CN115382538B - 一种用于有机废水催化降解制氢的新型金属基炭催化剂及其制备方法 - Google Patents
一种用于有机废水催化降解制氢的新型金属基炭催化剂及其制备方法 Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 239000002351 wastewater Substances 0.000 title claims abstract description 13
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
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- 238000000034 method Methods 0.000 claims abstract description 24
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种用于有机废水催化降解制氢的新型金属基炭催化剂及其制备方法。本发明将聚乙烯醇溶解于水中，加入金属盐溶液，得到前驱体溶液；所述金属盐为镍盐、铁盐、钯盐中的一种；将前驱体溶液置于在室温下干燥一段时间；干燥后的前驱体置于空气氛围中，在150～250℃下预处理得到热分解后产物；将热分解后产物置于氮气氛围中，在450～600℃下炭化处理0.5～2h，最终制备得到介孔金属基炭材料。本发明制得的金属基炭催化剂具有孔径丰富、高分散度，其催化性能优异，并且该制备工艺简单、还大大提高了材料的收率，具有工业应用前景。
Description
技术领域
本发明属于材料制备领域，具体涉及一种用于有机废水催化降解制氢的新型金属基炭催化剂及其制备方法。
背景技术
随着全球工业化进程的加快，含有难降解有机物的废水引发的生态问题愈发严重。这些废水来自于印染、石油化工、制药、农药以及制革等生产过程中，其成分复杂、难降解等特点，严重污染水环境。目前国内外处理有机废水的常用方法可归纳为物理法(吸附法、蒸汽法、溶液萃取法及膜萃取法)、化学法(化学氧化法和超声波、超临界和光催化等各种氧化法)以及生化法，这些传统的水处理方法在实际应用中存在一定的问题或不足。有机废水催化重整制氢的技术，具有选择性高、原料利用率高、能耗低的特点，具有广阔的潜在发展空间。该技术是在金属催化剂作用下，较温和的温度与压力条件下，通过水相重整反应制备氢气的新技术。该技术常用的活性物质为Ni、Pd、Pt、Ru、Rh和Fe等金属；常用催化剂载体为TiO2、炭黑、活性炭和Al2O3等。
本发明创新性地提出了一种用于有机废水催化降解制氢的新型金属基炭催化剂的制备方法，最终制得具有孔径丰富、高分散度的金属基炭催化剂，其催化性能优异，并且该制备工艺简单、还大大提高了材料的收率，具有工业应用前景。
发明内容
本发明的一个目的在于针对现有技术的不足，提供一种用于有机废水催化降解制氢的新型金属基炭材料的制备方法。所述方法能够实现金属基炭材料的高产率、高效率制备，同时所制备的改性金属基炭材料具有高表面积、孔径分布丰富、活性金属分散性高、催化性能好、稳定性强等特点。
本发明的目的通过下述方案实现：
本发明提供的一种新型金属基炭材料的制备方法：采用聚乙烯醇(PVA)为炭前驱体，以Ni(NO3)2、Fe(NO3)3、PdCl2为金属活性剂，于不同气体氛围进行处理，按照下述步骤依次进行：
步骤(1)、将聚乙烯醇(PVA)溶解于水中，溶解过程中加热至60-80℃，时间为1-2h，溶解成透明溶液；将上述溶液冷却至常温后，加入金属盐溶液，匀速搅拌均匀后得到前驱体溶液；
作为优选，所述聚乙烯醇(PVA)与金属盐的质量比为1:(0.5～3)；
作为优选，所述金属盐为镍盐、铁盐、钯盐中的一种；
作为优选，所述镍盐采用Ni(NO3)2，所述铁盐采用Fe(NO3)3，所述钯盐采用PdCl2；
作为优选，所述搅拌时间为30min～8h，更为优选为30min～2h；
步骤(2)、将前驱体溶液置于在室温下干燥一段时间；
作为优选，干燥时间为4-24h；更为优选为干燥的温度控制在20～100℃，干燥时间为8-24h；
步骤(3)、将步骤(2)干燥后的前驱体置于空气氛围中，在150～250℃温度下预处理一段时间，得到热分解后产物；
作为优选，预处理时间为1h～4h；
步骤(4)、将热分解后产物置于氮气氛围中，在450～600℃下炭化处理0.5～2h，最终制备得到介孔金属基炭材料。
本发明的另一个目的是提供一种用于有机废水催化降解制氢的新型金属基炭材料，采用以上方法制备得到。
本发明的又一个目的是提供上述金属基炭材料在有机废水催化降解制氢上的应用。
本方法制备金属基炭催化剂的关键技术在改性物质负载过程以及空气预处理、炭化过程的控制。具体原理如下：
通过均匀混合将目标离子均匀附着在PVA中进行改性，然后对其进行预处理、炭化制备，使金属基炭催化剂在整个过程中形成其基本结构及表面官能团，与此同时又实现了炭收率的提高，从而制备出高性能的介孔金属基炭催化剂。
相对于现有技术，本发明具有如下优点和有益效果：
1、本发明所采用的金属基炭催化剂的制备过程中，通过均匀混合将目标离子附着在载体上后，进行炭化、活化处理使得金属基炭催化剂具备高比表面积、分布丰富的孔径(介孔为主)。
2、此改性方法为原位生长，制备的催化剂可以充分发挥改性物质和活性炭本身的特性，克服由于改性物质占据活性炭原有点位导致活性降低及缺失的缺点，具有高催化性能。
3、此法可制备高含量金属-炭基催化剂，其工艺流程简单，绿色环保；另外，生产原料易得，生产成本低，产率高。
附图说明
图1是金属基炭材料的TEM图。
图2是金属基炭材料空气预处理的TG图。
具体实施方式
下面结合具体实施例对本发明做进一步的分析。
实施例1
取PVA(聚乙烯醇)20g，在60℃下溶解成透明液体，冷却后在常温下加入表1用量的Ni(NO3)2溶液中，并匀速搅拌，均匀混合2h后滤出粘稠的前驱体并将其放入培养皿中室温环境下干燥24h，然后将前驱体在空气氛围中190℃下进行预处理1h，接着将产物在氮气氛围中500℃下进行炭化处理1h。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。
将0.5g实施例1金属基炭催化剂产物加入到固定床反应器中(通过反应器的苯酚浓度1wt％)中，然后反应温度300℃、压力为20MPa(LHSV＝20h-1)条件下进行催化剂的性能评价。
表1.不同质量比的Ni(NO3)2和PVC对苯酚转化率的影响
实施例2
取PVA(聚乙烯醇)20g，在60℃下溶解成透明液体，冷却后在常温下加40g的Ni(NO3)2试剂，并匀速搅拌，按照表2均匀混合一段时间后滤出粘稠的前驱体并将其放入培养皿中室温下干燥12h，然后将前驱体在空气氛围中150℃下进行预处理2h，接着将产物在氮气氛围中450℃下进行炭化处理2h。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同混合时间对苯酚转化率的影响如表2所示。
表2.不同混合时间对苯酚转化率的影响
实施例3
取PVA(聚乙烯醇)20g，在60℃下溶解成透明液体，冷却后在常温下加10g的Ni(NO3)2试剂，并匀速搅拌，均匀混合6h后滤出粘稠的前驱体并将其放入培养皿中一定环境下干燥8h，然后将其在空气氛围中250℃下进行预处理1h，接着将产物在氮气氛围中600℃下进行炭化处理0.5h，最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同干燥温度对苯酚转化率的影响如表3所示。
表3.不同干燥温度对苯酚转化率的影响
实施例4
取PVA(聚乙烯醇)10g，在80℃下溶解成透明液体，冷却后在常温下分别加至一定量的30g的Ni(NO3)2试剂，并匀速搅拌，均匀混合8h后滤出粘稠的前驱体并将其放入培养皿中室温环境下干燥8h，然后将前驱体在空气氛围中按照表4温度下进行预处理1h，接着将产物在氮气氛围中500℃下进行炭化处理1h。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同空气预处理温度对苯酚转化率的影响如表4所示。
表4.不同空气预处理温度对苯酚转化率的影响
实施例5
取PVA(聚乙烯醇)20g，在80℃下溶解成透明液体，冷却后在常温下加20g的Ni(NO3)2试剂，并匀速搅拌，均匀混合1h后滤出粘稠的前驱体并将其放入培养皿中室温下干燥8h，然后将前驱体在空气氛围中200℃下进行预处理一段时间，接着将产物在氮气氛围中500℃下进行炭化处理1h。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同空气与处理时间对苯酚转化率的影响如表5所示。
表5.不同空气预处理时间对苯酚转化率的影响
实施例6
取PVA(聚乙烯醇)20g，在60℃下溶解成透明液体，冷却后在常温下加20g的PdCl2试剂，并匀速搅拌，均匀混合1h后滤出粘稠的前驱体并将其放入培养皿中室温下干燥8h，然后将前驱体在空气氛围中200℃下进行预处理1h，接着将产物在氮气氛围中一定温度下进行炭化处理1h。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同炭化温度对苯酚转化率的影响如表6所示
表6.不同活化温度对苯酚转化率的影响
实施例7
取PVA(聚乙烯醇)20g，在80℃下溶解成透明液体，冷却后在常温下加20g的Ni(NO3)2试剂，并匀速搅拌，均匀混合6h后滤出粘稠的前驱体并将其放入培养皿中室温下干燥8h，然后将前驱体在空气氛围中150度下进行预处理4h，接着将产物在氮气氛围中500℃下炭化处理一段时间。最后粉碎成0.25-0.5mm粒径，将制得的金属基炭催化剂用于催化制氢实验。不同炭化时间对苯酚转化率的影响如表6所示
表6.不同炭化时间对苯酚转化率的影响
图1Ni/PVA金属基炭材料(Ni：PVA为1:1，室温干燥24h；250℃、2h空气预处理，500℃、1h炭化处理)的TEM图，从图中可以看出金属活性物质均匀分布在炭材料上。图2是金属基炭材料空气预处理的TG图。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。
Claims (6)
1.一种新型金属基炭催化剂在有机废水催化降解制氢中的应用，其特征在于所述新型金属基炭催化剂采用以下方法制备得到：
步骤(1)、将聚乙烯醇PVA溶解于水中，溶解过程中加热至60～80℃，时间为1～2h，溶解成透明溶液；将上述溶液冷却至常温后，加入金属盐溶液，匀速搅拌均匀后得到前驱体溶液；所述金属盐为镍盐、铁盐、钯盐中的一种；所述聚乙烯醇PVA与金属盐的质量比为1:(0.5～3)；
步骤(2)、将前驱体溶液在20～100℃下干燥一段时间；
步骤(3)、将步骤(2)干燥后的前驱体置于空气氛围中，在150～250℃温度下预处理1～4h，得到热分解后产物；
步骤(4)、将热分解后产物置于氮气氛围中，在450～600℃下炭化处理0.5～2h，最终制备得到介孔金属基炭材料。
2.如权利要求1所述应用，其特征在于步骤(1)中，所述镍盐采用Ni(NO3)2，所述铁盐采用Fe(NO3)3，所述钯盐采用PdCl2。
3.如权利要求1所述应用，其特征在于步骤(1)中所述搅拌时间为30min～8h。
4.如权利要求3所述应用，其特征在于步骤(1)中所述搅拌时间为30min～2h。
5.如权利要求1所述应用，其特征在于步骤(2)中，干燥时间为4-24h。
6.如权利要求5所述应用，其特征在于步骤(2)中，干燥时间为8-24h。
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