CN106964356B - 用于光辅助催化甲醇和二氧化碳合成碳酸二甲酯的半导体催化剂 - Google Patents
用于光辅助催化甲醇和二氧化碳合成碳酸二甲酯的半导体催化剂 Download PDFInfo
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Abstract
本发明公开了用于光辅助催化甲醇和二氧化碳合成碳酸二甲酯的半导体催化剂。本发明以二氧化钛纳米管作为载体,以金属铜和氧化镍作为活性组元。二氧化钛与氧化镍之间形成p‑n异质结,促进光生载流子有效分离。铜与二氧化钛、氧化镍之间形成肖特基势垒使光生电子富集在金属铜上,促进对二氧化碳的活化作用。制备方法为:将载体浸渍到铜‑氨、镍‑氨混合络合物溶液中,超声分散,蒸干后煅烧,再经氢气还原。使用方法:将催化剂置于反应装置中,调节气相甲醇和二氧化碳的摩尔比为2:1~3:1,反应温度为110~140℃,反应压强为0~0.6MPa,采用500W紫外灯照射。该催化剂制备方法简单,甲醇转化率高,并且反应压强低,无需高压设备,极大降低了工业生产成本。
Description
技术领域
本发明属于光催化领域,具体涉及一种半导体催化剂的制备和使用方法,用于光辅助催化甲醇和二氧化碳直接合成碳酸二甲酯。
背景技术
利用二氧化碳合成燃料及化工品不仅可以有效利用工业废弃物,减少二氧化碳排放,又可以生产环境友好的新能源材料,具有环保、节能双重意义。碳酸二甲酯(DMC)是一种重要的环境友好型化工原料,具有广泛的应用,尤其是近年来,美国等发达国家相继出台了更加严格的清洁空气法案,对燃料的含氧量作了相应的限制,使得碳酸二甲酯这一新型燃油添加剂显示出了替代甲基叔丁基醚的良好发展势头。已经工业化生产碳酸二甲酯的方法主要分为三大类:光气法、甲醇氧化羰基化法和酯交换法。近年来,由二氧化碳和甲醇直接合成碳酸二甲酯受到了越来越广泛的注意。该方法具有以下优点:(a)可以资源化利用二氧化碳;(b)原料不使用石油产品,是完全的非石油路线;(c)原料甲醇廉价易得,合成路线简单,从而降低了碳酸二甲酯的成本。
对于热催化来说,由二氧化碳和甲醇直接合成碳酸二甲酯是热力学上是难以进行的反应。吉布斯自由能在0.1Mpa,0-800°C内均为正值,平衡常数Kp和平衡转化率都很小。因此,热催化反应需要在高温、高压条件下进行。目前,用于该反应的催化剂主要可以分为以下几大类:(1)有机烷氧金属催化剂;(2)碱性催化剂;(3)金属醋酸盐催化剂;(4)金属氧化物及固熔体催化剂;(5) 杂多酸催化剂;(6)金属负载型催化剂;(7)离子液体催化剂等。除了研制高效催化剂,设计催化工艺技术也能打破反应的化学平衡限制, 使反应顺利进行,从而提高碳酸二甲酯收率。目前所采用的工艺技术有如下:(1)超临界技术;(2)添加脱水剂和膜反应器;(3)微波技术;(4)光辅助催化技术等。以上无论是采用新型催化剂还是设计工艺催化技术,能使得碳酸二甲酯产率提高的共同原因是有效促进了二氧化碳的活化。紫外和可见光催化被证明是打破热力学限制或促进热力学不宜进行的反应的有效手段。近年来,有关纳米p-n型异质结催化剂报道,为高效光催化剂的设计提供了新思路。两种不同类型(p-或n-型)的半导体相互接触后,随着电子和空穴的各自扩散,p-型半导体能带上移而n-型半导体能带下移。当飘移电流与扩散电流相抵时,界面附近形成空间电荷区,产生内建电场。光照时,两种半导体同时被激发,在内建电场的作用下,光生电子快速流向n-型半导体,而光生空穴快速流向p-型半导体,从而促进了光生载流子的有效分离。
本项目拟根据光催化可在常压下活化二氧化碳的特性,设计纳米p-n型异质结半导体光催化剂(Cu-NiO/TiO2纳米管),利用半导体的复合效应及表面金属铜的肖特基势垒效应,提高光能利用率和光生载流子分离效率,实现0.1-0.6MPa下合成碳酸二甲酯。
发明内容
本发明的目的是针对现有技术中的不足,提供一种纳米p-n型半导体催化剂,通过光辅助催化技术,降低由二氧化碳和甲醇直接合成碳酸二甲酯的反应活化能,提高甲醇转化率,降低反应压强。
用于光辅助催化甲醇和二氧化碳合成碳酸二甲酯的半导体催化剂,由载体和活性组分组成,所述载体为二氧化钛纳米管作,所述活性组分为氧化镍和铜;所述活性组分的加入比例为载体质量的5%~40%,铜与镍的摩尔比为2:1。
上述半导体催化剂的制备方法,包括以下步骤:
(1)将二氧化钛与氢氧化钠溶液在一定温度下水热反应一定时间后,再经去离子水洗,盐酸浸泡,再去离子水洗后,得到二氧化钛纳米管;
(2)将硝酸铜和硝酸镍溶于氨水、去离子水中配成均一的溶液,将载体浸渍到铜-氨、镍-氨混合络合物溶液中,室温搅拌,超声分散,旋转蒸发干,干燥,煅烧后经氢气还原得到半导体催化剂。
在上述的制备方法中,步骤(1)中水热反应温度为110~150℃,反应时间为12~24h,盐酸浸泡时间为5h。
在上述的制备方法中,步骤(1)中采用的氢氧化钠溶液浓度为10mol/L, 盐酸浓度为0.1mol/L。
在上述的制备方法中,步骤(2)中煅烧温度是400~500℃,时间是3~6h,氢气还原的温度是300~400℃,时间是3~5h。
上述半导体催化剂的使用方法,包括以下步骤:
将半导体催化剂置于固定床反应装置中,调节气相甲醇和二氧化碳的摩尔比为2:1~3:1,催化剂床层的温度为110~140℃,反应压力为0.1~0.6MPa,辐射光源为500W高压汞灯,主波长为365nm。
与现有技术相比,本发明具有以下有益效果:
(1)本发明的催化剂载体比表面积大,具有纳米孔道结构,对活性组分的吸附能力强,活性组分在载体上分散性好。在催化过程中,活性组分不容易发生团聚,使得催化剂稳定性强。
(2)本发明的催化剂载体以及氧化镍都可作为紫外光吸收材料,吸收紫外光
产生电子-空穴对,二者之间形成的p-n异质结可以有效地分离电子-空穴对。并且金属铜与载体、氧化镍之间形成的肖特基势垒使光生电子进一步富集在金属铜上,促进对二氧化碳的活化作用,从而提高催化剂的催化活性。
(3)本发明的催化剂反应条件温和,无需高压设备,催化剂与产物容易分离,便于回收利用。
具体实施方式
以下通过具体的实施例进一步说明本发明的技术方案。
实施例1:
称取2 g锐钛矿二氧化钛粉体分散到80 mL 10mol/L的NaOH溶液中,室温搅拌1h后,转移到100 mL的高压反应釜中,在150℃烘箱中反应24 h。反应完毕后冷却至室温,取出白色沉淀物,用去离子水清洗数次,直至上清液pH值为7,过滤后得到的白色沉淀于0.1mol/L的盐酸溶液中浸泡5 h,再次用去离子水清洗白色沉淀数次,直至上清液pH值为7,最后将白色沉淀在60℃的真空干燥箱中烘干得到二氧化钛纳米管。
准确称量2g上述方法制备的二氧化钛纳米管载体,0.2492gNi(NO3)2·6H2O,0.4130g Cu(NO3)2·3H2O,25mL去离子水,5mL 25%的氨水,均置于100mL 的单口圆底烧瓶中,室温搅拌反应12h,然后超声分散1h,接着于60℃旋转蒸发至干,80℃干燥24h后研磨并于300目过筛。最后于450℃在马弗炉中煅烧3h,在管式还原炉中于氢氮混合气(N2/H2=95/5)下350℃还原活化3h。
称取2g上述还原活化的催化剂,装填在固定床反应器的反应管里,调节甲醇和二氧化碳的汽化混合温度100℃,甲醇和二氧化碳的摩尔比例为2/1,反应系统压力为0.6MPa,催化剂床层温度120℃,打开500W高压汞灯进行照射;反应产物采用102G-D 型气相色谱仪每隔5min进行实时检测,检测结果通过与气相色谱连接的计算机进行分析处理。
实施例2:
如实施例1,但Ni(NO3)2·6H2O、Cu(NO3)2·3H2O 的加入量分别为0.4894g和0.8259g。
实施例3:
如实施例1,但Ni(NO3)2·6H2O、Cu(NO3)2·3H2O 的加入量分别为0.7476g和1.2390g。
实施例4:
如实施例1,但Ni(NO3)2·6H2O、Cu(NO3)2·3H2O 的加入量分别为0.4894g和0.8259g,反应系统压强为0.1MPa。
实施例5:
如实施例1,但Ni(NO3)2·6H2O、Cu(NO3)2·3H2O 的加入量分别为0.4894g和0.8259g,反应系统压强为0.3MPa。
对比例1:
如实施例1,但Ni(NO3)2·6H2O、Cu(NO3)2·3H2O 的加入量分别为0.4894g和0.8259g,反应系统压强为0.6MPa,无光照。
实施例的检测结果见表1。
表1 光催化剂的催化效果
实施例 | 甲醇转化率(%) | DMC选择性(%) | DMC收率(%) |
1 | 11.53 | 83.54 | 9.63 |
2 | 13.48 | 87.88 | 11.84 |
3 | 8.87 | 84.78 | 7.51 |
4 | 12.94 | 60.45 | 7.82 |
5 | 12.87 | 77.65 | 9.99 |
对比例1 | 4.83 | 90.13 | 4.35 |
Claims (5)
1.一种用于光辅助催化甲醇和二氧化碳合成碳酸二甲酯的半导体催化剂的制备方法,其特征在于,半导体催化剂由载体和活性组分组成,所述载体为二氧化钛纳米管,所述活性组分为镍和铜;所述活性组分的加入比例为载体质量的5%~40%,铜与镍的摩尔比为2:1;
制备方法包括以下步骤:
(1)将二氧化钛与氢氧化钠溶液在一定温度下水热反应一定时间后,再经去离子水洗,盐酸浸泡,再去离子水洗后,得到二氧化钛纳米管;
(2)将硝酸铜和硝酸镍溶于氨水、去离子水中配成均一的溶液,将载体浸渍到铜-氨、镍-氨混合络合物溶液中,室温搅拌,超声分散,旋转蒸发干,干燥,煅烧后经氢气还原得到半导体催化剂。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中水热反应温度为110~150℃,反应时间为12~24h,盐酸浸泡时间为5h。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中采用的氢氧化钠溶液浓度为10mol/L, 盐酸浓度为0.1mol/L。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中煅烧温度是400~500℃,时间是3~6h,氢气还原的温度是300~400℃,时间是3~5h。
5.权利要求1 所述制备方法得到的半导体催化剂的使用方法,其特征在于包括以下步骤:
将半导体催化剂置于固定床反应装置中,调节气相甲醇和二氧化碳的摩尔比为2:1~3:1,催化剂床层的温度为110~140℃,反应压力为0.1~0.6MPa,辐射光源为500W高压汞灯,主波长为365nm。
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