CN104437443B - 一种提高吸附材料存储天然气性能的活化方法 - Google Patents

一种提高吸附材料存储天然气性能的活化方法 Download PDF

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CN104437443B
CN104437443B CN201410530129.3A CN201410530129A CN104437443B CN 104437443 B CN104437443 B CN 104437443B CN 201410530129 A CN201410530129 A CN 201410530129A CN 104437443 B CN104437443 B CN 104437443B
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sodium
ammonium
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CN104437443A (zh
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杨惠琳
马利海
陈磊
李国明
张立忠
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Ningxia Baota Petrochemical Technology Industry Development Co Ltd
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Abstract

本发明公开了一种提高吸附材料存储天然气性能的活化方法。本方法分为焙烧、酸处理、碱处理、盐处理四道工序，由盐酸、硝酸和氢氟酸配制的浓度为0.5～2.0mol/L酸溶液，和由氢氧化钠、氢氧化钾、氢氧化铵配制的浓度为0.5～2.5 mol/L碱溶液，以及氯化钠、氯化钾、氯化铵、硫酸钠、硫酸铵、硝酸钠、硝酸铵配制的盐溶液，分别对经过300～890℃焙烧后的吸附材料，进行活化处理。依此方法生产可获得具有高比表面积、天然气存储能力高、吸脱附性能良好、使用寿命长的高效天然气吸附材料。

Description

一种提高吸附材料存储天然气性能的活化方法
技术领域
本发明涉及吸附材料的活化处理方法，具体涉及为提高天然气吸附材料的活化方法，属于吸附材料技术领域。
背景技术
在吸附式存储天然气的研究中, 最主要的核心工作是高性能吸附剂的开发和其制备工艺的优化、调控，尤其对吸附材料的活化处理方法最为关键。
存储天然气的吸附材料被广泛开发和利用，如天然沸石、分子筛、活性氧化铝、硅胶、炭黑、活性炭、活性炭纤维、金属有机框架化合物等。但是目前被报道的吸附剂，其吸附性能还不是很理想。在吸附材料的活化处理中，活化方法主要为物理法( 水蒸气活化法、二氧化碳活化法和空气活化法等) 和化学法( 磷酸法、氯化锌法、氢氧化钾和碳酸钾等)。在不作任何处理时，吸附材料的孔、通道中往往被钙、镁等阳离子、水和有机物分子以及无机杂质所占据，孔通道被堵塞，活性位减少。因此，寻找合适的活化方法对吸附材料进行处理，以提高吸附材料的吸附性能成为必要。
发明内容
本发明公开一种天然气吸附材料的活化处理方法，其特征在于活化经焙烧、酸处理、碱处理、盐处理四道工序。每个工序为独立实施，并且为后序操作提供基础。在实际生产工艺中，可连续生产亦可间歇生产。
本发明的吸附材料不局限于炭基吸附材料，适应于天然沸石、分子筛、活性氧化铝、活性炭、活性炭纤维、石墨烯、离子交换树脂等吸附材料，尤其对沸石、活性炭吸附材料效果更佳。
本发明方法快速、简便，工艺流程短，同时经过本发明活化处理后的吸附材料，具有如下特点：
(1)具有高的比表面积和发达的微孔结构；
(2)吸附容量大，在3.5MPa下，吸附材料具有100 (体积比)以上的天然气有效存储能力；
(3)吸附和脱附的速率快，当压力下降到常压时，吸附剂内残留的“余气”少；
(4)导热性良好，使用寿命长，且能再生使用；
本发明通过以下方法实现：
首先，对经过预先制备的天然气吸附材料进行高温焙烧，焙烧的目的是清除材料孔穴和孔道的有机物等，焙烧温度为300～890℃，时间为2-8小时；
其次，对焙烧后的天然气吸附材料进行酸处理。酸处理工序所用酸为盐酸、硝酸和氢氟酸的水溶液，所配得到酸溶液浓度为0.5～2.0 mol/L，酸处理时间为2.5-16小时。
经过酸处理以达到如下目的：
(1) 清除天然气吸附材料孔穴和孔道的无机和有机杂质, 从而使孔穴和孔道得到疏通；
(2) 使半径小的H+ 置换半径大的阳离子, 使孔道的有效空间拓宽；
(3) 增加吸附活性中心。
然后，对吸附材料进行碱处理。调配氢氧化钠、氢氧化钾、氢氧化铵的水溶液，配制的碱溶液浓度为0.5～2.5 mol/L，碱处理时间为3.5-16小时。此条件下，调整了吸附材料的微孔孔径和孔道结构，改善了吸附材料的吸附性能。
最后，对吸附材料进行盐处理。采用一定浓度的无机盐，选用氯化钠、氯化钾、氯化铵、硫酸钠、硫酸铵、硝酸钠、硝酸铵配制盐溶液，配得离子浓度分别为：Na+浓度为0.5～3.0 mol/L，K+浓度为1.0～4.0 mol/L，NH4 +浓度为0.2~2.5 mol/L，盐处理时间为3.5-12小时。
具体实施方式
第一，选取20-100目的天然沸石进行焙烧，焙烧温度为790℃，时间为8小时。
第二，对焙烧后的天然气吸附材料进行酸处理。选用盐酸、硝酸和氢氟酸的水溶液，所配得到酸溶液浓度为1.0 mol/L，酸处理时间为5小时。
第三，调配氢氧化钠、氢氧化钾、氢氧化铵的水溶液，配制的碱溶液浓度为2.5 mol/L，碱处理时间为5小时。
第四，选用氯化钠、氯化钾、氯化铵、硫酸钠、硫酸铵、硝酸钠、硝酸铵配制盐溶液，配得离子浓度分别为：Na+浓度为3.0 mol/L，K+浓度为2.0 mol/L，NH4 +浓度为1.5 mol/L，盐处理时间为10小时。

Claims (1)

1.一种提高吸附材料存储天然气性能的活化方法，其特征在于活化经焙烧、酸处理、碱处理、盐处理四道工序，所述焙烧工序中焙烧温度为300～890℃，时间为2-8小时，所述酸处理工序所用酸为盐酸、硝酸和氢氟酸的水溶液，所配得到酸溶液浓度为0.5～2.0mol/L，酸处理时间为2.5-16小时，所述碱处理所用碱为氢氧化钠、氢氧化钾、氢氧化铵的水溶液，所配碱溶液浓度为0.5～2.5mol/L，碱处理时间为3.5-16小时，所述盐处理所用盐为氯化钠、氯化钾、氯化铵、硫酸钠、硫酸铵、硝酸钠、硝酸铵的水溶液，所配盐溶液中Na+浓度为0.5～3.0mol/L，K+浓度为1.0～4.0mol/L，NH4 +浓度为0.2～2.5mol/L，盐处理时间为3.5-12小时，所述吸附材料为沸石、活性氧化铝、活性炭、石墨烯或离子交换树脂。
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CN108097206B (zh) * 2017-12-07 2020-08-18 浙江海洋大学 一种对小分子烃类吸附力强的吸附剂的制备方法
CN108328706B (zh) * 2018-01-15 2021-12-21 浙江工业大学 一种mof衍生多孔碳/石墨烯复合电极材料的制备及应用
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CN108315835A (zh) * 2018-02-08 2018-07-24 深圳森阳环保材料科技有限公司 一种抗菌性能良好的聚酯纤维
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