CN112588290B - 一种草酸酯加氢制乙二醇用铜基催化剂及其制备方法 - Google Patents
一种草酸酯加氢制乙二醇用铜基催化剂及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种草酸酯加氢制乙二醇用铜基催化剂及其制备方法。该催化剂的化学表示为:Cu‑SiO2@SiO2,其中Cu‑SiO2为催化剂的活性组分,SiO2为载体;铜占催化剂质量百分含量5~20wt%,其余为二氧化硅。该催化剂采用离子交换法得到的催化剂前体中铜,以Si‑O‑Cu(NH3)2、[Cu(NH3)2]2+、[Cu(NH3)4]2+等形式存在,加入少量硅溶胶在催化剂前体表面形成保护层,能有效地增强活性组分铜与载体间的相互作用,防止铜颗粒在煅烧和反应过程中发生团聚,提高催化剂活性及稳定性。该铜基催化剂应用于草酸酯加氢制备乙二醇的反应中,在较低的反应温度下,乙二醇的选择性可以达到97%,连续反应500小时催化剂活性不变。
Description
技术领域
本发明属于催化技术领域,具体涉及一种采用离子交换-硅溶胶涂层-蒸氨水热方法得到的耐高温铜基催化剂及制备方法,特别是应用于草酸酯加氢制乙二醇的催化剂及其制备方法。
背景技术
乙二醇是一种重要的基础原料和化工中间体,主要用于合成聚酯树脂和纤维,也常用作溶剂、防冻剂、润滑剂、增塑剂、表面活性剂等。目前,乙二醇的年需求量超过2000万吨,而市场需求的一半左右在中国。由于其独特的性质和广泛的应用价值,近年来人们一直致力于开发高效合成乙二醇的方法。其中煤制乙二醇(CTEG)技术作为一条绿色生产乙二醇的C1化工路线成为时下研究的热点,已进入工业化阶段。煤制乙二醇技术是一个集成的反应路线,其中草酸酯加氢反应是确定最终产物的关键步骤。通过控制催化剂组成和反应条件,草酸酯加氢可以选择性合成乙醇酸甲酯、乙二醇和乙醇。因此加氢催化剂,特别是催化剂活性中心在决定加氢反应途径中起着关键作用。
在过去的十几年,越来越多的研究小组加入到煤制乙二醇技术的研发中,并设计了各种各样的加氢催化剂。在这些催化剂中目前应用最为广泛的是铜基催化剂。但是由于金属铜的Hüttig温度为134℃(Chem.Commun.,2013,49:5195–5197),高于该温度则金属铜开始发生晶格表面原子显著迁移,而草酸酯加氢制备乙二醇的反应温度一般在160~250℃之间,因此在反应过程中铜颗粒易发生迁移团聚从而导致催化剂逐渐失活。复旦大学(ChemCatChem,2010,2:206-213)以六方孔道HMS分子筛为载体,采用离子交换法制备的Cu/SiO2催化剂,草酸二甲酯转化率达到100%,乙二醇选择性达到98%。然而HMS分子筛载体的制备成本过高,而且也未有催化剂稳定性评价结果;厦门大学(Nat.Commun.2018,9,3367)采用介孔二氧化硅包封硅酸盐铜纳米管方法制备铜纳米催化剂,在液时空速为100h-1,氢酯比为80时,催化剂仍具有显著的催化活性,乙二醇选择性为92.3%。但是该方法制备流程长过程复杂,且很难进行大规模制备,催化剂稳定性评价也只有200小时;北京化工大学(Appl.Catal.B:Environmental,2019,248:394–404)利用CuMgAl层状水滑石前驱体的拓扑结构转变制备的铜基纳米催化剂,能使反应温度降低到165℃时,乙二醇选择性达到94.4%。但是该催化剂制备工艺复杂、成本高,而且未见催化剂使用寿命,工业化应用前景低。
在现阶段的研究中,铜基加氢催化剂失活率高、使用寿命短是制约草酸酯气相加氢制乙二醇工业化的重要因素。而要提高铜基加氢催化剂的稳定性,减缓金属颗粒间的迁移团聚,一般来说,除了增强金属与载体之间的相互作用力,还可以对金属颗粒进行限域,阻止活性结构褪变,从而保持催化剂的性能,提高催化剂的稳定性。因此,本发明尝试采用离子交换-硅溶胶涂层-蒸氨水热多步合成结合的方式,研究开发具有高热稳定性、高活性的铜基加氢催化剂,应用于草酸酯加氢制乙二醇反应中,延长催化剂的使用寿命。
发明内容
本发明的目的是提供一种草酸酯加氢制乙二醇用铜基催化剂及其制备方法,解决现有技术中催化剂稳定性差等问题。
本发明所提供的铜基催化剂,其化学表示式为:Cu-SiO2@SiO2,其中Cu-SiO2为催化剂的活性组分,SiO2为载体;其中铜占催化剂质量百分含量5~20wt%,优选为8~20%,其余为二氧化硅;所述SiO2载体为球状,比表面积为350~500m2/g,平均孔径为5~15nm,粒度为1-4cm。
上述铜基催化剂的制备方法,具体制备步骤为:
A.将氧化硅载体置于0.5~2mol/L的氨水中浸渍一周,过滤并干燥,于100~180℃干燥1~4小时;所述氧化硅载体为球状,其比表面积为250-400m2/g,平均孔径为5~15nm,粒度为1~4cm。
B.将步骤A处理过的氧化硅载体于120~180℃干燥1~4h后,按照设计的活性组分铜占催化剂质量百分含量,浸入铜氨溶液中,升温至40~90℃进行离子交换,时间为12~36h;过滤、洗涤,得到催化剂前体;
所述的铜氨溶液是将铜盐溶于去离子水中,再加入市售的氨水;铜氨溶液中Cu2+离子浓度为0.5~2mol/L,氨水的浓度为4~20mol/L,溶液的pH值为10~13;所述的铜盐是硝酸铜、醋酸铜中的一种;
C.将步骤B得到的催化剂前体浸入硅溶胶溶液中,在30~70℃下搅拌12~48h,升温至50~90℃蒸氨1~4h,转移至水热釜中,升温至100~200℃水热处理12~40h;过滤、洗涤,于50~180℃下进行分步干燥18~32h,其中于50~80℃干燥8~24h,于80~100℃干燥2~5h,于110~140℃干燥3~5h,于140~180℃干燥5~8h;再于300~700℃焙烧3~8h;粉碎、筛分出粒度为0.8~2.0cm,得到铜基催化剂,表示为Cu-SiO2@SiO2。
所述的硅溶胶溶液是将市售质量百分含量为20%硅溶胶加入去离子水配制的浓度为0.1~0.4mL/L溶液,硅溶胶溶液的用量应能使催化剂前体完全没入溶液中。
对得到的催化剂进行表征、应用效果测试,结果如下:
图1说明实施例2得到的Cu-SiO2@SiO2催化剂在650℃下焙烧后仍未发生铜物种的聚集,而对比例2得到的Cu-SiO2催化剂已经出现明显的CuO衍射峰,出现了团聚状的CuO颗粒;
图2说明实施例1得到的Cu-SiO2@SiO2催化剂相比对比例1得到的Cu-SiO2催化剂形成了更多的页硅酸铜(波长在670cm-1处的吸收峰为页硅酸的特征峰);
图3说明催化剂的性能在500小时的反应时间内均能保持稳定,未发生明显的失活;
图4说明实施例1得到的Cu-SiO2催化剂经过300℃还原后铜颗粒大小均匀,而经过500小时反应后铜颗粒仍然保持高度分散状态,并未发生明显的长大与团聚。
将上述催化剂应用于草酸二甲酯加氢制乙二醇反应进行应用效果测试,结果见表1,由表1可见,草酸酯转化率为90~100%,乙二醇选择性为85~100%。
与现有技术相比,本发明的有益效果为:
本发明所述催化剂通过离子交换、硅溶胶涂层、蒸氨固化分步制备的方法,利用离子交换法得到的催化剂前体中铜以Si-O-Cu(NH3)2、[Cu(NH3)2]2+、[Cu(NH3)4]2+等形式存在,加入少量硅溶胶在催化剂前体表面形成保护层,能有效地增强活性组分铜与载体间的相互作用,在焙烧及反应过程中阻碍活性组分铜的烧结团聚;前驱体表面的铜氨物种与硅溶胶与反应形成页硅酸铜,增加了还原后催化剂中Cu+的含量,可显著提高催化剂的低温活性、乙二醇的选择性以及热稳定性。本发明所采用制备原料价格低廉、制备过程简单、操作重现性高,因此具有较大工业化应用前景。
附图说明
图1为实施例2和对比例2得到的催化剂XRD谱图比较;
图2为实施例1和对比例1得到的Cu-SiO2催化剂红外谱图比较;
图3为实施例1得到的Cu-SiO2@SiO2催化剂500小时的寿命考察图;
图4为实施例1得到的Cu-SiO2@SiO2催化剂还原后和500小时反应后的透射电镜图;
具体实施方式
实施例1
A.采用的硅胶载体为市售青岛海洋化工有限公司的B-type氧化硅载体,其比表面积为300m2/g,平均孔径为12nm,粒度为1.5~2.5cm的氧化硅载体置于1mol/L的氨水中浸渍一周,过滤后在干燥箱中于120℃干燥24h,得到预处理的氧化硅载体;
B.将6g醋酸铜溶于30mL去离子水中,在60℃下搅拌至醋酸铜完全溶解,再加入30mL28%浓氨水,继续搅拌0.5h得到铜氨溶液;将入4g预处理的氧化硅载体于160℃干燥2小时后浸入铜氨溶液中,在60℃下浸渍24h后,过滤、洗涤3-4次,得到催化剂前体;
C.在120mL去离子水中加入7.2g质量分数为20%的硅溶胶配成浓度为0.2mol/L的硅溶胶溶液,搅拌使二者混合均匀;将步骤B得到的催化剂前体浸入到硅溶胶溶液中,在40℃的温度下搅拌48h后,升温至80℃进行蒸氨2h;将混合物转移至水热釜中,升温至100℃进行水热处理24h;待冷却至室温,经过滤后进行步干燥,具体干燥步骤为:60℃干燥12h,于85℃干燥3h,于120℃干燥3h,于160℃干燥5h;再置于马弗炉中500℃焙烧5h,得到Cu-SiO2@SiO2催化剂。用ICP测试催化剂中活性组分铜的含量,结果见表1。
将焙烧后的Cu-SiO2@SiO2催化剂粉碎过筛,筛分出粒度为0.8~2.0cm的催化剂颗粒用于下面应用实验。
催化剂应用效果测试:在气-固相固定床反应器中,取上述催化剂颗粒2ml装填入反应管的中部,用空速为3000h-1的氢气在300℃下还原5h;以质量含量为20%的草酸二甲酯的甲醇溶液为原料,在反应温度为180℃,草酸二甲酯液时空速为1.0h-1,氢酯比为100,反应压力为2.0MPa的条件下,反应物在催化剂表面发生反应,生成含乙二醇的产品,其评价结果见表1。
实施例2
A.同实施例1。
B.将9g醋酸铜溶于30mL去离子水中,在30℃下搅拌至醋酸铜完全溶解,再加入40mL28%浓氨水,继续搅拌0.5h得到铜氨溶液;将入4g预处理的氧化硅载体于180℃干燥1小时后浸入铜氨溶液中,在80℃下浸渍12h后,过滤、洗涤3-4次,得到催化剂前体;
C.在120mL去离子水中加入7.2g质量分数为20%的硅溶胶配成浓度为0.2mol/L的硅溶胶溶液,搅拌使二者混合均匀;将步骤B得到的催化剂前体浸入到硅溶胶溶液中,在60℃的温度下搅拌24h后,升温至90℃进行蒸氨1h;将混合物转移至水热釜中,升温至200℃进行水热处理12h;待冷却至室温,经过滤后进行步干燥,具体干燥步骤为:50℃干燥24h,于90℃干燥4h,于110℃干燥4h,于150℃干燥6h;再置于马弗炉中650℃焙烧5h,得到Cu-SiO2@SiO2催化剂。用ICP测试催化剂中活性组分铜的含量,结果见表1。
将焙烧后的Cu-SiO2@SiO2催化剂粉碎过筛,筛分出粒度为0.8~2.0cm的催化剂颗粒用于下面应用实验。
催化剂应用效果测试:在气-固相固定床反应器中,取上述催化剂颗粒2ml装填入反应管的中部,用空速为3000h-1的氢气在300℃下还原5h;以质量含量为20%的草酸二甲酯的甲醇溶液为原料,在反应温度为190℃,草酸二甲酯液时空速为1.0h-1,氢酯比为100,反应压力为2.0MPa的条件下,反应物在催化剂表面发生反应,生成含乙二醇的产品,其评价结果见表1。
实施例3
A.采用的硅胶载体为市售青岛海洋化工有限公司的B-type氧化硅载体,其比表面积为350m2/g,平均孔径为14nm,粒度为2~3cm的氧化硅载体置于2mol/L的氨水中浸渍一周,过滤后在干燥箱中于150℃干燥12h,得到预处理的氧化硅载体;
B.将12g醋酸铜溶于30mL去离子水中,在40℃下搅拌至醋酸铜完全溶解,再加入40mL28%浓氨水,继续搅拌0.5h得到铜氨溶液;将入4g预处理的氧化硅载体于150℃干燥3小时后浸入铜氨溶液中,在40℃下浸渍36h后,过滤、洗涤3-4次,得到催化剂前体;
C.在120mL去离子水中加入14.4g质量分数为20%的硅溶胶配成浓度为0.4mol/L的硅溶胶溶液,搅拌使二者混合均匀;将步骤B得到的催化剂前体浸入到硅溶胶溶液中,在60℃的温度下搅拌48h后,升温至80℃进行蒸氨2h;将混合物转移至水热釜中,升温至200℃进行水热处理24h;待冷却至室温,经过滤后进行步干燥,具体干燥步骤为:80℃干燥12h,于100℃干燥3h,于130℃干燥3h,于180℃干燥5h;再置于马弗炉中500℃焙烧5h,得到Cu-SiO2@SiO2催化剂。用ICP测试催化剂中活性组分铜的含量,结果见表1。
催化剂性能评价条件同实施例1,评价结果见表1。
对比例1
A.同实施例1。
B.将6g醋酸铜溶于30mL去离子水中,在60℃下搅拌至醋酸铜完全溶解,再加入30mL28%浓氨水,继续搅拌0.5h;在铜氨溶液中加入4g预处理的氧化硅载体,在60℃下浸渍24h后经多次过滤、洗涤;将混合物转移至水热釜中,升温至100℃进行水热处理24h;待冷却至室温,经过滤后于50~180℃下进行分步干燥18~32h,其中于60℃干燥12h,于85℃干燥3h,于120℃干燥3h,于160℃干燥5h;置于马弗炉中500℃焙烧5h,得到Cu-SiO2催化剂。用ICP测试催化剂中活性组分铜的含量,结果见表1。
催化剂性能评价条件同实施例1,评价结果见表1。
对比例2
A.同实施例1。
B.将6g醋酸铜溶于30mL去离子水中,在60℃下搅拌至醋酸铜完全溶解,再加入30mL28%浓氨水,继续搅拌0.5h;在铜氨溶液中加入4g预处理的氧化硅载体,在60℃下浸渍24h后经多次过滤、洗涤;将混合物转移至水热釜中,升温至100℃进行水热处理24h;待冷却至室温,经过滤后于50~180℃下进行分步干燥18~32h,其中于60℃干燥12h,于85℃干燥3h,于120℃干燥3h,于160℃干燥5h;置于马弗炉中650℃焙烧5h,得到Cu-SiO2催化剂。用ICP测试催化剂中活性组分铜的含量,结果见表1。
催化剂性能评价条件同实施例2,评价结果见表1。
表1
Claims (3)
1.一种草酸酯加氢制乙二醇用铜基催化剂的制备方法,其特征是采用如下步骤制备:
A.将氧化硅载体置于0.5~2mol/L的氨水中浸渍一周,过滤并干燥,于100~180℃干燥1~4小时;所述氧化硅载体为球状,其比表面积为250-400m2/g,平均孔径为5~15nm,粒度为1~4cm;
B.将步骤A处理过的氧化硅载体于120~180℃干燥1~4h后,按照设计的活性组分铜占催化剂质量百分含量,浸入铜氨溶液中,升温至40~90℃进行离子交换,时间为12~36h;过滤、洗涤,得到催化剂前体;
所述的铜氨溶液是将铜盐溶于去离子水中,再加入市售的氨水;铜氨溶液中Cu2+离子浓度为0.5~2mol/L,氨水的浓度为4~20mol/L,溶液的pH值为10~13;所述的铜盐是硝酸铜、醋酸铜中的一种;
C.将步骤B得到的催化剂前体浸入硅溶胶溶液中,在30~70℃下搅拌12~48h,升温至50~90℃蒸氨1~4h,转移至水热釜中,升温至100~200℃水热处理12~40h;过滤、洗涤,于50~180℃下进行分步干燥18~32h,其中于50~80℃干燥8~24h,于80~100℃干燥2~5h,于110~140℃干燥3~5h,于140~180℃干燥5~8h;再于300~700℃焙烧3~8h;粉碎、筛分出粒度为0.8~2.0cm,得到铜基催化剂,表示为Cu-SiO2@SiO2;
所述的硅溶胶溶液是将市售质量百分含量为20%硅溶胶加入去离子水配制的浓度为0.1~0.4mL/L溶液,硅溶胶溶液的用量应能使催化剂前体完全没入溶液中。
2.一种根据权利要求1所述的方法制备的草酸酯加氢制乙二醇用铜基催化剂,其特征是该催化剂的化学表示为:Cu-SiO2@SiO2,其中Cu-SiO2为催化剂的活性组分,SiO2为载体;其中铜占催化剂质量百分含量5~20wt%,其余为二氧化硅;所述SiO2载体为球状,比表面积为350~500m2/g,平均孔径为5~15nm,粒度为1-4cm。
3.根据权利要求2所述的草酸酯加氢制乙二醇用铜基催化剂,其特征是该催化剂中铜占催化剂的质量百分含量为8~20%,其余为二氧化硅。
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