CN106866985B - 一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 - Google Patents
一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 Download PDFInfo
- Publication number
- CN106866985B CN106866985B CN201710011593.5A CN201710011593A CN106866985B CN 106866985 B CN106866985 B CN 106866985B CN 201710011593 A CN201710011593 A CN 201710011593A CN 106866985 B CN106866985 B CN 106866985B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- acetylene
- preparation
- micropore metal
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 5
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract description 3
- 239000013336 microporous metal-organic framework Substances 0.000 abstract description 3
- 210000003850 cellular structure Anatomy 0.000 abstract 1
- 150000002394 hexacarboxylic acid derivatives Chemical class 0.000 abstract 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N hexane carboxylic acid Natural products CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BEDFIBPNPHRGDO-UHFFFAOYSA-N yttrium;hydrate Chemical compound O.[Y] BEDFIBPNPHRGDO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- -1 methane Alkynes Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SXFQCTMHFJARRW-UHFFFAOYSA-N acetylene;methane Chemical compound C.C#C SXFQCTMHFJARRW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明涉及无机有机杂化材料技术领域，具体一种新型微孔金属有机骨架材料及其制备方法与应用。该制备方法使用含有均草怕津(s‑heptazine)和亚氨基功能基团的六羧酸作为反应用有机配体，在水热条件下与硝酸钇发生反应得到一种新型微孔金属有机骨架材料。采用该制备方法得到的微孔金属有机骨架材料具有均匀而规则的孔道结构，以及优良的乙炔和甲烷吸附分离能力。
Description
技术领域
本发明涉及无机有机杂化材料技术领域，具体一种微孔金属有机骨架材料及其制备方法与应用。
背景技术
近年来能源危机受到全世界的广泛关注，能源短缺问题亟待解决。虽然新能源技术被积极的研究并开发利用，但化石能源(如煤、石油和天然气)仍然是人类社会的主要能源，如何提高化石能源的使用效率成为解决问题的关键途径。甲烷是天然气的主要成分，不仅是生活常用的清洁燃料，还是一种重要的化工原料。然而甲烷中杂质(如其他烷烃、烯烃、炔烃和非烃气体)的存在会影响甲烷的使用和转化效率。另外，甲烷裂解制乙炔是工业上制备乙炔的一种常用方法，主要方程式如下：
该反应不仅需要纯度较高的甲烷作为原料(90％以上)，而且甲烷转化为乙炔的产率只有40％～50％，产生的裂解气为包含大量甲烷和乙炔的混合气。所以，从甲烷中分离乙炔是一种重要的工业生产流程，不仅能提高天然气的纯度，还能为化工生产提供纯化的乙炔原料。
传统的分离工艺是裂解气深冷分离技术，利用裂解气中各类烃相对挥发度的差异，在低温下将除氢气外的烃类全部冷凝，之后转入精馏塔进行多组分精馏分离，不仅能耗较大，而且设备造价较高[CN205774195U、CN205700034U、CN1292486A、CN104534812A]。另外工业上也常用溶剂吸附法对乙炔进行分离，例如美国专利US1960326用苯衍生物和硫酸作为吸收溶剂对乙炔进行吸附分离；美国专利US3647843则使用含有配位金属化合物CuAlCl4的甲苯溶液与乙炔发生络合反应，从而对乙炔甲烷混合气进行分离。但这类方法用到大量有机溶剂，成本较高，对环境有污染。
为了提高分离效率、降低分离成本，开发新型选择性吸附材料是非常意义的。金属有机骨架材料(Metal-Organic Frameworks,MOF)具有比表面积大、孔结构可调节和孔道表面易于修饰等优点，可广泛的应用于气体吸附分离领域。由于MOFs材料对多种气体的捕获都有很好的效果，调节孔的功能性来选择性吸附某类气体从而进行分离成为研究的焦点。中国专利CN10505524083A公开了一种用于纯化天然气的锌金属有机骨架材料的制备方法，该方法以硝酸锌和双(3,5-二羧基苯基)次膦酸有机配体在N,N’-二甲基甲酰胺溶剂中反应制得一种金属有机骨架化合物，然后浸泡、真空干燥得到一种吸附材料，用于天然气的纯化。该制备方法用到有机溶剂N,N’-二甲基甲酰胺，非绿色环保，而且得到的多孔材料中缺少用于选择性分离的功能基团(如氨基、吡啶基等)。
发明内容
本发明要解决的技术问题是，弥补上诉原有技术的不足，提出一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法。
本发明的技术问题通过以下的技术方案予以解决:
一种微孔金属有机骨架材料，分子式为Y(C30N10O12H15)，其结构式如下：
该微孔金属有机骨架化合物属六方晶系，P31c空间群。
本发明提供了一种微孔金属有机骨架材料的制备方法：将硝酸钇与有机配体2,5,8-三(3,5-二羧基苯胺)-均草怕津(C30N10O10H18，H6TDPAH)溶于水中，于140～180℃反应24～48小时得到微孔金属有机骨架材料粗产品；用无水丙酮洗涤所述微孔金属有机骨架材料粗产品得到纯化的微孔金属有机骨架材料，于80℃～100℃烘干，得到无色块状晶体；有机配体H6TDPAH、硝酸钇、水的摩尔比为1:3～5:800～1200。
有益效果:
1.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料是基于Y(III)金属离子与有机配体2,5,8-三(3,5-二羧基苯胺)-均草怕津(C30N10O10H18，H6TDPAH)水热条件下合成得到的金属有机骨架材料，由于有机配体中包含均草怕津与亚氨基官能团，该材料既保持金属有机材料比表面积大、物理吸附能力强的特点，又通过均草怕津与亚氨基官能团共同作用提高孔道与乙炔相互作用。
2.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料预处理程序简单易操作。
3.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架材料可以实现常压下高效的选择性吸附。
4.本发明制备的用于乙炔和甲烷吸附分离的一种微孔金属有机骨架在吸附小分子气体后，通过简单的再加热的方式可以将吸附的气体分子去除，有利于反复使用。
5.反应用水做溶剂，环境友好。
附图说明
图1本发明微孔金属有机骨架材料晶体样品图；
图2本发明微孔金属有机骨架材料结构示意图；
图3本发明实施例1中制备的微孔金属有机骨架材料的XRD图谱；
图4本发明实施例1中制备的微孔金属有机骨架材料的红外图谱；
图5 77K、0～101324Pa条件下本发明实施例1所制备的微孔金属有机骨架材料的氮气吸附等温线；
图6在298K、0～101324Pa条件下本发明实施例1所制备的微孔金属有机骨架材料的乙炔和甲烷吸附等温线。
具体实施方式
以下结合附图与实施例对本发明作进一步详细描述，需要指出的是，其目的仅在于更好理解本发明的内容而非限制本发明的保护范围。
实施例1：
以下对本发明制备出的新型微孔金属有机骨架材料的合成具体条件做进一步详细说明。本实施例中，金属有机骨架微孔材料采用的合成条件如下：
反应用有机配体为C30N10O10H18(0.07g)；
金属钇盐为六水合硝酸钇Y(NO)3·6H2O(0.15g)；
反应溶剂为水(7ml)。
具体合成步骤如下：
顺序称量0.07g有机配体C30N10O10H18与0.15g六水合硝酸钇至10ml反应釜中，再加入1.8ml水，搅拌均匀，放入160℃烘箱中反应24小时后以3℃/小时降至室温过滤得到无色块状晶体，产率为90％(以有机配体H6TDPAH计算)。晶胞参数为15.0326，15.0326，13.4206，90，90，120。
实施例2：
将实施例1的溶液移至玻璃管中，将玻璃管抽真空，然后用酒精喷灯烧结封口，其他条件不变，得到与实施例1中所述相同材料。
实施例3
顺序称量0.07g有机配体C30N10O10H18与0.12g六水合硝酸钇至10ml反应釜中，再加入1.4ml水，搅拌均匀，放入180℃烘箱中反应24小时后以3℃/小时降至室温过滤得到实施例1中所述的金属有机骨架材料，产率为80％(以有机配体H6TDPAH计算)。
实施例4
顺序称量0.07g有机配体C30N10O10H18与0.19g六水合硝酸钇至15ml反应釜中，再加入2.2ml水，搅拌均匀，放入140℃烘箱中反应48小时后以3℃/小时降至室温过滤得到实施例1中所述的金属有机骨架材料，产率为65％(以有机配体H6TDPAH计算)。
综上所述，本发明利用简单环保的方法，合成了一种以Y(III)为中心，含均草怕津和亚氨基功能基团的微孔金属有机骨架材料，该材料具有较大的比表面积(798m2g-1)，孔道直径为常温常压下具有良好乙炔和甲烷吸附分离能力，可在工业生产中捕获C2H2作为重要的化工原料。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本领域的普通技术人员来说，可以根据本发明的技术方案和发明构思，做出相应改变和替代，而且性能或用途相同，都应当视为本发明的保护范围。
Claims (2)
1.一种用于乙炔和甲烷吸附分离的微孔金属有机骨架材料，其分子式为Y(C30N10O12H15)，其结构式如下：
该微孔金属有机骨架材料属六方晶系，P31c空间群。
2.根据权利要求1所述的一种用于乙炔和甲烷吸附分离的微孔金属有机骨架材料的制备方法，其特征在于，将硝酸钇与有机配体2,5,8-三(3,5-二羧基苯胺)-均草怕津(C30N10O10H18，H6TDPAH)溶于水中，于140～180℃反应24～48小时得到微孔金属有机骨架材料粗产品；用无水丙酮洗涤所述微孔金属有机骨架材料粗产品得到纯化的微孔金属有机骨架材料，于100℃烘干，得到无色块状晶体；有机配体H6TDPAH、硝酸钇、水的摩尔比为1:3～5:800～1200。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011593.5A CN106866985B (zh) | 2017-01-07 | 2017-01-07 | 一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710011593.5A CN106866985B (zh) | 2017-01-07 | 2017-01-07 | 一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106866985A CN106866985A (zh) | 2017-06-20 |
| CN106866985B true CN106866985B (zh) | 2019-11-26 |
Family
ID=59164547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710011593.5A Expired - Fee Related CN106866985B (zh) | 2017-01-07 | 2017-01-07 | 一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866985B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108276582B (zh) * | 2017-12-27 | 2021-01-19 | 华中科技大学 | 一种金属有机骨架材料及制备方法与吸附甲醛的应用 |
| US11905303B2 (en) * | 2018-12-21 | 2024-02-20 | Massey University | Metal-organic frameworks for gas adsorption |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2907569A1 (en) * | 2012-10-10 | 2015-08-19 | Nanjing Tech University | Regeneration method for cu-btc material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110168018A1 (en) * | 2010-01-14 | 2011-07-14 | Research Institute Of Petroleum Industry (Ripi) | Hybrid nano sorbent |
| CN103435620B (zh) * | 2013-08-02 | 2015-01-28 | 吉林大学 | 用于co2吸附与分离的多孔铜金属有机骨架材料及其制备方法 |
| CN104549160A (zh) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | 一种用于正、异构烷烃吸附分离的金属有机骨架多孔吸附材料的制法 |
| CN103933939A (zh) * | 2014-04-09 | 2014-07-23 | 同济大学 | 一种高甲烷吸附存储密度的金属-有机骨架mof材料 |
| KR101728809B1 (ko) * | 2014-09-25 | 2017-04-21 | 한국화학연구원 | 질소 선택적 흡착능을 갖는 유무기 하이브리드 나노세공체 및 이를 이용한 질소 함유 혼합기체의 분리 방법 |
| CN105713017A (zh) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | 一种高选择性金属有机骨架材料及其制备方法 |
-
2017
- 2017-01-07 CN CN201710011593.5A patent/CN106866985B/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2907569A1 (en) * | 2012-10-10 | 2015-08-19 | Nanjing Tech University | Regeneration method for cu-btc material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106866985A (zh) | 2017-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102962036A (zh) | 基于过渡金属钴的多孔金属有机骨架材料及其制备方法 | |
| CN109675526B (zh) | 一种超微孔金属有机骨架材料Zn(ox)0.5(mtz)及其制备方法与吸附分离应用 | |
| CN107500307B (zh) | 一种沸石分子筛的制备方法及其应用 | |
| CN111346611B (zh) | 一种新型多孔金属有机骨架材料及其制备方法和应用 | |
| Liu et al. | A microporous yttrium metal–organic framework of an unusual nia topology for high adsorption selectivity of C 2 H 2 and CO 2 over CH 4 at room temperature | |
| CN103435620B (zh) | 用于co2吸附与分离的多孔铜金属有机骨架材料及其制备方法 | |
| CN113019330A (zh) | 一种铜基金属-有机框架材料的制备及其乙炔/二氧化碳分离应用 | |
| CN102728331A (zh) | 吸附分离二氧化碳/甲烷的金属有机骨架材料的制备方法 | |
| CN115678027B (zh) | 一种镍基双配体的金属有机框架材料、制备方法及应用 | |
| CN115678024B (zh) | 一种氟硅酸盐mof材料及其制备方法与应用 | |
| CN113667136A (zh) | 一种用于高效分离乙炔/二氧化碳的超高稳定性、低成本金属-有机框架材料及其制备方法 | |
| CN105617978B (zh) | 室温吸附CO2的负载型MgO/γ-Al2O3吸附剂的制备方法 | |
| CN106866985B (zh) | 一种用于乙炔和甲烷吸附分离的金属有机骨架材料及其制备方法 | |
| CN110776522B (zh) | 一种铜金属有机框架材料及其制备方法、气体捕获方法、气体分离方法 | |
| CN115536857A (zh) | 一种选择性吸附二氧化碳的锌-有机框架材料及合成方法 | |
| CN110563957B (zh) | 一种三维铁基金属-有机骨架的制备方法及应用 | |
| Wang et al. | Mesoporous MgO enriched in Lewis base sites as effective catalysts for efficient CO2 capture | |
| CN108654564B (zh) | 一种配位聚合物多孔材料的制备方法及其应用 | |
| CN116284063A (zh) | 一种含氮羧酸过渡金属配合物及其制备方法与应用 | |
| CN110052116A (zh) | 一种富马酸基二氧化碳吸收剂及吸收解吸二氧化碳的方法 | |
| CN114989442A (zh) | 一种用于co2吸附捕获的新型超微孔多孔配位聚合物的制备方法 | |
| CN117126419B (zh) | 一种用于气体分离的钴金属有机框架晶体材料及其制备方法与应用 | |
| CN112778153A (zh) | 酰胺基桥连六羧酸配体和金属有机框架材料及其制备方法和应用 | |
| CN116082657B (zh) | 一种锌基金属有机框架材料及其制备方法和乙烯分离应用 | |
| CN116284823B (zh) | 一种晶态多孔材料及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191126 |