CN114772552A - 一种化学链甲烷重整制氢的结构化氧载体及制备方法 - Google Patents
一种化学链甲烷重整制氢的结构化氧载体及制备方法 Download PDFInfo
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Abstract
本发明涉及一种化学链甲烷重整制氢的结构化氧载体的制备方法,包括步骤:配置含有Ba离子、Sr离子和Co离子的硝酸盐溶液,再向得到的混合溶液中加入柠檬酸和乙二胺四乙酸,进行混合;将设定颗粒粒径的CeO2粉末加入制得的前驱体混合溶液中,在搅拌的条件下将加入CeO2粉末的前驱体混合溶液升温至设定温度,持续加热蒸发,直至形成溶胶状产物。本发明的有益效果是:对结构化氧载体活性组分的制备和涂敷方式进行了研究,对蜂窝载体材料进行调整,实现了感应加热下高效稳定的化学链甲烷重整制氢反应;采取的感应加热方式提升了反应过程响应速度和能源利用率,同时氧载体具备稳定性强、耐热冲击性好的优点;而且氧载体活性组分反应活性好、不易脱落。
Description
技术领域
本发明属于能源化工装置领域,尤其涉及一种用于感应加热条件下化学链甲烷重整制氢的结构化氧载体及制备方法。
背景技术
中国正在进行从高碳到低碳再到零碳的能源结构转型。在这一背景下,能源结构改革和低碳可再生能源的发展成为了必然的趋势。化石能源由于处于全球能源消费的主体地位,还将在很长一段时间作为全社会的主要能源,并且近年来天然气的占比还在逐步增加。如果能够将天然气转化为零碳能源和化学品,不但能够减少社会的碳排放量,还能够同时提供化工原料。因此在化石能源清洁转化领域,利用天然气制备氢气和合成气的新型工艺是一个热门领域。
为解决传统甲烷重整工艺的缺点,研究者们引入化学链(Chemical looping)的概念,设计了化学链甲烷蒸汽重整(Chemical~Lopping Steam Methane Reforming,简称CL-SMR)工艺。在CL-SMR反应循环中,氧载体首先在燃料反应器内对甲烷进行选择性氧化反应,生成合成气,随后进入水蒸气反应器反应,生成纯氢产物,反应后进入空气反应器中经过煅烧完全恢复晶格氧,氧载体随后可进行下一次循环反应。相比传统的甲烷重整工艺,CL-SMR工艺中氧载体替代氧气与甲烷反应能够减少制备纯氧的高成本,反应工艺的能耗较低,实现了合成气和氢气联产,而且合成气H2/CO=2,更适合下游的F-T合成工艺。由于CL-SMR工艺中不同反应阶段的氧化还原条件不同,对于氧载体的反应活性、反应选择性、热稳定性等因素有很高的要求。
目前钙钛矿氧载体材料具有较好的反应选择性和反应活性,但是钙钛矿氧载体存在着强度偏低的缺点,反应过程中的热交换会对氧载体带来明显的热冲击,气流冲刷也会带来损耗。通过将氧载体活性组分负载于具有较高热稳定性和比热容的蜂窝陶瓷上,能够减少局部过热现象,而且流道结构能够改善气固接触效果并减少床层压降,通过在蜂窝陶瓷内引入铁磁材料,还能够通过感应加热的方式提高氧载体的温度响应速度、降低加热能耗。而如何制备这种具有蜂窝孔道的结构化氧载体,正成为CL-SMR工艺在工业中规模化应用亟需解决的技术问题。
发明内容
本发明的目的是克服现有技术中的不足,提供一种化学链甲烷重整制氢的结构化氧载体及制备方法。
一种化学链甲烷重整制氢的结构化氧载体,包括蜂窝载体和氧载体活性组分,氧载体活性组分负载质量分数为10%~30%,其余为蜂窝载体;蜂窝载体含有氧化铝、氧化硅和铁磁性材料,质量分数分别为30%~35%、40%~55%、10%~30%;氧载体活性组分包含钙钛矿型氧化物和CeO2活性组分,钙钛矿型氧化物为Ba-Sr-Co基钙钛矿,CeO2为100~150目颗粒粒径的氧化铈,钙钛矿型氧化物和CeO2质量分数分别为10%~40%、60%~90%。
这种化学链甲烷重整制氢的结构化氧载体的制备方法,包括以下步骤:
步骤1、配置含有Ba离子、Sr离子和Co离子的硝酸盐溶液,再向得到的混合溶液中加入柠檬酸和乙二胺四乙酸,进行混合;调节混合溶液的pH值至设定范围,得到钙钛矿氧载体活性组分的前驱体混合溶液;
步骤2、将设定颗粒粒径的CeO2粉末加入步骤1制得的前驱体混合溶液中,在搅拌的条件下将加入CeO2粉末的前驱体混合溶液升温至设定温度,持续加热蒸发,直至形成溶胶状产物;
步骤3、将步骤2所得溶胶状产物在设定温度下烘干,然后进行升温煅烧处理:先升温至一设定温度,恒温下煅烧设定时长后,继续升温至另一设定温度,恒温下煅烧设定时长后,自然冷却;使用无水乙醇作为分散剂,对冷却后的煅烧产物进行设定时长的湿式球磨处理;球磨后取出并烘干,获得氧载体活性组分;
步骤4、制备带有铁磁性材料的堇青石蜂窝载体,然后使用草酸进行浸泡清洗处理;
步骤5、将氧载体活性组分、中性硅溶胶、羟丙甲基纤维素、甘油和水按设定质量比例混合制备成涂敷浆料;氧载体活性组分由步骤3制得;随后以负压抽吸和正压吹扫的方式对堇青石蜂窝载体孔道进行涂敷,将涂敷后的样品在设定温度下进行烘干处理;随后在空气气氛下以设定升温速率从常温升温至目标温度,恒温下煅烧设定时长;然后冷却得到结构化氧载体。
作为优选,步骤1中硝酸盐溶液里Ba离子浓度为0.03~0.05mol/L,Sr离子浓度0.05~0.07mol/L,Co离子浓度为0.1mol/L,柠檬酸和乙二胺四乙酸的浓度分别为0.3mol/L和0.2mol/L;加入柠檬酸和乙二胺四乙酸后,调节混合溶液的pH值至8~9。
作为优选,步骤2中CeO2粉末的颗粒粒径为100~150目;在搅拌条件下将加入CeO2粉末的前驱体混合溶液升温至70~85℃;CeO2在前驱体混合溶液中的添加量为0.3mol/L。
作为优选,步骤3中溶胶状产物的烘干温度为105℃~130℃。
作为优选,步骤3中进行煅烧处理时,首先以10℃/分钟升温至400℃,恒温下煅烧30分钟,随后以10℃/分钟升温至850℃,恒温下煅烧1小时后自然冷却。
作为优选,步骤4中铁磁性材料为Al-Ni-Co合金,Al-Ni-Co合金的质量分数为10%~30%;堇青石蜂窝载体中SiO2的质量分数为40%~55%,Al2O3的质量分数为30%~35%;使用草酸进行浸泡清洗处理时:草酸浓度为5mol/L,浸泡处理温度为70℃,浸泡处理时长为6小时。
作为优选,步骤5的涂敷浆料中,氧载体活性组分的质量分数为10~20%、中性硅溶胶的质量分数为1~3%、羟丙甲基纤维素的质量分数为0.2~0.4%、甘油的质量分数为0.5~1%,其余为水。
作为优选,步骤5中将涂覆样品烘干后,在空气气氛下以10℃/分钟从常温升温至850℃,恒温煅烧60分钟后冷却。
本发明的有益效果是:
本发明对结构化氧载体活性组分的制备和涂敷方式进行了研究,对蜂窝载体材料进行调整,实现了感应加热下高效稳定的化学链甲烷重整制氢反应,本发明采取的感应加热方式提升了反应过程响应速度和能源利用率,同时氧载体具备稳定性强、耐热冲击性好的优点;而且氧载体活性组分反应活性好、不易脱落。
附图说明
图1为本发明构建的氧载体的制备工艺流程图。
具体实施方式
下面结合实施例对本发明做进一步描述。下述实施例的说明只是用于帮助理解本发明。应当指出,对于本技术领域的普通人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
实施例一
本申请实施例一提供了一种化学链甲烷重整制氢的结构化氧载体,包括蜂窝载体和氧载体活性组分,氧载体活性组分负载质量分数为10%~30%,其余为蜂窝载体;蜂窝载体含有氧化铝、氧化硅和铁磁性材料,质量分数分别为30%~35%、40%~55%、10%~30%;氧载体活性组分包含钙钛矿型氧化物和CeO2活性组分,钙钛矿型氧化物为Ba-Sr-Co基钙钛矿,CeO2为100~150目颗粒粒径的氧化铈,钙钛矿型氧化物和CeO2质量分数分别为10%~40%、60%~90%。
实施例二
在实施例一的基础上,本申请实施例二提供了一种如图1所示化学链甲烷重整制氢的结构化氧载体的制备方法,包括以下步骤:
(1)配置Ba、Sr、Co硝酸盐混合溶液,Ba、Sr、Co的摩尔浓度为0.03mol/L、0.07mol/L、0.1mol/L,然后向该硝酸盐溶液中添加适当的柠檬酸和乙二胺四乙酸,使混合溶液内柠檬酸和乙二胺四乙酸的浓度分别为0.3mol/L和0.2mol/L,随后添加氨水使得该混合溶液的pH值为8~9;
(2)以51.6g/L的比例将颗粒粒径为100-150目的CeO2粉末加入混合溶液中,在搅拌的条件下将混合液升温至约85℃,持续加热蒸发直至形成溶胶状产物;
(3)将形成的溶胶产物在105℃的温度下烘干形成凝胶,随后以10℃/min的升温速率在空气气氛下升温至400℃,恒温30min进行煅烧,随后继续以10℃/min升温速率在空气气氛下升温至850℃,恒温1h后自然冷却。对冷却后的煅烧产物进行湿式球磨处理,分散剂使用无水乙醇,球磨5小时后取出并烘干样品,获得氧载体活性组分。
(4)制备带有铁磁材料成分的堇青石蜂窝载体,控制Al-Ni-Co合金质量分数为20%,SiO2质量分数为:50%、Al2O3质量分数控制为:30%,使用草酸进行浸泡清洗处理,草酸浓度为5mol/L,处理温度为70℃,处理时间为6小时。
按质量百分比20%、2%、0.25%、0.5%、77.25%的比例将氧载体活性组分、中性硅溶胶、羟丙甲基纤维素、甘油、水混合制备成涂敷浆料,随后以负压抽吸和正压吹扫的方法对蜂窝载体孔道进行涂敷,涂敷后样品在105℃进行烘干处理,随后在空气气氛下以10℃/min的升温速率从常温升温到850℃煅烧处理,冷却后即获得所需结构化氧载体。
Claims (9)
1.一种化学链甲烷重整制氢的结构化氧载体,其特征在于:包括蜂窝载体和氧载体活性组分,氧载体活性组分负载质量分数为10%~30%,其余为蜂窝载体;蜂窝载体含有氧化铝、氧化硅和铁磁性材料,质量分数分别为30%~35%、40%~55%、10%~30%;氧载体活性组分包含钙钛矿型氧化物和CeO2活性组分,钙钛矿型氧化物为Ba-Sr-Co基钙钛矿,CeO2为100~150目颗粒粒径的氧化铈,钙钛矿型氧化物和CeO2质量分数分别为10%~40%、60%~90%。
2.一种如权利要求1所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于,包括以下步骤:
步骤1、配置含有Ba离子、Sr离子和Co离子的硝酸盐溶液,再向得到的混合溶液中加入柠檬酸和乙二胺四乙酸,进行混合;调节混合溶液的pH值至设定范围,得到钙钛矿氧载体活性组分的前驱体混合溶液;
步骤2、将设定颗粒粒径的CeO2粉末加入步骤1制得的前驱体混合溶液中,在搅拌的条件下将加入CeO2粉末的前驱体混合溶液升温至设定温度,持续加热蒸发,直至形成溶胶状产物;
步骤3、将步骤2所得溶胶状产物在设定温度下烘干,然后进行升温煅烧处理:先升温至一设定温度,恒温下煅烧设定时长后,继续升温至另一设定温度,恒温下煅烧设定时长后,自然冷却;使用无水乙醇作为分散剂,对冷却后的煅烧产物进行设定时长的湿式球磨处理;球磨后取出并烘干,获得氧载体活性组分;
步骤4、制备带有铁磁性材料的堇青石蜂窝载体,然后使用草酸进行浸泡清洗处理;
步骤5、将氧载体活性组分、中性硅溶胶、羟丙甲基纤维素、甘油和水按设定质量比例混合制备成涂敷浆料;氧载体活性组分由步骤3制得;随后以负压抽吸和正压吹扫的方式对堇青石蜂窝载体孔道进行涂敷,将涂敷后的样品在设定温度下进行烘干处理;随后在空气气氛下以设定升温速率从常温升温至目标温度,恒温下煅烧设定时长;然后冷却得到结构化氧载体。
3.根据权利要求2所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤1中硝酸盐溶液里Ba离子浓度为0.03~0.05mol/L,Sr离子浓度0.05~0.07mol/L,Co离子浓度为0.1mol/L,柠檬酸和乙二胺四乙酸的浓度分别为0.3mol/L和0.2mol/L;加入柠檬酸和乙二胺四乙酸后,调节混合溶液的pH值至8~9。
4.根据权利要求2所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤2中CeO2粉末的颗粒粒径为100~150目;在搅拌条件下将加入CeO2粉末的前驱体混合溶液升温至70~85℃;CeO2在前驱体混合溶液中的添加量为0.3mol/L。
5.根据权利要求2所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤3中溶胶状产物的烘干温度为105℃~130℃。
6.根据权利要求5所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤3中进行煅烧处理时,首先以10℃/分钟升温至400℃,恒温下煅烧30分钟,随后以10℃/分钟升温至850℃,恒温下煅烧1小时后自然冷却。
7.根据权利要求1所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤4中铁磁性材料为Al-Ni-Co合金,Al-Ni-Co合金的质量分数为10%~30%;堇青石蜂窝载体中SiO2的质量分数为40%~55%,Al2O3的质量分数为30%~35%;使用草酸进行浸泡清洗处理时:草酸浓度为5mol/L,浸泡处理温度为70℃,浸泡处理时长为6小时。
8.根据权利要求1所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤5的涂敷浆料中,氧载体活性组分的质量分数为10~20%、中性硅溶胶的质量分数为1~3%、羟丙甲基纤维素的质量分数为0.2~0.4%、甘油的质量分数为0.5~1%,其余为水。
9.根据权利要求8所述化学链甲烷重整制氢的结构化氧载体的制备方法,其特征在于:步骤5中将涂覆样品烘干后,在空气气氛下以10℃/分钟从常温升温至850℃,恒温煅烧60分钟后冷却。
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