CN108557760A - 利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法 - Google Patents
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Abstract
利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，利用纳米CaCO3浸渍Ni2(NO)3溶液负载Ni2+，再在氢气气氛下高温加热纳米碳酸钙使其分解，同时使Ni2+还原成Ni0，得到负载Ni0的纳米CaO，用于催化生物质/塑料共气化过程以提高生物质/塑料共气化H2产率并减少结焦；生物质/塑料于650℃共气化时纳米CaO通过反应CaO+CO2→CaCO3实时吸附气体中CO2，促使生物质/塑料共气化制氢反应平衡向右移动，从而提高气相产物中H2含量；共气化完成后的负载Ni的CaCO3在850℃及H2气氛中加热再生，重新得到负载Ni0的纳米CaO(Ni‑CaO)，从而有效提高原料利用率。
Description
技术领域
本发明涉及新能源技术领域，尤其涉及一种利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法。
背景技术
农林生产加工废弃的生物质(如木屑、秸杆等)及工业生产废弃的塑料(如聚乙烯、聚丙烯等)来源极为丰富，而此类生物质和废塑料也是城市垃圾的主要组成部分，通常采用填埋、焚烧等方法处理废弃的生物质及塑料不仅占用大量的土地，同时也带来较严重的环境污染。利用气化将废弃生物质及塑料转化为高附加值燃气或富氢合成气是极为有效的处理方法，但生物质气化时所得气体热值较低，塑料分解温度高，气化时易结焦；利用生物质/塑料共气化技术使生物质与塑料同时转化，可得到具有高热值气体，同时有效减少气化结焦，因此成为具有良好应用前景的新技术。
生物质/塑料共气化所得产物气体主要成分包括H2、CH4、CO和CO2，利用Ni催化剂催化生物质/塑料共气化过程可得到高含氢量的富氢合成气，富氢合成气可用于F-T合成制备烃类燃料，也可用于生产醇类等化学品。
目前用于生物质/塑料共气化制氢的Ni催化剂通常利用氧化铝为催化剂载体，但此类Ni催化剂成本较高，且在气化时易于积碳结焦，进而导致Ni催化剂失活，从而影响其催化效果，也由此降低了生物质/塑料共气化制备H2的产率。
发明内容
本发明所解决的技术问题在于提供一种利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，以解决上述背景技术中的缺点。
本发明所解决的技术问题采用以下技术方案来实现：
利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，具体步骤如下：
(1)制备负载Ni0的纳米氧化钙
1)将适量纳米CaCO3加至Ni2(NO)3溶液中，于室温下充分搅拌12h混匀得固相产物，而后将固相产物过滤分离，于110℃条件下真空干燥后，再进一步研磨分散，得负载Ni2+的纳米氧化钙；
2)将步骤1)制备的负载Ni2+的纳米氧化钙置于高温炉中，在氢气气氛下高温加热，促使纳米碳酸钙分解成CaO，同时使Ni2+还原成Ni0，得负载Ni0的纳米氧化钙；
(2)将干生物质粉末、塑料粉末及步骤2)制备的负载Ni0的纳米氧化钙按照一定质量比充分混匀后，加至管式反应器中，通N2载气吹扫30min；
(3)利用电加热将管式反应器加热至650℃，以N2为载气，使生物质/塑料在650℃下共气化，而后收集气相产物。
在本发明中，步骤1)中，Ni2(NO)3溶液浓度为1mol/L。
在本发明中，步骤2)中，在氢气气氛下对负载Ni2+的纳米氧化钙加热温度为850℃。
在本发明中，步骤(2)中，干生物质粉末与塑料粉末的质量比为5:1，干生物质粉末与负载Ni0的纳米氧化钙的质量比为5:0.5～2。
在本发明中，步骤(2)中，通N2载气的速度为50mL/min。
在本发明中，待步骤(3)的生物质/塑料共气化完成后，利用N2载气继续吹扫30min，通N2载气的速度为50mL/min。
有益效果：
1)本发明利用纳米碳酸钙浸渍Ni2(NO)3溶液以负载Ni2+，再在氢气气氛下高温加热纳米碳酸钙使其分解，同时利用氢气气氛使Ni2+还原成Ni0纳米晶，得负载Ni0的纳米CaO，用于催化生物质/塑料共气化过程，由此降低催化剂成本(氧化钙价格低于氧化铝载体)、提高H2产率并减少催化剂结焦和失活；
2)本发明中生物质/塑料于650℃共气化时，纳米CaO通过反应CaO+CO2→CaCO3实时吸附气体中CO2，以促使生物质/塑料共气化制氢反应平衡向右移动，从而进一步提高气相产物(富氢合成气)中H2含量；
3)本发明中共气化完成后的负载Ni2+的CaCO3在850℃及H2气氛中加热再生，促使纳米碳酸钙分解，重新得到负载Ni0的纳米CaO(Ni-CaO)，因此可有效提高原料利用率。
附图说明
图1为本发明的最佳实施例的制氢示意图。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体图示，进一步阐述本发明。
实施例1(按Ni–CaO/生物质质量比为10％实施)
利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，具体步骤如下：
(1)制备负载Ni0的纳米CaO(简称Ni-CaO)
1)将5.0g纳米CaCO3加至1mol/L的Ni2(NO)3溶液中，于室温下充分搅拌12h混匀得固相产物，而后将固相产物过滤分离，于110℃条件下真空干燥12h后，再进一步研磨分散，得负载Ni2+的纳米氧化钙(简称Ni2+-CaCO3，Ni2+负载量约105mg Ni/g CaCO3)；
2)将步骤1)制备的Ni2+-CaCO3置于高温炉中，在氢气气氛下高温(850℃)加热，促使纳米碳酸钙分解成CaO，同时使Ni2+还原成Ni0，得负载Ni0的纳米CaO(Ni-CaO)；
(2)将5.0g干生物质(松木屑)粉末、1.0g塑料(低密度聚乙烯)粉末、及0.5g Ni-CaO(Ni–CaO/生物质质量比10％)充分混匀后，加至管式反应器中，通N2载气(50mL/min)吹扫30min；
(3)在利用电加热将管式反应器加热至650℃，以N2为载气，使生物质/塑料在650℃下共气化，收集气相产物，利用气相色谱测定气体中氢含量；
(4)待生物质/塑料共气化完成后(共气化约需30min完成)，利用N2载气(50mL/min)继续吹扫30min，气化结束；在共气化完成后继续吹扫N2，使管式反应器在惰性气氛中冷却，用于防止生物质焦接触空气燃烧进而发生危险。
实验结果表明，在气化温度650℃、气化时间30min、生物质/塑料质量比5：1、Ni–CaO/生物质质量比为10％条件下，气相中H2含量为41％(体积分率)。
实施例2(按Ni–CaO/生物质质量比为20％实施)
利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，具体步骤如下：
(1)负载Ni0的纳米氧化钙(简称Ni-CaO)制备
1)将5.0g纳米CaCO3加至1mol/L的Ni2(NO)3溶液中，于室温下充分搅拌12h混匀得固相产物，而后将固相产物过滤分离，于110℃条件下真空干燥12h后，再进一步研磨分散，得负载Ni2+的纳米氧化钙(简称Ni2+-CaCO3，Ni2+负载量约105mg Ni/g CaCO3)；
2)将步骤1)制备的Ni2+-CaCO3置于高温炉中，在氢气气氛下高温(850℃)加热，促使纳米碳酸钙分解成CaO，同时使Ni2+还原成Ni0，得负载Ni0的纳米CaO(Ni-CaO)；
(2)将5.0g干生物质(松木屑)粉末、1.0g塑料(低密度聚乙烯)粉末、以及1.0g Ni-CaO(Ni–CaO/生物质质量比20％)充分混匀后，加至管式反应器中，通N2载气(50mL/min)吹扫30min；
(3)在利用电加热将管式反应器加热至650℃，以N2为载气，使生物质/塑料在650℃下共气化，收集气相产物，利用气相色谱测定气体中氢含量；
(4)待生物质/塑料共气化完成后(共气化约需30min完成)，利用N2载气(50mL/min)继续吹扫30min，气化结束。
实验结果表明，在气化温度650℃、气化时间30min、生物质/塑料质量比5：1、Ni–CaO/生物质质量比为20％条件下，气相中H2含量为53％(体积分率)。
实施例3(按Ni–CaO/生物质质量比为30％实施)
利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，具体步骤如下：
(1)负载Ni0的纳米氧化钙(简称Ni-CaO)制备
1)将5.0g纳米CaCO3加至1mol/L的Ni2(NO)3溶液中，于室温下充分搅拌12h混匀得固相产物，而后将固相产物过滤分离，于110℃条件下真空干燥12h后，再进一步研磨分散，得负载Ni2+的纳米氧化钙(简称Ni2+-CaCO3，Ni2+负载量约105mg Ni/g CaCO3)；
2)将步骤1)制备的Ni2+-CaCO3置于高温炉中，在氢气气氛下高温(850℃)加热，促使纳米碳酸钙分解成CaO，同时使Ni2+还原成Ni0，得负载Ni0的纳米CaO(Ni-CaO)；
(2)将5.0g干生物质(松木屑)粉末、1.0g塑料(低密度聚乙烯)粉末、以及1.5g的Ni-CaO(Ni–CaO/生物质质量比为30％)充分混匀后，加至管式反应器中，通N2载气(50mL/min)吹扫30min；
(3)在利用电加热将管式反应器加热至650℃，以N2为载气，使生物质/塑料在650℃下共气化，收集气相产物，利用气相色谱测定气体中氢含量；
(4)待生物质/塑料共气化完成后(共气化约需30min完成)，利用N2载气(50mL/min)继续吹扫30min，气化结束。
实验结果表明，在气化温度650℃、气化时间30min、生物质/塑料质量比5：1、Ni–CaO/生物质质量比30％条件下，气相中H2含量达61％(体积分率)。
通过对实施例1～实施例3制备的气相产物测试可知：Ni–CaO/生物质质量比为30％时，气相产物中H2含量最高，达61％(体积分率)；进一步实验结果表明，适当增加Ni–CaO，有利于提高生物质/塑料共气化H2含量，但当进一步增加Ni–CaO/生物质质量比(如40％)，此时H2含量为64％(体积分率)，说明再增加Ni–CaO用量对H2含量提高幅度影响不大。
以上显示和描述了本发明的基本原理、主要特征和主要优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (7)
1.利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，具体步骤如下：
(1)制备负载Ni0的纳米氧化钙
1)将适量纳米CaCO3加至Ni2(NO)3溶液中，于室温下充分搅拌12h混匀得固相产物，而后将固相产物过滤分离，于110℃条件下真空干燥后，再进一步研磨分散，得负载Ni2+的纳米氧化钙；
2)将步骤1)制备的负载Ni2+的纳米氧化钙置于高温炉中，在氢气气氛下高温加热，促使纳米碳酸钙分解成CaO，同时使Ni2+还原成Ni0，得负载Ni0的纳米氧化钙；
(2)将干生物质粉末、塑料粉末及步骤2)制备的负载Ni0的纳米氧化钙按照一定质量比充分混匀后，加至管式反应器中，通N2载气吹扫30min；
(3)利用电加热将管式反应器加热至650℃，以N2为载气，使生物质/塑料在650℃下共气化，而后收集气相产物。
2.根据权利要求1所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，步骤1)中，Ni2(NO)3溶液浓度为1mol/L。
3.根据权利要求1所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，步骤2)中，在氢气气氛下对负载Ni2+的纳米氧化钙加热温度为850℃。
4.根据权利要求1所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，步骤(2)中，干生物质粉末与塑料粉末的质量比为5:1，干生物质粉末与负载Ni0的纳米氧化钙的质量比为5:0.5～2。
5.根据权利要求4所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，干生物质粉末与负载Ni0的纳米氧化钙的最佳质量比为5:1.5。
6.根据权利要求1所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，步骤(2)中，通N2载气的速度为50mL/min。
7.根据权利要求1所述的利用纳米氧化钙负载Ni0催化生物质/塑料共气化制氢的方法，其特征在于，待步骤(3)的生物质/塑料共气化完成后，利用N2载气继续吹扫30min，通N2载气的速度为50mL/min。
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