CN116351416A - 一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法 - Google Patents
一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法 Download PDFInfo
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Abstract
本发明属于无机功能材料制备技术领域,公开一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法。所述催化剂由载体SiO2以及负载在其上的金属Cu纳米颗粒组成。制备方法:将水溶性金属Cu盐置于容器中,先加入浓氨水,再加水,搅拌混合均匀,获得金属前驱体溶液;将硅胶加入所得溶液中,室温下搅拌酸碱吸附浸渍;将浸渍过的固体进行过滤水洗、干燥、焙烧、氢气气氛下还原、研磨,即得目标催化剂。使用方法:将底物糠醛加入到异丙醇中,配制成反应底物溶液;将反应底物溶液和催化剂混合置于密闭高压反应釜中,用氢气置换排出空气,在110‑150℃、氢压0.5‑2MPa下搅拌密闭反应2‑8h。本发明催化剂催化活性高、易于分离,整个过程操作简单,成本低。
Description
技术领域
本发明属于无机功能材料制备技术领域,具体涉及一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法。
背景技术
化石燃料的大量消耗加剧了温室气体的排放,这引起了人们对安全环保的生物燃料的重视。生物质因其可再生性、无污染性成为了化石能源的理想替代品。其中,糠醛是最重要的生物质衍生物之一,是一种重要的化工原料,通过加氢、氧化、醚化等可以制备一系列高附加值化学品或燃料。近年来,醚类化合物引起了极大关注。醚类化合物可以被用作燃料添加剂。其中,糠醛和不同醇溶剂的醚化产物可作为柴油添加剂。然而,目前关于非贵金属催化糠醛还原醚化的技术报道较少。Wu等人报道了一种卤素改性的Pd/Al2O3催化剂,产物异丙基糠醚的收率可达85%。Pd基催化剂对异丙基糠醚的活性较高,然而钯价格昂贵。因此,迫切需要发展高效催化糠醛与醇还原醚化制备糠醚的非贵金属催化剂,以降低经济成本。
发明内容
为了克服现有技术的不足,本发明的目的在于提供一种糠醛醚化制糠醚用非贵金属催化剂及其制备方法和使用方法。
为实现上述目的,本发明采取的技术方案如下:
一种糠醛醚化制糠醚用非贵金属催化剂,所述催化剂由载体SiO2以及负载在其上的金属Cu纳米颗粒组成,金属Cu纳米颗粒的负载量为3-5wt%,负载量是指金属Cu纳米颗粒在整个催化剂中占有的质量百分含量。
一种糠醛醚化制糠醚用非贵金属催化剂的制备方法,制备步骤如下:
(1)、金属前驱体溶液的配制:将水溶性金属Cu盐置于容器中,先加入浓氨水(浓度25-28 wt%),再加水,搅拌混合均匀,获得金属前驱体溶液,保存备用;
(2)、将硅胶加入步骤(1)所得溶液中,室温下搅拌酸碱吸附浸渍;
(3)、将步骤(2)浸渍过的固体进行过滤水洗、干燥、焙烧,焙烧温度为120-150℃,焙烧时间为4-6h;
(4)、将步骤(3)焙烧所得固体在氢气气氛下还原、研磨,即得目标催化剂;
其中,原料的用量配比为水溶性铜盐以其提供的金属Cu计量,水溶性金属Cu盐∶浓氨水∶水=(8-12)mmol∶(30-40)mL∶(300-450)mL;水溶性金属Cu盐∶硅胶=(8-12)mmol∶(5-15)g。
较好地,步骤(2)中,硅胶使用前用2.5-20 wt%硫酸浸泡3-12 h。
较好地,步骤(2)中,搅拌时间为1-3h。
较好地,步骤(4)中,还原温度为250-450℃,还原时间为1-2h,升温速率为5-10℃/min,结束后自然冷却至室温。
一种糠醛醚化制糠醚用非贵金属催化剂的使用方法,使用步骤如下:
(1)、将底物糠醛加入到异丙醇中,配制成反应底物溶液;
(2)、将步骤(1)所得反应底物溶液和所述糠醛醚化制糠醚用非贵金属催化剂混合置于密闭高压反应釜中,用氢气置换排出空气,在110-150℃、氢压0.5-2MPa下搅拌密闭反应2-8h,冷却至室温后,过滤取滤液,蒸馏分离(蒸馏温度为对应糠醚的沸点温度),获得糠醚;其中,原料的用量配比为糠醛∶异丙醇∶催化剂=(600-700)mg∶(30-50)mL∶(350-450)mg。
本发明引入浓氨水的作用有两点:(1)由于硅胶本身为酸性,因此本发明引入浓氨水增加金属前驱体溶液的碱性,在搅拌过程中,前驱体金属阳离子通过酸碱吸附在酸性硅胶上,再经过焙烧、还原合成金属纳米催化剂;(2)作为扩孔剂,扩大所得催化剂的孔径,而糠醛醚化制糠醚时糠醛是在催化剂表面进行吸附脱附的,催化剂孔径大有利于表面分子的及时移除,从而提高催化活性。
本发明的有益效果:
(1)、本发明开发了一种糠醛醚化制糠醚用非贵金属催化剂,该催化剂为SiO2负载纳米铜催化剂,对糠醛醚化制糠醚反应的催化活性高、催化剂易于分离,整个过程操作简单,成本低;
(2)、本发明制得的催化剂属于非贵金属负载型催化剂,催化剂的制备原料廉价,金属粒径小,大大地降低了经济成本。
附图说明
图1:实施例1制备的4.5wt%Cu/SiO2催化剂的XRD图谱。
图2:实施例1制备的4.5wt%Cu/SiO2催化剂的HAADF图(上图)和粒径统计图(下图)。
图3:实施例1制备的4.5wt%Cu/SiO2催化剂用于糠醛醚化的反应路线图。
图4:实施例1催化糠醛醚化所得产物异丙基糠醚的质谱图。
具体实施方式
下面结合本发明具体的实施例,对本发明技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
以下实施例中所用硅胶为市售硅胶。
实施例1
Cu/SiO2催化剂(载体为SiO2,载体上负载金属Cu纳米颗粒)的制备方法,步骤如下:
(1)、金属前驱体溶液的配制:称量2.8517g Cu(NO3)2·3H2O于500mL烧杯中,加入37mL质量浓度28%的浓氨水,再加入434mL去离子水,搅拌混合均匀,保存备用;
(2)、将15g硅胶(直接使用,没有经过硫酸浸泡处理)加入步骤(1)所得溶液中,室温下搅拌3h酸碱吸附浸渍;
(3)、将步骤(2)所得固体进行过滤水洗,然后置于烘箱中60℃下干燥4h;
(4)、将步骤(3)所得固体在马弗炉中120℃下焙烧4h,最后在氢气炉中,以10℃/min速率升温至450℃,恒温2h,结束之后自然降至室温,研磨,即得目标催化剂;紫外测试步骤(2)吸附后剩余溶液中的Cu离子浓度,计算得出目标催化剂的实际负载量为4.5wt%。本实施例1制备的催化剂标记为4.5wt%Cu/SiO2。
图1为本实施例1制备的4.5wt%Cu/SiO2催化剂的XRD图谱。由图1可以看出:该催化剂在2θ=22.5°出现一个宽衍射峰,归属于SiO2;另外,在2θ = 43.3°、 50.4°、74.1°出现了三个衍射峰,分别归属于Cu (111), Cu (200), Cu (220)晶面。
图2为本实施例1制备的4.5wt%Cu/SiO2催化剂的HAADF图(上图)和粒径统计图(下图),经过粒径统计,得知实施例1中金属Cu纳米颗粒粒径范围在1.5-7nm,平均粒径约等于3.34nm,证明了此种方法合成的金属Cu纳米颗粒粒径很小,具有较高的原子利用率。
表1为原料硅胶和本实施例1制备的4.5wt%Cu/SiO2催化剂的BET和孔径对比结果,可知:与原料硅胶相比,4.5wt%Cu/SiO2的比表面积显著减小,这是因为金属Cu纳米颗粒堵塞了硅胶孔道,而孔径的增大是因为氨水作为扩孔剂扩大了孔径。
4.5wt%Cu/SiO2催化剂的使用方法:
将420mg催化剂、700mg糠醛、40mL异丙醇加入不锈钢高压釜中,用氢气置换空气4-5次,并最终将氢气反应压力调整为2MPa,在150℃下反应8h,结束后自然冷却至室温,经过滤得到液体混合物,送去气相色谱分析。
反应路线如图3所示,产物异丙基糠醚的质谱图见图4,和zhang等人研究的糠醛加氢所得副产物异丙基糠醚的质谱图(文献:Highly Selective Conversion of Furfuralto Furfural Alcohol or Levulinate Ester in OnePot over ZrO2@SBA-15 and ItsKinetic Behavior,ACS Sustainable Chem. Eng)一致。
对照例1
Cu-Ni /SiO2催化剂(载体为SiO2,载体上同时负载金属Cu和Ni纳米颗粒)的制备方法,其过程基本同实施例1,不同之处在于:将步骤(1)加入的“2.8517g Cu(NO3)2·3H2O”改为“0.5878g Cu(NO3)2·3H2O和0.7660g·Ni(NO3)2·6H2O”,15g硅胶改为5g硅胶;其它步骤同实施例1。目标催化剂中Cu和Ni的理论负载量均为3wt%。本对照例1制备的催化剂标记为3wt%Cu-3wt%Ni/SiO2。
催化剂的使用方法同实施例1。
对照例2
实施例1制备的4.5wt% Cu/SiO2催化剂的使用方法,其过程基本同实施例1,不同之处在于:将“异丙醇”替换为“甲醇”;其它同实施例1。对应的产物糠醚为甲基糠醚。
对照例3
实施例1制备的4.5wt% Cu/SiO2催化剂的使用方法,其过程基本同实施例1,不同之处在于:将“异丙醇”替换为“正丙醇”;其它同实施例1。对应的产物糠醚为正丙基糠醚。
对照例4
实施例1制备的4.5wt% Cu/SiO2催化剂的使用方法,其过程基本同实施例1,不同之处在于:将“异丙醇”替换为“正丁醇”;其它同实施例1。对应的产物糠醚为正丁基糠醚。
对照例5
实施例1制备的4.5wt% Cu/SiO2催化剂的使用方法,其过程基本同实施例1,不同之处在于:将“异丙醇”替换为“仲丁醇”;其它同实施例1。对应的产物糠醚为仲丁基糠醚。
实施例1以及对照例1-5催化剂活性结果见表2。
由表2可知:实施例1制备的4.5wt% Cu/SiO2催化剂在糠醛醚化制糠醚中,当醇溶剂为异丙醇时表现出了良好的活性,糠醛转化率>99%,糠醚选择性>80%,而对照例1制备的3wt%Cu-3wt%Ni/SiO2催化剂糠醚选择性明显下降,说明引入第二种金属Ni并不能提高活性甚至有所降低;对于对照例2-5中所使用的其它醇溶剂甲醇、正丙醇、正丁醇、仲丁醇,糠醚选择性降低,说明异丙醇作溶剂时,催化活性最好,但该催化剂也可应用于制备其它糠醚,具有广阔的应用前景。
Claims (6)
1.一种糠醛醚化制糠醚用非贵金属催化剂,其特征在于:所述催化剂由载体SiO2以及负载在其上的金属Cu纳米颗粒组成,金属Cu纳米颗粒的负载量为3-5wt%。
2.一种如权利要求1所述糠醛醚化制糠醚用非贵金属催化剂的制备方法,其特征在于,制备步骤如下:
(1)、金属前驱体溶液的配制:将水溶性金属Cu盐置于容器中,先加入浓氨水,再加水,搅拌混合均匀,获得金属前驱体溶液,保存备用;
(2)、将硅胶加入步骤(1)所得溶液中,室温下搅拌酸碱吸附浸渍;
(3)、将步骤(2)浸渍过的固体进行过滤水洗、干燥、焙烧,焙烧温度为120-150℃,焙烧时间为4-6h;
(4)、将步骤(3)焙烧所得固体在氢气气氛下还原、研磨,即得目标催化剂;
其中,原料的用量配比为水溶性金属Cu盐以其提供的金属Cu计量,水溶性金属Cu盐∶浓氨水∶水=(8-12)mmol∶(30-40)mL∶(300-450)mL;水溶性金属Cu盐∶硅胶=(8-12)mmol∶(5-15)g。
3.如权利要求2所述的糠醛醚化制糠醚用非贵金属催化剂的制备方法,其特征在于:步骤(2)中,硅胶使用前用2.5-20 wt%硫酸浸泡3-12 h。
4.如权利要求2所述的糠醛醚化制糠醚用非贵金属催化剂的制备方法,其特征在于:步骤(2)中,搅拌时间为1-3h。
5.如权利要求2所述的糠醛醚化制糠醚用非贵金属催化剂的制备方法,其特征在于:步骤(4)中,还原温度为250-450℃,还原时间为1-2h,升温速率为5-10℃/min,结束后自然冷却至室温。
6.一种如权利要求1所述的糠醛醚化制糠醚用非贵金属催化剂的使用方法,其特征在于,使用步骤如下:
(1)、将底物糠醛加入到异丙醇中,配制成反应底物溶液;
(2)、将步骤(1)所得反应底物溶液和所述糠醛醚化制糠醚用非贵金属催化剂混合置于密闭高压反应釜中,用氢气置换排出空气,在110-150℃、氢压0.5-2MPa下搅拌密闭反应2-8h,冷却至室温后,过滤取滤液,蒸馏分离,获得糠醚;其中,原料的用量配比为糠醛∶异丙醇∶催化剂=(600-700)mg∶(30-50)mL∶(350-450)mg。
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