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