CN106984267A - 一种吸附co2的氮掺杂炭吸附剂的制备方法 - Google Patents
一种吸附co2的氮掺杂炭吸附剂的制备方法 Download PDFInfo
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Abstract
一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：以速生杨木树皮为原料，含氮化合物为氮源，纯水为溶剂，高温高压水热条件处理后，离心、分离得到深棕色固体产物，将棕色固体产物用蒸馏水、无水乙醇洗涤数次至滤液澄清，80℃烘干后在氮气保护下高温煅烧，得到氮掺杂的微孔结构发达的吸附剂，对气体CO2有较高的吸附容量。本操作工艺的主要特点是林木废弃物树皮为原料，环保廉价易得，水为溶剂，含氮化合物为氮源，惰性气体保护下经高温煅烧能够得到较高的比表面积和发达的微孔结构，利于对CO2气体的吸附作用。通过调控水热制备条件，氮源掺杂比例，高温炭化参数可以控制制备吸附剂的表面官能团组成和孔尺寸分布，得到吸附性能优异的吸附剂。本法采用的水热反应操作过程简单，成本低廉，微孔结构发达且可控，具有优良的吸附效果。
Description
所属技术领域：
本发明涉及纳米材料制备领域，特别是涉及一种吸附CO2的氮掺杂炭吸附剂的制备方法
背景技术：
CO2，N2O和CH4是影响温室效应的主要有害气体，然而近些年这些气体的排放量与日俱增，将会引起明显的气候变化，包括全球温度升高，海平面上升，厄尔尼诺现象。其中化石燃料燃烧生成的CO2是主要的有害气体，占到了百分之五十，在找到合适的可再生替代能源之前，对CO2气体进行有效捕获以减少排放很有必要。常用的有效CO2捕获方法包括化学吸附，强碱中和，低温存储等等，但是所用设备和化学试剂成本高，不可再生甚至有毒等限制了实际应用。使用多孔的固体吸附剂进行的物理吸附提供了一种有效的吸附CO2方式，CO2分子与多孔结构之间强烈的相互作用能有效增强选择性吸附和吸附容量。
近期研究指出使用不同方法制备的得到的具有不同性质的多孔碳材料均对 CO2气体表现出优异的吸附性能。对于炭吸附剂，多孔结构和表面特性等化学性质决定了他们对气体的吸附容量。尤其是含氮官能团的吸附剂，有利于对H2S, CO2,HCl等酸性气体的吸附，主要源于含氮官能团表现出的碱性性质能与酸性气体反应，同时炭材料表面与气体间有很强的氢键作用，均能增加二者之间的吸引力。具有发达孔结构和高比表面积的碳质吸附剂通过促进缺陷位的配位和范德华力作用有效促进物理吸附过程。
美国专利(WO 2013022521 A1)介绍了一种有效去除CO2气体的吸附剂。该发明为一种复合吸附剂，包含一种含沸石的CO2吸附剂以及热容至少83.7 J/(mol.K)的浓度为10％的金属氧化物。该吸附剂有效用于循环吸附过程中的多层吸附，第一层主要是金属氧化物等去除水蒸气的吸附剂，第二层为CO2吸附剂，该复合吸附剂有效应用于低温空气分离之前的预纯化过程，但是该吸附剂对于纯CO2的饱和吸附量较低。
公开号为CN103501891 A的中国专利介绍了一种利用高温热解聚偏二氯乙烯系聚合物或共聚物或其他合适的树脂材料，得到微粒状的富碳热解固体吸附剂的制备方法。在常温常压下，对CO2气体的吸附容量大于105cc/克，同时对 CO2/N2的选择吸附亨利定律分离因子大于5，适宜用于CO2气体的吸附尤其对燃煤发电厂的烟道气有很好的吸附作用，反应涉及高温热解，且伴随着有害物质的产生，不利于可持续发展。
公开号为CN105817197 A的中国专利介绍了一种高效分离CO2的粉煤灰基吸附剂的制备方法。以粉煤灰为原料，采用碱熔融水热法制备得到粉煤灰基吸附剂，对气体CO2/N2以及CO2/CH4有很好的选择吸附性。充分利用了粉煤灰制备的高附加值产品，制备的吸附剂廉价易得，但是反应需要碱性反应试剂，提高了后期处理的成本。
公开号为CN103464099 A的中国专利介绍了一种变压吸附分离CO2/N2用活性炭的制备方法。将煤粉与煤焦油、水、复合催化剂经混捏、成型、炭化、活化后得到柱状活性炭吸附剂。活化主要采用水蒸气，高速的蒸汽将炭化过程产生并积蓄在活性炭孔隙结构中的焦油物质及裂解产物清除，使活性炭封闭的孔结构打开，同时在硝酸盐和氯化物配伍的混合物符合催化剂的作用下，进一步改善活性炭的微孔分布，提高孔容和比表面积，吸附容量较高。但是反应步骤冗长，过程涉及有机试剂，对环境负荷较大。
公开号为CN1676210A的中国专利介绍了一种高钙基CO2吸收剂及其制备方法。以醇，水，铝盐及氧化钙为原料，先在800～1000℃煅烧1-4h，加入醇和水并干燥后在500-700℃中煅烧3h，磨碎磨细后在700～1100℃煅烧1～3h，再次磨碎研细即为高活性钙基CO2吸收剂。该吸收剂反应活性较稳定，是天然气重整制氢反应工艺的理想吸收剂，但是反应分多步进行，且均涉及高温活化，不易控制且温度对产物的性能影响较大。
综上所述，目前制备的CO2吸附剂主要以聚合物，煤粉，金属盐，沸石等为原料，有机溶剂为试剂，经酸碱处理后通过高温或者几步复杂的处理过程，得到多孔或者富含利于与CO2结合的官能团的吸附剂，这些方法通常反应需要多步骤进行，反应条件对产物吸附性能有很大影响，增加了反应成本，且不利于大规模的开发生产利用。而具有碱性官能团的碳质基材料作为吸附剂在污染气体处理方面展现出优异且稳定的性能，因此，寻求一种简单易行、环保的方法制备具有碱性官能团的高CO2吸附性能的新型碳质材料具有重要意义。
发明内容：
本发明的目的在于提供一种吸附CO2的氮掺杂炭吸附剂的制备方法。
为了达到上述目的，本发明采用的技术方案包括：一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：以速生杨木树皮为原料，含氮化合物为氮源，纯水为溶剂，高温高压水热条件处理后，离心、分离得到深棕色固体产物，将棕色固体产物用蒸馏水、无水乙醇洗涤数次至滤液澄清，80℃烘干后在氮气保护下高温煅烧，得到氮掺杂的微孔结构发达的吸附剂，对气体CO2有较高的吸附容量。本操作工艺的主要特点是林木废弃物树皮为原料，环保廉价易得，水为溶剂，含氮化合物为氮源，惰性气体保护下经高温煅烧能够得到较高的比表面积和发达的微孔结构，利于对CO2气体的吸附作用。通过调控水热制备条件，氮源掺杂比例，高温炭化参数可以控制制备吸附剂的表面官能团组成和孔尺寸分布，得到吸附性能优异的吸附剂。本法采用的水热反应操作过程简单，成本低廉，微孔结构发达且可控，具有优良的吸附效果。
本发明的优点是：
1、以速生杨木树皮为原料，充分利用农林废弃物，原料丰富廉价可再生，环保天然无污染；
2、本发明克服了现有技术中的不足，改变了传统的生产工艺，使用水热反应，以水为溶剂，原料不需预处理，反应条件温和，过程操作简单，生产成本低，得率高。
3、本发明以氮源为掺杂源，得到的吸附剂比表面积介于1200-1800m2/g之间,微孔结构发达，符合高CO2吸附性能吸附剂的要求。
4、本发明反应中不涉及有害的化学试剂和化学活化步骤，对环境无污染，生成的含氮官能团和发达的微孔结构协同作用使其对CO2有较高的吸附容量。
附图说明：
图1为本发明实施例1制备得到的氮掺杂炭吸附剂SEM图片；
图2为本发明实施例1制备得到的氮掺杂炭吸附剂TEM图片；
图3为本发明实施例1制备得到的氮掺杂炭吸附剂的各项参数。
具体实施方式：
下面对本发明实施作进一步详细描述：
一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：以速生杨木树皮为原料，含氮化合物为氮源，纯水为溶剂，高温高压水热条件处理后，离心、分离得到深棕色固体产物，将棕色固体产物用蒸馏水、无水乙醇洗涤数次至滤液澄清，80℃烘干后在氮气保护下高温煅烧，得到氮掺杂的微孔结构发达的吸附剂，对气体CO2有较高的吸附容量。
下面，本发明将用实施例进行进一步的说明，但是它并不限于这些实施例的任一个或类似实例。
实施例1：
将杨木树皮磨成木粉，筛选40-60目木粉为原料，取3g上述木粉溶于40ml 水溶液中，加入尿素作为氮源，浓度为4％，搅拌均匀后倒入聚四氟乙烯内衬的反应釜中，保证溶液体积与反应釜容积比为3:5，升温至240℃后恒温反应12h，冷却降至室温后，以5000r/min的转速离心分离2次，得到棕色固体产物。先后用蒸馏水和无水乙醇洗涤3次，80℃真空干燥后得到氮掺杂水热碳前驱体，放入管式电阻炉中，以5℃/min升温至目标温度800℃，恒温2h，得到微孔结构发达的氮掺杂炭吸附剂，比表面积为1625m2/g，平均孔径为2.05nm。
利用麦克公司ASPS 2020N2吸附仪测试制备吸附剂对CO2的吸附性能，吸附测试前，将吸附剂在200℃条件下脱气4h，除去水分和杂质，后测试其在室温条件下(25℃)的CO2吸附性能。结果表明，实例1中的吸附剂对CO2的饱和吸附值为138mg/g。
实施例2：
将杨木树皮磨成木粉，筛选40-60目木粉为原料，取4g上述木粉溶于50ml 水溶液中，加入尿素作为氮源，浓度为6％，搅拌均匀后倒入聚四氟乙烯内衬的反应釜中，保证溶液体积与反应釜容积比为3:5，升温至260℃后恒温反应10h，冷却降至室温后，以8000r/min的转速离心分离2次，得到棕色固体产物。先后用蒸馏水和无水乙醇洗涤2次，80℃真空干燥后得到氮掺杂水热碳前驱体，放入管式电阻炉中，以5℃/min升温至目标温度900℃，恒温1.5h，得到微孔结构发达的氮掺杂炭吸附剂，比表面积为1755m2/g，平均孔径为2.03nm。
利用麦克公司ASPS 2020N2吸附仪测试制备吸附剂对CO2的吸附性能，吸附测试前，将吸附剂在200℃条件下脱气4h，除去水分和杂质，后测试其在室温条件下(25℃)的CO2吸附性能。结果表明，实例1中的吸附剂对CO2的饱和吸附值为158mg/g。
Claims (8)
1.一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：以速生杨木树皮为原料，含氮化合物为氮源，纯水为溶剂，高温高压水热条件处理后，离心、分离得到深棕色固体产物，将棕色固体产物用蒸馏水、无水乙醇洗涤数次至滤液澄清，80℃烘干后在氮气保护下高温煅烧，得到氮掺杂的微孔结构发达的吸附剂，对气体CO2有较高的吸附容量。
2.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：水热反应中原料浓度为3％～8％，溶剂容量与反应器容量比为2:5～4:5。
3.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：掺杂源可以是尿素，三聚氰胺等任意含氮化合物，添加浓度为2％～10％。
4.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：制备反应温度在220～260℃，反应时间10～16小时。
5.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：本法制备的氮掺杂吸附剂的离心分离速率为4000～12000rpm，离心时间为15～30min。
6.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：本法制备的氮掺杂吸附剂吸附剂先用蒸馏水洗涤1-5次，再用无水乙醇洗涤1-5次。
7.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：本法制备的氮掺杂吸附剂高温煅烧所需的温度在700-1000℃之间，炭化时间在1-4h。
8.按照权利要求1所述的一种吸附CO2的氮掺杂炭吸附剂的制备方法，其特征在于：本法制备的氮掺杂吸附剂比表面积介于1200-1800m2/g之间。
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