CN115006968A - 一种海洋生物质气体分离膜的应用 - Google Patents
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Abstract
本发明公开了一种海洋生物质膜在气体分离中的应用,属于膜分离领域。该方法旨在开发一种高通量、高分离比的气体分离膜,通过提取海藻中的海藻酸钠制备海藻酸钙纤维纸(Ca‑AFP)膜。利用海藻酸结构中的α‑L‑古罗糖醛酸(G段)可以与二价阳离子通过络合作用形成特殊的“蛋‑壳”结构,该结构可以有效降低海藻酸自身通过氢键作用引起的结晶度,以提供更多的可用于气体吸附及传输的无定形区域。本说明所制备的Ca‑AFP膜表现出高的气体通量和分离比。进行H2/CO2混合气体分离时,表现出超高的通量(H2:1.07×10‑5mol m‑2 s‑1Pa‑1;CO2:5.21×10‑ 7mol m‑2 s‑1Pa‑1)、优异的分离比(20.5)和稳定性。
Description
技术领域
本发明属于膜的气体分离领域,具体涉及一种由海洋生物质膜在气体分离中的应用。
背景技术
由于精细有机合成、航空航天等多种行业的发展需求,氢气特别是高纯氢气的应用将更为广泛,因此氢气的纯化受到人们极大的关注。如水煤气转化制氢过程中离开反应器的产品主要含有H2和CO2,所以从H2/CO2混合气中高效地分离H2就至关重要。氢气的纯化可以通过多种方法实现,其中膜分离纯化氢气以其能耗少、投资少、安装面积小而且氢纯度和产量亦不逊色而占据着相当的优势。半个世纪来,聚合物膜因其低廉的成本及良好的加工性占据了主要的气体分离市场。然而聚合物膜由致密状态或较少多孔相导致了它的通量及分离比通常存在此消彼长的关系。为了高效的将CO2从混合气中分离出来,学者们在聚合物膜表面引入大量的亲CO2分子的基团,如-NH2, -COOH,-OH。这些基团通过范德华力对CO2分子具有较高的亲和力。然而这些基团的存在也会增强聚合物链间的氢键作用,而是聚合物具有一定的结晶度,聚合物结晶性会产生大量紧密排列的区域,会限制气体分子的有效传输路径,从而降低材料的气体渗透性。因此,如何制备具有大量亲CO2基团且超低结晶性的聚合物材料迫在眉睫!本发明基于以上背景,通过从海藻中提取出的海藻酸钠制备出海藻酸钙纤维纸膜(Ca-AFP),该纸膜中存在大量亲CO2基团(-COOH和-OH),此外海藻酸中的α-L-古罗糖醛酸(G段)可以与Ca2+通过络合作用形成特殊的“蛋-壳”结构进而破坏氢键而降低材料本身的结晶度,提高材料对气体分子的渗透及分离性能。此类膜可以有效分离混合气体(高的气体通量和高的分离比)。
发明内容
为了实现上述目的,本发明将制备的Ca-AFP膜应用到混合气体分离中,表现出优异的气体分离性能(H2:1.07×10-5mol m-2s-1Pa-1;CO2:5.21×10-7mol m-2s-1Pa-1,优异的H2/CO2分离比:20.5)。
本发明主要涉及海藻酸钙纤维纸(Ca-AFP)膜在气体分离中的应用,所述气体为体积比为 1∶1的H2和CO2混合气。将待测膜用O型硅胶圈密封,放在膜分离装置上,一侧连接到进料系统,其中进料气体流速保持在100mL/min,吹扫气体Ar的流速为50mL/min,另一侧连接到气相色谱,根据色谱结果计算气体的通量及分离比。
Ca-AFP膜的制备具体包括以下步骤:
(1)配制海藻酸钠水溶液SA;
(2)利用湿法纺丝技术通过喷丝孔挤出SA到氯化钙作为凝固浴的水溶液中,制备海藻酸钙纤维Ca-AFs长丝;
(3)将步骤(2)中制得的Ca-AFs长丝束切成长度为3-5mm的短束,取Ca-AFs短束放入去离子水中浸泡,得悬浮液;
(4)将步骤(3)中制得的悬浮液通过瓦力打浆机打浆,然后再放入标准纤维解离器中解离;
(5)将步骤(4)中制得的溶液放入纸页成型器中抄纸,真空热压下干燥。
本发明的Ca-AFP膜材料用于H2/CO2气体分离,利用海藻酸中丰富的亲CO2基团及可以与高价金属离子形成特殊的“蛋-壳”结构,且海藻酸钠来源广泛、成本低、安全性高,膜制备过程简单。本发明方法制备的Ca-AFP具有很高的通量和气体分离比。
附图说明
图1是具体实施得到的Ca-AFP膜及形貌表征的SEM图;
图2是具体实施得到的Ca-AFP膜的气体通量和分离比的表征;
图3是具体实施得到的Ca-AFP的气体分离性能稳定性的表征。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例的附图,对本发明实施例的技术方案进行清楚、完整地描述。显然,所描述的实施例是本发明的一部分实施例,而不是全部的实施例。基于所描述的本发明的实施例,本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明所采用的技术方案是:利用从海藻中提取的海藻酸钠作为原料,通过湿法纺丝制备纤维,利用海藻酸结构中大量的亲CO2基团(-OH,-COOH)及可以与Ca2+形成特殊的“蛋-壳”结构可以降低材料的结晶度,提高膜的H2/CO2分离性能。
本发明主要涉及海藻酸钙纤维纸(Ca-AFP)膜在气体分离中的应用,所述气体为体积比为 1∶1的H2和CO2混合气。将待测膜用O型硅胶圈密封,放在膜分离装置上,一侧连接到进料系统,其中进料气体流速保持在100mL/min,吹扫气体Ar的流速为50mL/min,另一侧连接到气相色谱,根据色谱结果计算气体的通量及分离比。Ca-AFP膜的制备具体包括以下步骤:
(1)配制海藻酸钠水溶液SA;
(2)利用湿法纺丝技术通过喷丝孔挤出SA到氯化钙作为凝固浴的水溶液中,制备海藻酸钙纤维Ca-AFs长丝;
(3)将步骤(2)中制得的Ca-AFs长丝束切成长度为3-5mm的短束,取Ca-AFs短束放入去离子水中浸泡,得悬浮液;
(4)将步骤(3)中制得的悬浮液通过瓦力打浆机打浆,然后再放入标准纤维解离器中解离;
(5)将步骤(4)中制得的溶液放入纸页成型器中抄纸,真空热压下干燥。
所述使用的海藻酸钠溶液需要过滤,打浆10min,所用气体为体积比为1∶1的H2和CO2混合气。
应该理解,尽管参考其示例性的实施方案,已经对本发明进行具体地显示和描述,但是本领域的普通技术人员应该理解,在不背离由权利要求书所定义的本发明的精神和范围的条件下,可以在其中进行各种形式和细节的变化,可以进行各种实施方案的任意组合。
Claims (6)
1.一种海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,Ca-AFP膜应用于气体分离性能的测试。
2.根据权利要求书1所述的海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,所述气体为体积比为1∶1的H2和CO2混合气。
3.根据权利要求1或2所述的一种海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,气体分离的操作如下:
将Ca-AFP膜用0型硅胶圈密封,放在膜分离装置上,一侧连接到进料系统,其中进料气体流速保持在100mL/min,吹扫气体Ar的流速为50mL/min,另一侧连接到气相色谱,根据色谱结果计算气体的通量及分离比。
4.根据权利要求书1所述的海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,所述Ca-AFP膜的制备方法包括以下步骤:
(1)配制海藻酸钠水溶液SA;
(2)利用湿法纺丝技术通过喷丝孔挤出SA到氯化钙作为凝固浴的水溶液中,制备海藻酸钙纤维Ca-AFs长丝;
(3)将步骤(2)中制得的Ca-AFs长丝束切成长度为3-5mm的短束,取Ca-AFs短束放入去离子水中浸泡,得悬浮液;
(4)将步骤(3)中制得的悬浮液通过瓦力打浆机打浆,然后再放入标准纤维解离器中解离;
(5)将步骤(4)中制得的溶液放入纸页成型器中抄纸,真空热压下干燥。
5.根据权利要求书4所述的海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,步骤(1)中对SA溶液过滤后使用。
6.根据权利要求书5所述的海藻酸钙纤维纸Ca-AFP膜在气体分离中的应用,其特征在于,步骤(4)中瓦力打浆10min。
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Citations (6)
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GB552770A (en) * | 1941-10-21 | 1943-04-23 | Cefoil Ltd | Improvements in or relating to the manufacture of transparent alginate films |
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