CN105524083B - 一种用于纯化天然气的金属‑有机框架材料的制备 - Google Patents
一种用于纯化天然气的金属‑有机框架材料的制备 Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 26
- 239000003345 natural gas Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
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- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
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- 238000000926 separation method Methods 0.000 abstract description 5
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- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 13
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- 229910052751 metal Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- SAOPTAQUONRHEV-UHFFFAOYSA-N gold zinc Chemical compound [Zn].[Au] SAOPTAQUONRHEV-UHFFFAOYSA-N 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
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- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
本发明提供了一种用于纯化天然气的金属‑有机框架材料的制备，通过溶剂热合成方法得到了微孔的基于金属锌的锌金属‑有机框架材料，该材料是一种具有高度水稳定性,由双(3,5‑二羧基苯基)次膦酸离子、锌离子、和二甲基胺阳离子组成，该材料制备简单，在室温常压下对轻质烃包括甲烷、乙烯、乙炔、乙烷、丙烷具有较高的吸附量，并且乙烯、乙炔、乙烷和丙烷对甲烷具有很高的选择性分离性能。该材料可用于天然气纯化，成本低廉，操作方便，应用效果好。
Description
技术领域
本发明属于气体吸附分离技术领域，具体涉及一种基于金属锌的金属-有机框架材料的制备方法和其在纯化天然气方面的应用。
背景技术
天然气是一种较清洁的能源，其主要成分是甲烷并且含有少量的轻质脂肪烃和二氧化碳。轻质脂肪烃是重要的工业原料，但其具有相近的分子大小、分子量和沸点，非常难以分离。传统的工艺是采用低温蒸馏的方法，但该方法需要在较低的温度和高压下实现，浪费了大量的成本。而采用吸附分离的方法可以在较低压力和室温下实现，节省了能源，具有重要的意义。并且，吸附性材料的水稳定性在适用性方面也是很重要的。
发明内容
本发明提出了一种由双(3,5-二羧基苯基)次膦酸(结构如下)和锌盐合成的具有多孔的锌金属-有机框架材料制备方法，并研究了该材料在纯化天然气方面对轻质烃和二氧化碳的选择性分离的应用。所述的锌金属-有机框架材料制备步骤如下：
将双(3,5-二羧基苯基)次膦酸和六水合硝酸锌按照一定的物质的量之比，加入到N,N’-二甲基甲酰胺，乙醇和水的混合溶剂中，逐渐升温至70-100℃，反应24-72小时，降至室温，过滤。用丙酮连续浸泡3天，每24小时换一次新鲜的丙酮溶液，真空干燥，得到该锌金属-有机框架材料，该锌金属有机框架材料具有高度水稳定性并有高度的孔隙率。
双(3,5-二羧基苯基)次膦酸的结构式
本发明提出的锌金属-有机框架材料吸附分离气体测试步骤如下：在比表面及孔隙度分析仪上，在室温常压下将轻质烃(甲烷、乙烯、乙炔、乙烷、丙烷等)通入到含有该锌金属-有机框架材料的吸附管中进行吸附测试，计算吸附量及分离系数。
附图说明
图1为实施例1所得锌金属-有机框架材料配体的配位模式图；
图2为实施例1所得锌金属-有机框架材料的晶体结构堆积图及其一维通道。
具体实施方式
实施例1：锌金属-有机框架材料的制备方法
将双(3,5-二羧基苯基)次膦酸和六水合硝酸锌(物质的量之比为10：1)，加入到N,N’-二甲基甲酰胺，乙醇和水(体积比为1:1:1)的混合溶剂中，逐渐升温至85℃，反应36小时，降至室温，过滤。用丙酮连续浸泡3天，每24小时换一次新鲜的丙酮溶液，真空干燥，得到该锌金属-有机框架材料。
实施例2：锌金属-有机框架材料吸附甲烷气体测试
在比表面及孔隙度分析仪上，在室温常压下将甲烷通入到含有100mg锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为22.5cm3g-1。
实施例3：锌金属-有机框架材料吸附丙烷测试
在比表面及孔隙度分析仪上，在室温常压下将甲烷通入到含有100mg的锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为76cm3g-1，根据理想吸附溶液理论(IAST)对等摩尔的双组份体系计算丙烷/甲烷的选择性系数为285.1。实施例4：锌金属-有机框架材料吸附乙炔气体测试
在比表面及孔隙度分析仪上，在室温常压下将乙炔通入到含有100mg的锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为78.5cm3g-1，根据理想吸附溶液理论(IAST)对等摩尔的双组份体系计算乙炔/甲烷的选择性系数为43.2。实施例5：锌金属-有机框架材料吸附乙烯气体测试
在比表面及孔隙度分析仪上，在室温常压下将乙烯通入到含有100mg的锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为64.0cm3g-1，根据理想吸附溶液理论(IAST)对等摩尔的双组份体系计算乙烯/甲烷的选择性系数为29.1。实施例6：锌金属-有机框架材料吸附乙烷气体测试
在比表面及孔隙度分析仪上，在室温常压下将乙烷通入到含有100mg的锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为59.6cm3g-1，根据理想吸附溶液理论(IAST)对等摩尔的双组份体系计算乙烷/甲烷的选择性系数为27.0。实施例7：锌金属-有机框架材料吸附二氧化碳气体测试
在比表面及孔隙度分析仪上，在室温常压下将二氧化碳通入到含有100mg的锌金属-有机框架材料的吸附筒中进行吸附测试，吸附量为111.0cm3g-1，根据理想吸附溶液理论(IAST)对等摩尔的双组份体系计算二氧化碳/甲烷的选择性系数为5.9。
实施例8:锌金属-有机框架材料水稳定性测试
在10ml的小玻璃瓶中，在室温常压下将20mg的锌金属-有机框架材料在去离子水中浸泡3天，然后过滤出来用粉末x-射线衍射仪测试，其衍射峰与模拟的衍射峰相一致，证明了其结构没有被破坏。另外，在圆底烧瓶中，将20mg的锌金属-有机框架材料浸泡在去离子水中，并且加热至100度，36h之后过滤出来用粉末x-射线衍射仪测试，其衍射峰与模拟的衍射峰相一致，证明了其结构没有被破坏。
Claims (3)
1.一种基于金属锌的锌金属-有机框架材料，分子式为：[Zn4(hpdia)2]·[NH2(CH3)2]2·3DMF·4H2O，该材料是具有水稳定性的三维的框架材料，其中包含的一维通道，其中hpdia代表双(3,5-二羧基苯基)次磷酸离子,DMF代表N,N’-二甲基甲酰胺。
2.一种如权利要求1所述的锌金属-有机框架材料的制备方法，其特质在于具体步骤如下：将双(3,5-二羧基苯基)次磷酸和硝酸锌加入到N,N’-二甲基甲酰胺、乙醇、水的混合溶剂中，逐渐升温至70-100℃，反应24-72小时，降至室温，过滤，用有机溶剂浸泡，每隔24小时换一次新鲜的丙酮溶液，重复三次，真空干燥后，得到锌金属-有机框架材料。
3.一种如权利要求1所述的锌金属-有机框架材料用于天然气的纯化。
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| TW201924766A (zh) * | 2017-10-05 | 2019-07-01 | 美商紐麥特科技公司 | 電子氣體之原位純化 |
| CN110615817B (zh) * | 2019-08-02 | 2020-11-03 | 浙江大学 | 一种二茂铁基金属有机框架材料的制备及其在水体处理中的应用 |
| CN111996521B (zh) * | 2020-08-26 | 2021-05-18 | 西南交通大学 | 一种在生物可降解锌表面构建无机微米花嵌合金属-有机复合纳米簇改性功能层的方法 |
| CN114907230B (zh) * | 2021-02-08 | 2023-02-28 | 北京化工大学 | 有机软多孔框架材料及其制备方法和应用 |
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