CN111185134B - 一种复合MgO-CdO中温CO2吸附剂及其制备方法 - Google Patents
一种复合MgO-CdO中温CO2吸附剂及其制备方法 Download PDFInfo
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Abstract
本发明为一种复合MgO‑CdO中温CO2吸附剂及制备方法,该吸附剂为[MgxCdy]‑[(LiaNabKc)‑(NadKe)]m。x与y分别为MgO和CdO在MgO‑CdO复合氧化物中所占的摩尔百分比,x为50~90,y为10~50;a,b,c,d,e分别为LiNO3,NaNO3,KNO3,Na2CO3和K2CO3在所有碱金属碳酸盐和硝酸盐中所占的摩尔百分比,a为20~35,b为5~15,c为20~35,d为5~15,e为5~15;m为所有碱金属碳酸盐和硝酸盐与MgO‑CdO复合氧化物的摩尔百分比,m为15~25。本发明制备复合载体MgO‑CdO将五种碱金属盐负载其上,其吸附容量大吸附速率高。
Description
技术领域
本发明涉及一种复合MgO-CdO中温CO2吸附剂及其制备方法,尤其涉及一种用于中温CO2捕集的高性能吸附剂及其制备方法,该吸附剂的一部分是单分散的片状结构复合载体MgO-CdO,另一部分是负载在MgO-CdO上具有特定比例的碱金属盐助剂。
背景技术
众所周知,CO2为温室气体之一,其大量排放会加剧全球气候变暖,引发一系列的自然灾害。在各个领域中,工业与化石燃料燃烧的电力方面所排放的CO2占据了主要地位。因此,如何将工业与燃煤电厂所排放的CO2进行有效捕集成为国内外关注的研究热点。
目前工业CO2捕集最常用的技术主要有胺吸收法、膜分离法、变压吸附法、固体吸附法。其中胺吸收法的工艺技术成熟、操作简单、国内外应用较多,但是此方法的溶剂再生能耗高,且一定程度会腐蚀设备;膜分离法则由于对原料气要求高、分离效率较低、工业放大困难等问题难以实现工业化应用;变压吸附法技术较为成熟,操作过程程序化,但是装置投资成本高,能耗也较大。与前三者相比,固体吸附法对工业中CO2的进行捕集,具有适用范围广、成本低廉、便于自动化操作等优点,具有广阔的应用前景。
针对现有的工业燃煤发电体系,燃煤电厂的CO2捕集主要有三条技术路线,分别为燃烧前捕集、燃烧后捕集和富氧燃烧。其中富氧燃烧是指CO2捕集是在燃料燃烧过程中,以高纯度的氧气代替空气作为助燃剂,以提高烟道尾气中的 CO2浓度,但是此方法由于制氧成本较高而受到限制;燃烧后捕集是指在燃料燃烧后将工业尾气中的CO2分离,但由于尾气中的CO2浓度较低,所以CO2分离成本较高;燃烧前捕集则是在燃料燃烧前将CO2分离,该方法主要应用于整体煤气化联合循环发电系统。与传统煤电技术相比,整体煤气化联合循环发电系统将煤气化和燃气-蒸汽联合循环发电技术有机结合起来,具有发电效率高、污染物排放低,CO2捕集成本低等优势,是目前国际上被验证的、能够工业化的、最具发展前景的清洁高效煤电技术。在该系统中,经煤气化单元产生的合成气通过水气变换反应得到较高浓度的CO2,此时反应器出口的气体通常在250-450℃,若能在此阶段进行CO2捕集,可以降低能耗并提高过程效率。
MgO作为中温CO2固体吸附剂中的代表,其具有理论CO2吸附量高、廉价易得、制备简易、且吸附CO2温度与工业水汽变换气体的出口温度一致等优势,被认为是最具有潜力的燃烧前捕集的固体CO2吸附剂。然而局限于纯MgO的实际低CO2吸附量、较慢的吸附速率、较差的吸附-再生循环稳定性,MgO基吸附剂实际应用受到了很大的限制。因此,为了提升MgO基吸附剂的CO2吸附量、吸附速率与循环稳定性,可以用熔融碱金属硝酸盐与碳酸盐(硝酸锂、硝酸钠、硝酸钾、碳酸钠、碳酸钾)进行修饰促进、掺杂其他组分(氧化镉、氧化钙)等。为此开发出高性能的MgO基吸附剂,从而对CO2进行高效捕集。
发明内容
本发明的目的是制备出一种负载碱金属盐的片状结构复合MgO-CdO中温 CO2吸附剂,且其具有优异的CO2吸附性能。
一种复合MgO-CdO中温CO2吸附剂,其特征在于,所述的吸附剂由五种碱金属盐和具有片状结构MgO-CdO组成,表示如下:
[MgxCdy]-[(LiaNabKc)-(NadKe)]m
[MgxCdy]代表MgO与CdO;(Li,Na,K)代表LiNO3,NaNO3和KNO3;(Na,K) 代表Na2CO3和K2CO3;
x与y分别代表MgO和CdO在MgO-CdO复合氧化物中所占的摩尔百分比, x介于50~90之间,y介于10~50之间;
a,b,c,d,e分别代表LiNO3,NaNO3,KNO3,Na2CO3和K2CO3在所有碱金属碳酸盐和硝酸盐中所占的摩尔百分比,a介于20~35之间,b介于5~15 之间,c介于20~35之间,d介于5~15之间,e介于5~15之间;
m代表所有碱金属碳酸盐和硝酸盐与MgO-CdO复合氧化物的摩尔百分比, m介于15~25之间。
本发明还提供上述吸附剂的制备方法,所述方法包括如下步骤:
(1)分别称量镁盐和镉盐,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清,
其中:所述镁盐为乙酸镁和硝酸镁的一种,镉盐为乙酸镉和硝酸镉的一种,镁盐的摩尔数介于0.01~0.02之间;
(2)分别称量碳酸钠和氢氧化钠,量取100mL去离子水与平均分子量为400 的聚乙二醇即PEG400于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清;
其中:所述碳酸钠的摩尔数介于0.02~0.025之间,碳酸钠和氢氧化钠的摩尔比介于1.5~2之间,PEG400的体积介于5~15mL之间;
(3)将步骤(1)所得的澄清液逐滴加入到步骤(2)的500mL三口烧瓶内的混合溶液内,水浴恒温50℃保持4h后,取出在室温下老化4h;
(4)将步骤(3)所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次;
(5)将步骤(4)所得的白色沉淀物进行放入真空烘箱中,恒温60℃保持12h 后取出研磨,得到的干燥白色固体粉末;
(6)将步骤(5)所得的白色固体粉末进行放入马弗炉中进行煅烧,以5℃/min 的升温速率升到500℃,恒温4h,煅烧后便得到片状结构MgO-CdO;
(7)按所述比例分别称量硝酸锂,硝酸钠,硝酸钾,碳酸钠与碳酸钾,放入 150mL单口烧瓶中,加入60~100mL无水甲醇,超声使碱金属盐完全溶解;
(8)按所述比例称量步骤(6)所得的MgO-CdO,加入步骤(7)的溶液中,磁力搅拌12h;
(9)将步骤(8)所得含MgO-CdO的悬浮液在60℃下进行旋转蒸发,除去甲醇溶剂后制得所述的吸附剂。
有益效果
本方法制备的复合MgO-CdO吸附剂在五种碱金属盐的共同作用下表现出了优异的CO2吸附性能。主要优点在于,其一,本发明制备的负载碱金属盐的复合MgO-CdO吸附剂具有吸附容量大、吸附速率高、制备方法简便等特点;其二,碱金属盐在中温CO2吸附过程中处于熔融态,而复合MgO-CdO所特有的片形结构能够让熔融碱金属盐均匀分布在其表面,从而提升其CO2吸附性能,并能有效地抑制碱金属盐在多次吸附-再生循环中的流动;此外,掺入的CdO能抑制MgO的烧结,从而提升其稳定性;其三,MgO与CdO具有协同效应,掺入的 CdO作为活性组分,也能参与CO2吸附反应,从而进一步提升吸附速率。
附图说明
图1为本发明实施例1中[Mg90Cd10]-[(Li30Na15K30)-(Na10K15)]20的扫描电镜图
图2(a)为本发明实施例1中[Mg90Cd10]-[(Li30Na15K30)-(Na10K15)]20的吸附/再生循环性能图
图2(b)为本发明对比例1中[Mg100]-[(Li30Na15K30)-(Na10K15)]20的吸附/再生循环性能图
吸附条件:350℃,100%CO2,30min;再生条件:400℃,100%N2,10min
图3为本发明实施例1中[Mg90Cd10]-[(Li30Na15K30)-(Na10K15)]20的吸附等温线
吸附条件:275/300/325/350℃,100%CO2,60min
图4为本发明实施例2中[Mg80Cd20]-[(Li35Na10K30)-(Na15K10)]20的吸附/再生循环性能图
吸附条件:350℃,100%CO2,30min;再生条件:400℃,100%N2,10min
图5为本发明实施例3中[Mg50Cd50]-[(Li35Na10K30)-(Na15K10)]25的吸附/再生循环性能图
吸附条件:350℃,100%CO2,30min;再生条件:400℃,100%N2,10min
图6比较本发明实施例1、实施例2、对比例1、对比例2、对比例3的吸附速率
吸附条件:350℃,100%CO2,30min
图7为本发明实施例2与对比例3的XRD图
具体实施方式
本发明具体实施例叙述于下,但本发明不限于此。
实施例1
称量0.018mol四水乙酸镁和0.002mol二水乙酸镉,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水与10mL PEG400于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的乙酸镁与乙酸镉溶液,水浴依旧恒温50℃保持4h后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到片状载体[Mg90Cd10]。称量0.30mmol硝酸锂,0.15mmol硝酸钠,0.30mmol硝酸钾,0.10mmol碳酸钠, 0.15mmol碳酸钾放入250mL单口烧瓶中,加入100mL无水甲醇,超声仪中超声2h,使碱金属盐完全溶解。称量0.244g上述[Mg90Cd10]粉末,加入上述碱金属盐溶液中,磁力搅拌12h。然后将上述含MgO的悬浮液在60℃下真空旋转蒸发,除去甲醇溶剂后得到吸附剂[Mg90Cd10]-[(Li30Na15K30)-(Na10K15)]20,其扫描电镜图如图1所示。
性能测试:在热重分析仪上对所制得的吸附剂进行吸附-再生循环实验,记录10次循环过程的吸附容量。
循环稳定性性能测试方法:
本发明采用热重分析仪测试的吸附剂吸附-再生各个循环的吸附容量。热重分析的条件是:(1)在热天平内装入约5mg吸附剂样品,在N2气氛下以10℃/min 升温至350℃,然后进行CO2吸附,通入的气体为50mL CO2。吸附时间为30min; (2)吸附结束后,切换气体为50mL N2,使体系温度升高到400℃(20℃/min) 进行吸附剂再生,时间10min;(3)再生结束后,以20℃/min的速率将加热炉温度降至350℃,切换气体为50mL CO2进行吸附,如此循环往复则可进行吸附剂的循环稳定性考察,本实例进行了10个循环。实验结果如图2(a)所示。
吸附等温线性能测试方法:
在热天平内装入约5mg吸附剂样品,在N2气氛下以10℃/min升温至 275/300/325/350℃,然后进行CO2吸附,通入的气体为50mL CO2,吸附时间为 60min。实验结果如图3所示。
根据实验过程中记录的吸附剂质量变化数据,计算吸附剂的吸附容量,其定义如下:
实施例2
称量0.016mol六水硝酸镁和0.004mol四水硝酸镉,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水与12mL PEG400于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的硝酸镁与硝酸镉溶液,水浴依旧恒温50℃保持4h后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到纳米片状[Mg80Cd20]。称量0.35mmol硝酸锂,0.10mmol硝酸钠,0.3mmol硝酸钾,0.15mmol碳酸钠, 0.10mmol碳酸钾放入250mL单口烧瓶中,加入100mL无水甲醇,超声仪中超声2h,使碱金属盐完全溶解。称量0.288g上述[Mg80Cd20]粉末,加入上述碱金属盐溶液中,磁力搅拌12h。然后将上述含MgO的悬浮液在60℃下真空旋转蒸发,除去甲醇溶剂后得到吸附剂[Mg80Cd20]-[(Li35Na10K30)-(Na15K10)]20,其XRD 谱图如图7所示。
性能测试:在热重分析仪上对所制得的吸附剂进行吸附-再生循环实验,记录10次循环过程的吸附容量。实验结果如图4所示。吸附温度为350℃,时间为30min,50mL CO2;再生温度为400℃,时间为10min,50mL N2;
实施例3
称量0.010mol四水乙酸镁和0.010mol二水乙酸镉,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水与10mL PEG400于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的乙酸镁与乙酸镁溶液,水浴依旧恒温50℃保持4h后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到纳米片状[Mg50Cd50]。称量0.35mmol硝酸锂,0.10mmol硝酸钠,0.3mmol硝酸钾,0.15mmol碳酸钠,0.10mmol碳酸钾放入250mL单口烧瓶中,加入100mL无水甲醇,超声仪中超声2h,使碱金属盐完全溶解。称量0.336g上述[Mg50Cd50]粉末,加入上述碱金属盐溶液中,磁力搅拌12h。然后将上述含MgO的悬浮液在60℃下真空旋转蒸发,除去甲醇溶剂后得到吸附剂[Mg50Cd50]-[(Li35Na10K30)-(Na15K10)]25。
性能测试:在热重分析仪上对所制得的吸附剂进行吸附-再生循环实验,记录10次循环过程的吸附容量。实验结果如图5所示。吸附温度为350℃,时间为30min,50mL CO2;再生温度为400℃,时间为10min,50mL N2;
对比例1
称量0.02mol四水乙酸镁,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的乙酸镁与乙酸镁溶液,水浴依旧恒温50℃保持4h 后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到MgO。称量0.30mmol硝酸锂,0.15mmol硝酸钠,0.30mmol 硝酸钾,0.10mmol碳酸钠,0.15mmol碳酸钾放入250mL单口烧瓶中,加入100mL 无水甲醇,超声仪中超声2h,使碱金属盐完全溶解。称量0.200g上述MgO粉末,加入上述碱金属盐溶液中,磁力搅拌12h。然后将上述含MgO的悬浮液在 60℃下真空旋转蒸发,得到吸附剂[Mg100]-[(Li30Na15K30)-(Na10K15)]20。
性能测试:在热重分析仪上对所制得的吸附剂进行吸附-再生循环实验,记录10次循环过程的吸附容量。实验结果如图2(b)所示。吸附化温度为350℃,时间为30min,50mLCO2;再生温度为400℃,时间为10min,50mL N2;
对比例2
称量0.02mol二水乙酸镉,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的乙酸镁与乙酸镁溶液,水浴依旧恒温50℃保持4h 后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到CdO。称量0.3mmol硝酸锂,0.15mmol硝酸钠,0.3mmol 硝酸钾,0.10mmol碳酸钠,0.15mmol碳酸钾放入250mL单口烧瓶中,加入100mL 无水甲醇,超声仪中超声2h,使碱金属盐完全溶解。称量0.200g上述CdO粉末,加入上述碱金属盐溶液中,磁力搅拌12h。然后将上述含MgO的悬浮液在60℃下真空旋转蒸发,得到吸附剂[Cd100]-[(Li30Na15K30)-(Na10K15)]20。
对比例3
称量0.016mol六水硝酸镁和0.004mol四水硝酸镉,溶于100mL去离子水中,磁力搅拌约20min至溶液透明澄清。然后称量0.024mol碳酸钠和0.012mol氢氧化钠,量取100mL去离子水与12mL PEG400于500mL三口烧瓶内,在50℃水浴下搅拌10min至溶液透明澄清,在搅拌条件下,逐滴加入上述的乙酸镁与乙酸镁溶液,水浴依旧恒温50℃保持4h后,取出在室温下老化4h。将所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次后,放入真空烘箱中,恒温60℃保持12h后取出研磨,得到的干燥白色固体粉末放进马弗炉中,以5℃/min的升温速率升到500℃,恒温4h,煅烧后便得到纳米片状[Mg80Cd20]。
由上述附图和实例可见,相比于纯MgO负载碱金属盐后所制备的吸附剂(对比例1),复合MgO-CdO负载碱金属盐后所制备的吸附剂(实施例1)具有较高的吸附速率和循环稳定性,10次循环后稳定在0.4克CO2/克吸附剂;纯CdO负载碱金属盐后所制备的吸附剂(对比例2),对于CO2吸附也显示出一定的活性;相比于复合MgO-CdO所制备的吸附剂(对比例3),复合MgO/CdO负载碱金属盐后所制备的吸附剂(实施例1和实施例2)具有较高的CO2吸附容量和吸附速率。本发明是一种中温CO2吸附容量和吸附速率较高,吸附-再生循环稳定性良好的吸附剂。
Claims (2)
1.一种复合MgO-CdO中温CO2吸附剂,其特征在于,所述的吸附剂由五种碱金属盐和具有片状结构MgO-CdO组成,表示如下:
[MgxCdy]-[(LiaNabKc)-(NadKe)]m
[MgxCdy]代表MgO与CdO;(Li,Na,K)代表LiNO3,NaNO3和KNO3;(Na,K)代表Na2CO3和K2CO3;
x与y分别代表MgO和CdO在MgO-CdO复合氧化物中所占的摩尔百分比,x介于50~90之间,y介于10~50之间;
a,b,c,d,e分别代表LiNO3,NaNO3,KNO3,Na2CO3和K2CO3在所有碱金属碳酸盐和硝酸盐中所占的摩尔百分比,a介于20~35之间,b介于5~15之间,c介于20~35之间,d介于5~15之间,e介于5~15之间;
m代表所有碱金属碳酸盐和硝酸盐与MgO-CdO复合氧化物的摩尔百分比,m介于15~25之间。
2.如权利要求1所述的复合MgO-CdO中温CO2吸附剂的制备方法,其特征在于,所述方法包括如下步骤:
(1)分别称量镁盐和镉盐,溶于100mL去离子水中,磁力搅拌20min至溶液透明澄清,
其中:所述镁盐为乙酸镁和硝酸镁的一种,镉盐为乙酸镉和硝酸镉的一种,镁盐的摩尔数介于0.01~0.02之间;
(2)分别称量碳酸钠和氢氧化钠,量取100mL去离子水与平均分子量为400的聚乙二醇即PEG400于500mL三口烧瓶内,在50 °C水浴下搅拌10min至溶液透明澄清;
其中:所述碳酸钠的摩尔数介于0.02~0.025之间,碳酸钠和氢氧化钠的摩尔比介于1.5~2之间,PEG400的体积介于5~15mL之间;
(3)将步骤(1)所得的澄清液逐滴加入到步骤(2)的500mL三口烧瓶内的混合溶液内,水浴恒温50 °C保持4h后,取出在室温下老化4h;
(4)将步骤(3)所得的液固混合物进行抽滤分离,并分别用水和乙醇洗涤白色沉淀物两次;
(5)将步骤(4)所得的白色沉淀物进行放入真空烘箱中,恒温60 °C保持12h后取出研磨,得到的干燥白色固体粉末;
(6)将步骤(5)所得的白色固体粉末进行放入马弗炉中进行煅烧,以5 °C /min的升温速率升到500 °C,恒温4h,煅烧后便得到片状结构MgO-CdO;
(7)按比例分别称量硝酸锂,硝酸钠,硝酸钾,碳酸钠与碳酸钾,放入150 mL单口烧瓶中,加入60~100mL无水甲醇,超声使碱金属盐完全溶解;
(8)按比例称量步骤(6)所得的MgO-CdO,加入步骤(7)的溶液中,磁力搅拌12h;
(9)将步骤(8)所得含MgO-CdO的悬浮液在60 °C下进行旋转蒸发,除去甲醇溶剂后制得所述的吸附剂。
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