在石墨烯上,在引入具有较强碳链增长能力的VIII族元素,以及过渡金属、碱金属或碱土金属、稀土金属,从而提高CO加氢反应的活性,改善C2 +醇和C4 +烃的选择性,并同时抑制CO2和甲烷等副产物的生成,石墨烯的加入提高催化剂时传热效率和提高催化剂稳定性,提高反应总醇选择性。
本发明制备的催化剂重量百分比组成为:
石墨烯:5-25%,Cu:20-40%,Fe:10-30%,Mn:5-15%,Zn:5-15%,Zr:5-10%,Co:1-4%,M:0.1-5%;其中M为碱金属或碱土金属一种,其中碱金属为Na、K、Li或Cs;碱土金属为Mg或Ba等。
如上所述的石墨烯为机械剥离法制备、取向生长法、化学气相沉积法、电弧法、电化学法和氧化-还原法制备的石墨烯。包括单层石墨烯、双层石墨烯和多层石墨烯。
本发明提供的催化剂的制备方法包括以下步骤:
按催化剂组成,将石墨烯载体和金属(Cu,Fe,Mn,Zn,Zr,Co)的硝酸盐溶液先混合成悬浮液,在沉淀温度为60-90℃与碱性溶液共沉淀,沉淀过程需搅拌,保持pH=8-9,沉淀经蒸馏水洗涤至中性为止,然后在干燥温度为80-120℃下干燥,在350-400℃下焙烧3h-6h。
如上所述的沉淀温度最佳沉淀温度为60-80℃。
如上所述的碱最好为碳酸钠或碳酸钾等。其碱性溶液适宜浓度为30%-60%的水溶液。
如上所述的干燥温度最好在80-110℃下干燥。
如上所述的焙烧最好在350-380℃温度下焙烧。
本发明催化剂进行低碳醇合成的应用条件为:反应温度为220-280℃,压力为4.5-12.0MPa,空速为1000-7500h-1,H2/CO体积比=0.5-2.0。
用本发明催化剂进行低碳醇的合成,CO转化率30-45%,总醇选择性为45-65%,总烃选择性20-30%,CO2选择性10-18%。总醇时空产率为0.15-0.40g/h.mL.cat;产物中水含量为15-30%;C2 +醇含量为40-60%,C4 +烃在总烃中所占百分含量60-70%。
本发明具有如下优点:
1、制备方法简单,易于操作,并且催化剂反应性能稳定性,重复性好。
2、本发明的催化剂各组分分布比较均匀,并各组分间存在强相互作用,抗烧结性能比较好,成本低,稳定性好,寿命长。
3、本发明的催化剂在还原和反应过程中,不需要添加CO2气体,大大降低了操作费用。
具体实施方式
实施例1
按催化剂组成,将10wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.8:0.5:0.3:0.4:0.1溶于该溶液当中形成80wt%石墨烯悬浮溶液,在60℃下与浓度为30wt%碳酸钾溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8。沉淀经蒸馏水洗涤至中性为止。经80℃干燥后在350℃空气气氛下焙烧3h,破碎至40-60目,得到催化剂1#,所得催化剂各组成石墨烯:10wt%,Cu:30wt%,Fe:25wt%,Mn:wt10%,Zn:wt8%,Zr:12wt%,Co:4wt%,K:1wt%。反应条件如下:T=220℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例2
按催化剂组成,将15wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.4:0.5:0.4:0.3:0.1溶于该溶液当中形成70wt%石墨烯悬浮溶液,在65℃下与浓度为40wt%碳酸钾溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8.5。沉淀经蒸馏水洗涤至中性为止。经90℃干燥后在380℃空气气氛下焙烧4h,破碎至40-60目,得到催化剂2#,所得催化剂组成石墨烯:15wt%,Cu:40wt%,Fe:12wt%,Mn:8wt%,Zn:15wt%,Zr:10wt%,Co:4wt%,K:1wt%,反应条件如下:T=230℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例3
将占催化剂总组成质量的5wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.8:0.5:0.3:0.4:0.1溶于该溶液当中形成75wt%石墨烯悬浮溶液,在70℃下与50wt%碳酸钠溶液共沉淀,沉淀过程需充分搅拌,并保持pH=9。沉淀经蒸馏水洗涤至中性为止。经100℃干燥后在400℃空气气氛下焙烧5h,破碎至40-60目,得到催化剂3#,所得催化剂组成石墨烯:wt5%,Cu:wt35%,Fe:wt25%,Mn:wt10%,Zn:wt10%,Zr:wt10%,Co:wt2.5%,Na:2.5%,反应条件如下:T=260℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例4
将占催化剂总组成质量的8wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.7:0.5:0.4:0.3:0.1溶于该溶液当中形成80wt%石墨烯悬浮溶液,在75℃下与55wt%碳酸锂溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8.5。沉淀经蒸馏水洗涤至中性为止。经110℃干燥后在400℃空气气氛下焙烧5h,破碎至40-60目,得到催化剂4#,所得催化剂中组成石墨烯:wt8%,Cu:wt30%,Fe:wt20%,Mn:wt15%,Zn:wt12%,Zr:wt10%,Co:wt4%,Li:1%,反应条件如下:T=240℃,P=5.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例5
将占催化剂总组成质量的12wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.7:0.6:0.4:0.2:0.1溶于该溶液当中形成70wt%石墨烯悬浮溶液,在80℃下与45wt%碳酸铯溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8.5。沉淀经蒸馏水洗涤至中性为止。所得催化剂中组成石墨烯:wt12%,Cu:wt30%,Fe:wt20%,Mn:wt15%,Zn:wt10%,Zr:wt8%,Co:wt1%,Cs:4%,经120℃干燥后在400℃空气气氛下焙烧6h,破碎至40-60目,得到催化剂5#。反应条件如下:T=250℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例6
将占催化剂总组成质量的15wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.8:0.6:0.3:0.1:0.1的硝酸盐溶液配成75wt%的石墨烯悬浮溶液,在85℃下与35wt%碳酸镁溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8。沉淀经蒸馏水洗涤至中性为止。所得催化剂组成石墨烯:wt15%,Cu:wt30%,Fe:wt25%,Mn:wt12%,Zn:wt8%,Zr:wt5%,Co:wt3.9%,Mg:1.1%,经120℃干燥后在380℃空气气氛下焙烧6h,破碎至40-60目,得到催化剂6#。反应条件如下:T=260℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例7
将占催化剂总组成质量的18wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.4:0.6:0.5:0.1:0.1的硝酸盐溶液配成80wt%的石墨烯悬浮溶液,在85℃下与40wt%碳酸镁溶液共沉淀,沉淀过程需充分搅拌,并保持pH=9。沉淀经蒸馏水洗涤至中性为止。所得催化剂组成石墨烯:wt18%,Cu:wt35%,Fe:wt12%,Mn:wt15%,Zn:wt10%,Zr:wt5%,Co:wt4%,Mg:1%,经110℃干燥后在400℃空气气氛下焙烧6h,破碎至40-60目,得到催化剂7#。反应条件如下:T=270℃,P=7.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例8
将占催化剂总组成质量的20wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:1.5:0.5:0.3:0.1:0.02的硝酸盐溶液配成70wt%的石墨烯悬浮溶液,在90℃下与50wt%碳酸钡溶液共沉淀,沉淀过程需充分搅拌,并保持pH=9。沉淀经蒸馏水洗涤至中性为止。所得催化剂中组成石墨烯:wt20%,Cu:wt20%,Fe:wt30%,Mn:wt10%,Zn:wt10%,Zr:wt5%,Co:wt1%,Ba:4%,经120℃干燥后在350℃空气气氛下焙烧4h,破碎至40-60目,得到催化剂8#。反应条件如下:T=280℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例9
将占催化剂总组成质量的22wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.6:0.5:0.3:0.4:0.1的硝酸盐溶液配成75wt%的石墨烯悬浮溶液,在80℃下与50wt%碳酸钾溶液共沉淀,沉淀过程需充分搅拌,并保持pH=8。沉淀经蒸馏水洗涤至中性为止。所得催化剂组成石墨烯:wt22%,Cu:wt25%,Fe:wt18%,Mn:wt12%,Zn:wt8%,Zr:wt10%,Co:wt4%,K:1%,经120℃干燥后在400℃空气气氛下焙烧4h,破碎至40-60目,得到催化剂9#。反应条件如下:T=280℃,P=6.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
实施例10
将占催化剂总组成质量的25wt%的石墨烯与金属原子以硝酸盐的形式按摩尔比Cu:Fe:Mn:Zn:Zr:Co=1.0:0.5:0.8:0.6:0.2:0.1的硝酸盐溶液配成80wt%的石墨烯悬浮溶液,在90℃下与55wt%碳酸钾溶液共沉淀,沉淀过程需充分搅拌,并保持pH=9。沉淀经蒸馏水洗涤至中性为止。所得催化剂组成石墨烯:wt25%,Cu:wt25%,Fe:wt10%,Mn:wt15%,Zn:wt12%,Zr:wt8%,Co:wt4%,K:1%,经110℃干燥后在400℃空气气氛下焙烧6h,破碎至40-60目,得到催化剂10#。反应条件如下:T=280℃,P=7.0MPa,GHSV=7500h-1,H2/CO体积比=2.0。反应结果见表1。
表1 实施例反应结果
Claims (10)
1.一种合成气制低碳混合醇的石墨烯负载催化剂,其特征在于催化剂重量百分比组成为:
石墨烯:5-25%,Cu:20-40%, Fe:10-30%, Mn:5-15%, Zn:5-15%, Zr:5-10%, Co: 1-4%, M: 0.1-5%;其中M为碱金属或碱土金属一种,其中碱金属为Na、 K、Li或Cs; 碱土金属为Mg或Ba。
2.如权利要求1所述的一种合成气制低碳混合醇的石墨烯负载催化剂,其特征在于所述的石墨烯为机械剥离法制备、取向生长法、化学气相沉积法、电弧法、电化学法和氧化-还原法制备的石墨烯;包括单层石墨烯、双层石墨烯和多层石墨烯。
3.如权利要求1或2所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于包括以下步骤:
按催化剂组成,将石墨烯载体和金属硝酸盐溶液先混合成悬浮液,在沉淀温度为60-90℃与碱性溶液共沉淀,沉淀过程需搅拌,保持pH=8-9,沉淀经蒸馏水洗涤至中性为止,然后在干燥温度为80-120℃下干燥,在350-400℃下焙烧3h-6h。
4.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于对于M为碱金属时,碱金属配成可溶性碳酸盐溶液做为沉淀剂,引入到上述共沉淀过程中。
5.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于所述的沉淀温度为60-90℃。
6.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于所述的碱性溶液为碳酸钠、氨水或碳酸钾。
7.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于pH为8-9。
8.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于所述的干燥温度为80-120℃。
9.如权利要求3所述的一种合成气制低碳混合醇的石墨烯负载催化剂的制备方法,其特征在于所述的焙烧温度为350-400℃。
10.如权利要求1或2所述的一种合成气制低碳混合醇的石墨烯负载催化剂的应用,其特征在于反应温度为220-280℃, 压力为5.0-7.0MPa, 空速为1000-7500h-1, H2/CO体积比=2.0。
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