CN101816924A - Metal organic framework material used for absorbing and separating CO2 and preparation method thereof - Google Patents
Metal organic framework material used for absorbing and separating CO2 and preparation method thereof Download PDFInfo
- Publication number
- CN101816924A CN101816924A CN201010145406A CN201010145406A CN101816924A CN 101816924 A CN101816924 A CN 101816924A CN 201010145406 A CN201010145406 A CN 201010145406A CN 201010145406 A CN201010145406 A CN 201010145406A CN 101816924 A CN101816924 A CN 101816924A
- Authority
- CN
- China
- Prior art keywords
- metal
- organic framework
- absorption
- framework materials
- separates
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention provides a metal organic framework material used for absorbing and separating CO2 and a preparation method thereof. The metal organic framework material is a rigid metal carboxyl compound cluster-like structure which is formed by transition metal ions and multidentate organic ligands through covalent bonds and intermolecular forces. An amine polymer is modified on the metal organic framework material; and the metal organic framework material used for absorbing and separating the CO2 has a specific surface area of 1,000 to 1,200 m<2>/g, and a pore volume of 0.4 to 0.6 cm<3>/g. The preparation method comprises the following steps of: respectively dissolving the nitrate, the chloride or the carbonate of copper or zinc and 1,3,5-trimesic acid together in a stoichiometric ratio in water or an organic solvent; mixing uniformly and sufficiently to react to obtain a BTC bridged complex crystal; and applying a product obtained by reacting an obtained BTC bridged complex crystal with the solution of polyethyleneimine to the metal organic framework material used for absorbing and separating the CO2. The material can realize selective absorption of a gas under a low pressure.
Description
Technical field
The invention belongs to the preparation field of metal-organic framework materials, particularly a kind of modification that is used for the porous metals framework material of carbon dioxide absorption.
Background technology
Along with the quickening of process of industrialization, global CO2 emissions are increasing, and cause environmental hazard.The whole world faces the urgent task of GHG emissions mitigation at present.Various countries are falling over each other to develop CO
2Reclaim and when utilizing technology, new technology and industry are also arisen at the historic moment.
Existing way of disposing of CO2 to flue gas mainly is Physical Absorption method and chemical absorption method.The Physical Absorption method adopts solid absorbent, and specific area is big, and the adsorbents adsorb capacity of unit volume is big, and shortcoming is that adsorbed gas is not had selectivity, and adsorption efficiency is low; Chemical absorption method adopts liquid to absorb, adsorbate had than high selectivity, and solvent utilization rate height, good separating effect, shortcoming is because solvent and CO
2Contact area is little, thereby causes solvent molecule and CO
2Intermolecular exchange rate is low, and absorption rate is low, and perishable reaction vessels.And utilize the amine solvent catching carbon dioxide also to have a troubling problem:, just to be difficult to again the two be separated in case carbon dioxide combines with amine solvent.Therefore, recycling amine solvent also becomes very difficult.If want, need to consume big energy with the two separation.Be expected to adopt the cellular solid of a new generation to substitute amine solvent at present.The MOFs of a new generation, its carbon dioxide capture and storage capacity and amine solvent differ do not have own, still very easily with carbon dioxide separation.
Porous metals-organic coordination polymer or porous organo-metallic skeleton (MOF) are a kind of new function materials, with traditional porose material for example zeolite, molecular sieve etc. compare, MOF has the pore passage structure of homogeneous, huge specific area and framework internal pore volume.It is worth noting most and can regulate and control hole size, shape and surface characteristic by the combination of its building-block molecule such as metal ion and organic ligand molecule, thereby give its particular structure and characteristic, all have application promise in clinical practice at aspects such as gas storage.
MOF can capture CO effectively
2Synthesized multiple MOF compounds abroad, one of its compound MOF-177 stores CO under room temperature and middle pressure
2Ability is considerably beyond any other porous material.The CO that captures
2Gas can easily discharge through heating a little.This class complex mainly synthesizes by hydrothermal synthesis method, solvent thermal synthesis method, water-solvent thermal synthesis method, diffusion synthetic method or electrochemical preparation method.Wherein, hydrothermal synthesis method is a reaction medium with water, has low, the eco-friendly characteristics of cost.
Existing carbon dioxide absorber just has adsorption effect preferably under condition of high voltage, and selectivity is relatively poor.For this reason, the design a kind of can under the low pressure condition, have than high adsorption capacity and the good adsorbent of selectivity have great importance.
Summary of the invention
In order to solve the CO that prior art exists
2Adsorbent needs the problem of use under high pressure and poor selectivity, the invention provides a kind of CO of being used for
2Absorption and metal-organic framework materials that separates and preparation method thereof can under low pressure be used, and selectivity is good, easily take off suction.
Technical scheme of the present invention is: a kind of CO that is used for
2Absorption and the metal-organic framework materials that separates, wherein, metal-organic framework materials is the metal carboxyl compound bunch shape structure of the rigidity that is made of by covalent bond or intermolecular force transition metal ions and multiple tooth organic ligand, on metal-organic framework materials, be modified with amine polymer, the described CO that is used for
2Absorption is 1000～1200m with the specific area of the metal-organic framework materials that separates
2/ g, pore volume 0.4～0.6cm
3/ g.Transition metal ions is preferably Cu
2+Or Zn
2+Multiple tooth organic ligand is preferably BTC.The amine polymer of modifying on metal-organic framework materials can be selected polymine, and weight average molecular weight is 25000.
Can adopt hydro-thermal or solvent thermal reaction to divide a step or two steps to prepare.Concrete steps with the two-step method preparation are: elder generation is with nitrate, chloride or the carbonate and 1 of copper or zinc, 3, in the mixed solution that the equal benzene tricarbonic acid of 5-or other have that at least two energy form in the water-soluble or organic solvent of the coordination center part of coordinate bond with metal or the two mixes with certain proportion, fully mix, regulating the pH value with NaOH, potassium hydroxide, sodium acetate, acetic acid or watery hydrochloric acid then is about 6, and reaction obtains BTC bridged complex crystal; In order to improve the adsorption efficiency of carbon dioxide, the present invention introduces polymine by modes such as interactional mode such as covalent bond, ionic bond, intermolecular force and static in porous material, and makes these amino high degree of dispersion in poromerics.Specific practice is exactly that the BTC bridged complex crystal that will obtain and polymine solution reaction obtain product and be used for CO
2Absorption and the metal-organic framework materials that separates.
Adopt the concrete steps of one-step method preparation to be: with nitrate, chloride or the carbonate and 1,3 of copper or zinc, equal benzene tricarbonic acid of 5-and polymine one arise to react in water or the organic solvent and obtain being used for CO
2Absorption and the metal-organic framework materials that separates.
The organic solvent that uses in the reaction as in methyl alcohol, ethanol, DMF, triethylamine, ethylene glycol, the pyrimidine any one or arbitrarily several any than mixing.
Beneficial effect:
1. the Organometallic framework material that is used for carbon dioxide absorption of the present invention's preparation is based on transition metal ions and multiple tooth organic ligand effect hydro-thermal or solvent thermal synthesis and obtains metal-organic framework materials, and adopt amine polymer that metal-organic framework materials is modified, because electronegative static self assembly of the electropositive of amine substance and ligand surface interacts, promoted the interaction of metal organic ligand and amine substance greatly, it is big to have obtained a kind of specific area of metal-organic framework materials that both kept, the characteristics of high adsorption capacity improve the carbon dioxide absorber of gas-selectively again by amine substance.
The Organometallic framework material that is used for carbon dioxide absorption of the present invention preparation can realize low pressure, optionally, absorption efficiently.
3. the Organometallic framework material that is used for carbon dioxide absorption of the present invention preparation can be easily after having adsorbed behind the carbon dioxide heating again discharge the carbon dioxide of absorption again, can recycle.
4. the Organometallic framework material that is used for carbon dioxide absorption of the present invention's preparation has supported amine polymers such as polymine, because this base polymer can be in the duct of material, so that all there is reduction in various degree in the specific area of metal organic ligand, pore volume and aperture, illustrate that functional group major part that the grafting effect is got on is distributed in the inner surface of metal organic ligand, and the duct is high-sequential still, no duct clogging.Because the introducing of amine polymer, the existence of wherein a large amount of nitrogen base active sites make the metal organic ligand absorption property after modifying that tangible increase be arranged, more easily regeneration.
5. reaction condition gentleness, method is easy.
Description of drawings
The thermogravimetric analysis figure of Fig. 1 Cu-BTC crystal.Fig. 1 is at N
2Be increased to 500 ℃ thermal multigraph in the atmosphere from room temperature with the temperature rise rate of 5 ℃/min.Among the figure as can be seen the temperature between the room temperature to 100 ℃ be reduced to removing of physical absorption water in the crystal and some organic solvents, it is the removing of water between the lattice that weight between 100 ℃ to 300 ℃ reduces, and 300 ℃ of later losses in weight are the decomposition of Cu-BTC.
CO during Fig. 2 273K
2Adsorption isotherm on the Cu-BTC crystal.Fig. 2 be the Cu-BTC crystal under 273K, pressure limit rises to an atmospheric absorption isotherm from vacuum.
Fig. 3 is the molecular model of the prepared metallo organic material of the present invention, and wherein the chain on junior unit four limits is organic bridge crosslinking structure that trimesic acid forms, and is in the CuO that is between four chains
4Metal cluster.
The specific embodiment
Further specify the present invention by the following examples.
The concrete operations step of two-step method preparation is:
(1) adopts the synthetic metal organic ligand of hydro-thermal (solvent heat) method: by stoichiometric proportion, nitrate, chloride or carbonate solution and ligand 1 with copper or zinc, 3, the equal benzene tricarbonic acid of 5-mixes in the reactor internal reaction after 24 hours in the aqueous solution or organic solvent, filtration obtains BTC bridged complex crystal, organic solvent can select in methyl alcohol, ethanol, DMF, triethylamine, ethylene glycol, the pyrimidine any one or arbitrarily several arbitrarily than mixed liquor.
(2) polymine is soluble in water, add in the polyethyleneimine: amine aqueous solution by the solution of stoichiometric proportion BTC bridged complex crystal or BTC bridged complex crystal, mix, leave standstill reaction 3～15 hours after the sealing, obtain the target product crystal.
Embodiment 1: two step synthetic method prepares the Cu-BTC/PEI complex
The first step, synthetic Cu-BTC crystal
1.7922g (7.71mmol) Cu (NO
3)
22.5H
2O is dissolved in the 24ml deionized water, and 0.8806g (4.19mmol) trimesic acid is dissolved in the 24ml ethanol, then two kinds of solution is mixed in the polytetrafluoroethylene (PTFE) reactor of 125ml.Reactor is warming up to 140 ℃ from room temperature, continues heating 24 hours afterwards, be cooled to room temperature then and obtain solution.
Above-mentioned solution is filtered out behind the Cu-BTC blue colored crystal of generation respectively water and washed with methanol three times.At last product is placed 45 ℃ of vacuum drying ovens to continue dry 2 days, store in the drier.Specific area is 1000m
2/ g, pore volume are 0.41cm
3/ g.
More than be three monodentates of some possible coordination modes (a) of BTC and metal ion; (b) three bidentates; (c) chelating bidentate and two monodentates; (d) two chelating bidentates and a monodentate; (e) three chelating bidentates; (f) chelating/bridging bidentate and a monodentate, wherein M is copper or zinc.
Second step, synthetic Cu-BTC/PEI complex
With a certain amount of polymine (PEI) dissolved in distilled water, dilution, obtaining concentration is the PEI aqueous solution of 0.05g/ml.Get 1g Cu-BTC dissolution of crystals and in 20ml ethanol, join among the PEI aqueous solution 6ml and mix, leave standstill reaction 3～15 hours after the sealing; With reacted product vacuum drying 12 hours.Specific area is 1000～1200m
2/ g, pore volume 0.4～0.6cm
3/ g.
Embodiment 2 one-step synthesis prepare the Cu-BTC/PEI complex
With 1.7922g (7.71mmol) Cu (NO
3)
22.5H
2O is dissolved in the 24ml deionized water, 0.8806g (4.19mmol) 1,3, the 5-trimesic acid is dissolved in the 24ml ethanol, a certain amount of polymine PEI is obtained the PEI aqueous solution that concentration is 0.05g/ml with dissolved in distilled water, and the PEI aqueous solution and other two kinds of solution of getting 6ml then are mixed together in the polytetrafluoroethylene (PTFE) reactor of 125ml.Reactor is warming up to 140 ℃ from room temperature, continues heating 24 hours afterwards, be cooled to room temperature then and obtain solution.Above-mentioned solution is filtered out behind the crystal of generation respectively water and washed with methanol crystal three times.At last product is placed 45 ℃ of vacuum drying ovens to continue dry 2 days, store in the drier.
Embodiment 3 one-step synthesis prepare the Zn-BTC/PEI complex
With 2.2936g (7.71mmol) Zn (NO
3)
26H
2O is dissolved in the 24ml deionized water, 0.8806g (4.19mmol) 1,3, the 5-trimesic acid is dissolved in the 24ml ethanol, a certain amount of polymine PEI is obtained the PEI aqueous solution that concentration is 0.05g/ml with dissolved in distilled water, and the PEI aqueous solution and other two kinds of solution of getting 6ml then are mixed together in the polytetrafluoroethylene (PTFE) reactor of 125ml.Reactor is warming up to 140 ℃ from room temperature, continues heating 24 hours afterwards, be cooled to room temperature then and obtain solution.Above-mentioned solution is filtered out behind the crystal of generation respectively water and washed with methanol crystal three times.At last product is placed 45 ℃ of vacuum drying ovens to continue dry 2 days, store in the drier.
Embodiment 4 one step mixed solution synthetic method prepares the Cu-BTC/PEI complex
With 1.7922g (7.71mmol) Cu (NO
3)
22.5H
2O is dissolved in the 24ml deionized water, 0.8806g (4.19mmol) 1,3, the 5-trimesic acid is dissolved in dimethyl formamide (DMF) mixed organic solvents of 12ml ethanol and 12ml, a certain amount of polymine PEI is obtained the PEI aqueous solution that concentration is 0.05g/ml with dissolved in distilled water, and the PEI aqueous solution and other two kinds of solution of getting 6ml then are mixed together in the polytetrafluoroethylene (PTFE) reactor of 125ml.Reactor is warming up to 140 ℃ from room temperature, continues heating 24 hours afterwards, be cooled to room temperature then and obtain solution.Above-mentioned solution is filtered out behind the crystal of generation respectively water and washed with methanol crystal three times.At last product is placed 45 ℃ of vacuum drying ovens to continue dry 2 days, store in the drier.
Claims (7)
1. one kind is used for CO
2Absorption and the metal-organic framework materials that separates, it is characterized in that, metal-organic framework materials is the metal carboxyl compound bunch shape structure of the rigidity that is made of by covalent bond or intermolecular force transition metal ions and multiple tooth organic ligand, on metal-organic framework materials, be modified with amine polymer, the described CO that is used for
2Absorption is 1000～1200m with the specific area of the metal-organic framework materials that separates
2/ g, pore volume 0.4～0.6cm
3/ g.
2. the CO that is used for according to claim 1
2Absorption and the metal-organic framework materials that separates is characterized in that, described transition metal ions is Cu
2+Or Zn
2+
3. the CO that is used for according to claim 1
2Absorption and the metal-organic framework materials that separates is characterized in that, described multiple tooth organic ligand is BTC.
4. the CO that is used for according to claim 1
2Absorption and the metal-organic framework materials that separates is characterized in that, described amine polymer is a polymine, and weight average molecular weight is 25000.
5. one kind prepares the described CO of being used for of claim 1
2The method of absorption and the metal-organic framework materials that separates, it is characterized in that, prepare in two steps with hydro-thermal or solvent thermal reaction, concrete steps are: with stoichiometric proportion, elder generation is with nitrate, chloride or the carbonate and 1 of copper or zinc, 3, the equal benzene tricarbonic acid of 5-fully mixes reaction and obtains BTC bridged complex crystal together or in respectively water-soluble or the organic solvent; Then the BTC bridged complex crystal that obtains and polymine solution reaction are obtained product and be used for CO
2Absorption and the metal-organic framework materials that separates.
6. one kind prepares the described CO of being used for of claim 1
2The method of absorption and the metal-organic framework materials that separates, it is characterized in that, with hydro-thermal or the preparation of solvent thermal reaction one-step method, concrete steps are: by stoichiometric proportion, nitrate, chloride or carbonate and 1 with copper or zinc, 3, equal benzene tricarbonic acid of 5-and polymine one arise to react in water or the organic solvent and obtain being used for CO
2Absorption and the metal-organic framework materials that separates.
7. as claim 5 or the described CO that is used for of 6 described preparation claims 1
2The method of absorption and the metal-organic framework materials that separates is characterized in that, described organic solvent be in methyl alcohol, ethanol, DMF, triethylamine, ethylene glycol, the pyrimidine any one or several arbitrarily any than mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010145406A CN101816924A (en) | 2010-04-13 | 2010-04-13 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010145406A CN101816924A (en) | 2010-04-13 | 2010-04-13 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101816924A true CN101816924A (en) | 2010-09-01 |
Family
ID=42652287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010145406A Pending CN101816924A (en) | 2010-04-13 | 2010-04-13 | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101816924A (en) |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102423600A (en) * | 2011-10-28 | 2012-04-25 | 中国石油大学(北京) | Method for improving adsorption separation efficiency of CO2-containing mixed gas |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN102614737A (en) * | 2012-03-05 | 2012-08-01 | 江西师范大学 | Method for gas storage and release of metal-organic framework material |
| CN102728331A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
| CN102921377A (en) * | 2012-06-01 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nitrogen-rich ZMOF type metal-organic framework porous material |
| CN103007889A (en) * | 2012-12-31 | 2013-04-03 | 湖南大学 | Preparation method of metal-organic frame material La-BDC adsorbing CO2 and modified product of metal-organic frame material La-BDC |
| CN103285827A (en) * | 2013-05-09 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide capture material as well as preparation method and applications thereof |
| CN103418164A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for removing oxygen-containing compound in hydrocarbon stream |
| CN103626655A (en) * | 2013-11-27 | 2014-03-12 | 安徽大学 | Preparation method of exposed crystal face controllable metal-organic framework material |
| CN103736455A (en) * | 2013-12-13 | 2014-04-23 | 北京化工大学常州先进材料研究院 | Copper-iron modified metal organic skeleton adsorbent and preparation method thereof |
| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| CN104785210A (en) * | 2015-04-16 | 2015-07-22 | 南京信息工程大学 | Polyamine-modified UiO-66 composite adsorbent capable of efficiently purifying trace phosphorus and arsenic in water, and preparation method for adsorbent |
| CN105056895A (en) * | 2015-08-17 | 2015-11-18 | 中国科学院上海高等研究院 | Preparation method and application of metal organic frameworks-mesoporous silica composite material |
| CN105536574A (en) * | 2015-12-15 | 2016-05-04 | 中能科泰（北京）科技有限公司 | Filter membrane as well as preparation method and application |
| CN106117593A (en) * | 2016-06-16 | 2016-11-16 | 南京工业大学 | A kind of method preparing nano material@metal-organic framework materials |
| CN106457120A (en) * | 2014-04-22 | 2017-02-22 | 加利福尼亚大学董事会 | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
| CN106622150A (en) * | 2017-02-25 | 2017-05-10 | 华南理工大学 | C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof |
| CN106673992A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院大连化学物理研究所 | Bimetal organic framework material as well as preparation and application thereof |
| CN106807329A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | The preparation and composite and application of NACF-metal organic frame composite |
| CN108314788A (en) * | 2018-03-23 | 2018-07-24 | 北京工业大学 | A kind of method that in-situ polymerization prepares copolymer/HKUST-1 hybrid materials |
| CN108409977A (en) * | 2018-02-26 | 2018-08-17 | 武汉大学 | Synthesis with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture |
| CN108786755A (en) * | 2018-05-30 | 2018-11-13 | 浙江大学 | A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application |
| CN109642094A (en) * | 2016-08-23 | 2019-04-16 | 巴斯夫欧洲公司 | Composite material |
| CN109701498A (en) * | 2019-01-29 | 2019-05-03 | 河南中烟工业有限责任公司 | A kind of MOF-Cu@porous-starch composite material and preparation method and the application in cigarette |
| CN110270315A (en) * | 2019-07-01 | 2019-09-24 | 香港中文大学（深圳） | MOF- polymer composites, preparation method and application |
| CN110723720A (en) * | 2019-10-16 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Light broadband electromagnetic wave absorbing material and preparation method thereof |
| CN111093824A (en) * | 2017-08-04 | 2020-05-01 | 加利福尼亚大学董事会 | Metal-organic framework with attached cyclic diamine for carbon dioxide capture |
| CN111511466A (en) * | 2017-12-28 | 2020-08-07 | 株式会社可乐丽 | Adsorption filter |
| CN111821955A (en) * | 2020-07-31 | 2020-10-27 | 武汉汇碳科技有限公司 | For CO2Adsorption separated composite material and preparation method thereof |
| CN113578063A (en) * | 2021-07-30 | 2021-11-02 | 浙江迪萧科技有限公司 | Preparation method of novel multilayer solvent-resistant composite membrane |
| CN113617334A (en) * | 2021-08-10 | 2021-11-09 | 黑龙江省科学院石油化学研究院 | Preparation method of metal organic framework material |
| CN113651969A (en) * | 2021-08-23 | 2021-11-16 | 山东能源集团有限公司 | Metal-organic framework material modified by organic amine cations and preparation method thereof |
| CN114479095A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Cu-based metal-organic framework material and preparation method and application thereof |
| CN114849665A (en) * | 2022-04-29 | 2022-08-05 | 浙江大学 | Amino metal organic framework adsorbent capable of adsorbing carbon dioxide in air and preparation and application thereof |
| CN116173749A (en) * | 2022-12-03 | 2023-05-30 | 天津工业大学 | Preparation method of high-performance porous coordination polymer membrane |
| CN116603513A (en) * | 2023-06-12 | 2023-08-18 | 深碳科技(深圳)有限公司 | Solid amine adsorbent and preparation method thereof |
| US11845058B2 (en) | 2011-10-18 | 2023-12-19 | The Regents Of The University Of California | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617761A (en) * | 2002-02-01 | 2005-05-18 | 巴斯福股份公司 | Method for storing, absorbing and emitting gases using novel framework materials |
| WO2008082087A1 (en) * | 2007-01-03 | 2008-07-10 | Insilicotech Co., Ltd | Coordination polymer crystal with porous metal-organic frameworks and preperation method thereof |
| CN101330978A (en) * | 2005-11-14 | 2008-12-24 | 巴斯夫欧洲公司 | Porous organo-metallic skeleton material containing an additional polymer |
| US20090178558A1 (en) * | 2008-01-04 | 2009-07-16 | Northwestren University | Gas adsorption and gas mixture separatoins using mixed-ligand MOF material |
| US7637983B1 (en) * | 2006-06-30 | 2009-12-29 | Uop Llc | Metal organic framework—polymer mixed matrix membranes |
-
2010
- 2010-04-13 CN CN201010145406A patent/CN101816924A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1617761A (en) * | 2002-02-01 | 2005-05-18 | 巴斯福股份公司 | Method for storing, absorbing and emitting gases using novel framework materials |
| CN101330978A (en) * | 2005-11-14 | 2008-12-24 | 巴斯夫欧洲公司 | Porous organo-metallic skeleton material containing an additional polymer |
| US7637983B1 (en) * | 2006-06-30 | 2009-12-29 | Uop Llc | Metal organic framework—polymer mixed matrix membranes |
| WO2008082087A1 (en) * | 2007-01-03 | 2008-07-10 | Insilicotech Co., Ltd | Coordination polymer crystal with porous metal-organic frameworks and preperation method thereof |
| US20090178558A1 (en) * | 2008-01-04 | 2009-07-16 | Northwestren University | Gas adsorption and gas mixture separatoins using mixed-ligand MOF material |
Non-Patent Citations (1)
| Title |
|---|
| 《安徽教育学院学报》 20071130 李健 金属有机多孔配位聚合物的控制合成研究进展 第60-62页 5-7 第25卷, 第6期 2 * |
Cited By (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11845058B2 (en) | 2011-10-18 | 2023-12-19 | The Regents Of The University Of California | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
| CN102423600A (en) * | 2011-10-28 | 2012-04-25 | 中国石油大学(北京) | Method for improving adsorption separation efficiency of CO2-containing mixed gas |
| CN102617646A (en) * | 2012-02-29 | 2012-08-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of nanoscale metal organic framework materials |
| CN102614737A (en) * | 2012-03-05 | 2012-08-01 | 江西师范大学 | Method for gas storage and release of metal-organic framework material |
| CN102614737B (en) * | 2012-03-05 | 2014-06-25 | 江西师范大学 | Method for gas storage and release of metal-organic framework material |
| CN103418164B (en) * | 2012-05-16 | 2015-07-08 | 中国石油化工股份有限公司 | Method for removing oxygen-containing compound in hydrocarbon stream |
| CN103418164A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for removing oxygen-containing compound in hydrocarbon stream |
| CN102921377B (en) * | 2012-06-01 | 2015-07-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nitrogen-rich ZMOF type metal-organic framework porous material |
| CN102921377A (en) * | 2012-06-01 | 2013-02-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nitrogen-rich ZMOF type metal-organic framework porous material |
| CN102728331A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
| CN102728331B (en) * | 2012-07-20 | 2014-10-29 | 清华大学深圳研究生院 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
| CN103007889B (en) * | 2012-12-31 | 2014-08-13 | 湖南大学 | Preparation method of metal-organic frame material La-BDC adsorbing CO2 and modified product of metal-organic frame material La-BDC |
| CN103007889A (en) * | 2012-12-31 | 2013-04-03 | 湖南大学 | Preparation method of metal-organic frame material La-BDC adsorbing CO2 and modified product of metal-organic frame material La-BDC |
| CN103285827A (en) * | 2013-05-09 | 2013-09-11 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide capture material as well as preparation method and applications thereof |
| CN104415670A (en) * | 2013-08-23 | 2015-03-18 | 中国科学院宁波材料技术与工程研究所 | Metal organic framework membrane and preparation method and application thereof |
| CN103626655A (en) * | 2013-11-27 | 2014-03-12 | 安徽大学 | Preparation method of exposed crystal face controllable metal-organic framework material |
| CN103736455A (en) * | 2013-12-13 | 2014-04-23 | 北京化工大学常州先进材料研究院 | Copper-iron modified metal organic skeleton adsorbent and preparation method thereof |
| CN106457120A (en) * | 2014-04-22 | 2017-02-22 | 加利福尼亚大学董事会 | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
| CN104785210A (en) * | 2015-04-16 | 2015-07-22 | 南京信息工程大学 | Polyamine-modified UiO-66 composite adsorbent capable of efficiently purifying trace phosphorus and arsenic in water, and preparation method for adsorbent |
| CN105056895A (en) * | 2015-08-17 | 2015-11-18 | 中国科学院上海高等研究院 | Preparation method and application of metal organic frameworks-mesoporous silica composite material |
| CN106673992A (en) * | 2015-11-11 | 2017-05-17 | 中国科学院大连化学物理研究所 | Bimetal organic framework material as well as preparation and application thereof |
| CN106807329A (en) * | 2015-11-27 | 2017-06-09 | 中国科学院大连化学物理研究所 | The preparation and composite and application of NACF-metal organic frame composite |
| CN106807329B (en) * | 2015-11-27 | 2019-07-02 | 中国科学院大连化学物理研究所 | The preparation of activated carbon fibre-metal organic frame composite material and composite material and application |
| CN105536574B (en) * | 2015-12-15 | 2019-12-03 | 中能科泰（北京）科技有限公司 | Filter membrane and its preparation method and application |
| CN105536574A (en) * | 2015-12-15 | 2016-05-04 | 中能科泰（北京）科技有限公司 | Filter membrane as well as preparation method and application |
| CN106117593A (en) * | 2016-06-16 | 2016-11-16 | 南京工业大学 | A kind of method preparing nano material@metal-organic framework materials |
| CN106117593B (en) * | 2016-06-16 | 2019-07-16 | 南京工业大学 | A method of preparing nano material@metal-organic framework materials |
| CN109642094A (en) * | 2016-08-23 | 2019-04-16 | 巴斯夫欧洲公司 | Composite material |
| CN106622150A (en) * | 2017-02-25 | 2017-05-10 | 华南理工大学 | C2H3N@Ni(2-MTPA)(TED)0.5 material capable of adsorbing ethane preferentially, and preparation method thereof |
| CN111093824B (en) * | 2017-08-04 | 2023-05-26 | 加利福尼亚大学董事会 | Cyclic diamine-attached metal-organic frameworks for carbon dioxide capture |
| CN111093824A (en) * | 2017-08-04 | 2020-05-01 | 加利福尼亚大学董事会 | Metal-organic framework with attached cyclic diamine for carbon dioxide capture |
| CN111511466B (en) * | 2017-12-28 | 2022-06-24 | 株式会社可乐丽 | Adsorption filter |
| CN111511466A (en) * | 2017-12-28 | 2020-08-07 | 株式会社可乐丽 | Adsorption filter |
| CN108409977A (en) * | 2018-02-26 | 2018-08-17 | 武汉大学 | Synthesis with the adjustable Ni bases MOF nano particles in low cytotoxicity aperture |
| CN108314788A (en) * | 2018-03-23 | 2018-07-24 | 北京工业大学 | A kind of method that in-situ polymerization prepares copolymer/HKUST-1 hybrid materials |
| CN108786755A (en) * | 2018-05-30 | 2018-11-13 | 浙江大学 | A kind of metal organic frame-porous polymer composite material and preparation method of organic amine load and application |
| CN108786755B (en) * | 2018-05-30 | 2020-08-04 | 浙江大学 | Organic amine loaded metal organic framework-porous polymer composite material and preparation method and application thereof |
| CN109701498A (en) * | 2019-01-29 | 2019-05-03 | 河南中烟工业有限责任公司 | A kind of MOF-Cu@porous-starch composite material and preparation method and the application in cigarette |
| CN110270315A (en) * | 2019-07-01 | 2019-09-24 | 香港中文大学（深圳） | MOF- polymer composites, preparation method and application |
| CN110723720A (en) * | 2019-10-16 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Light broadband electromagnetic wave absorbing material and preparation method thereof |
| CN111821955A (en) * | 2020-07-31 | 2020-10-27 | 武汉汇碳科技有限公司 | For CO2Adsorption separated composite material and preparation method thereof |
| CN111821955B (en) * | 2020-07-31 | 2023-03-21 | 武汉汇碳科技有限公司 | For CO 2 Adsorption separated composite material and preparation method thereof |
| CN114479095A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Cu-based metal-organic framework material and preparation method and application thereof |
| CN114479095B (en) * | 2020-10-26 | 2023-08-08 | 中国石油化工股份有限公司 | Cu-based metal-organic framework material and preparation method and application thereof |
| CN113578063A (en) * | 2021-07-30 | 2021-11-02 | 浙江迪萧科技有限公司 | Preparation method of novel multilayer solvent-resistant composite membrane |
| CN113617334A (en) * | 2021-08-10 | 2021-11-09 | 黑龙江省科学院石油化学研究院 | Preparation method of metal organic framework material |
| CN113651969B (en) * | 2021-08-23 | 2023-02-21 | 山东能源集团有限公司 | Metal-organic framework material modified by organic amine cations and preparation method thereof |
| CN113651969A (en) * | 2021-08-23 | 2021-11-16 | 山东能源集团有限公司 | Metal-organic framework material modified by organic amine cations and preparation method thereof |
| CN114849665A (en) * | 2022-04-29 | 2022-08-05 | 浙江大学 | Amino metal organic framework adsorbent capable of adsorbing carbon dioxide in air and preparation and application thereof |
| CN116173749A (en) * | 2022-12-03 | 2023-05-30 | 天津工业大学 | Preparation method of high-performance porous coordination polymer membrane |
| CN116603513A (en) * | 2023-06-12 | 2023-08-18 | 深碳科技(深圳)有限公司 | Solid amine adsorbent and preparation method thereof |
| CN116603513B (en) * | 2023-06-12 | 2024-02-20 | 深碳科技(深圳)有限公司 | Solid amine adsorbent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101816924A (en) | Metal organic framework material used for absorbing and separating CO2 and preparation method thereof | |
| Abid et al. | Nanosize Zr-metal organic framework (UiO-66) for hydrogen and carbon dioxide storage | |
| Chaemchuen et al. | Metal–organic frameworks for upgrading biogas via CO 2 adsorption to biogas green energy | |
| US11066435B2 (en) | Green methods for preparing highly CO2 selective and H2S tolerant metal organic frameworks | |
| Abdelhamid | Removal of carbon dioxide using zeolitic imidazolate frameworks: adsorption and conversion via catalysis | |
| Augustus et al. | Metal-organic frameworks as novel adsorbents: A preview | |
| Ghosh et al. | Recent progress in materials development for CO 2 conversion: issues and challenges | |
| D'Alessandro et al. | Toward carbon dioxide capture using nanoporous materials | |
| CN101816925B (en) | Organic-inorganic hybrid material for CO2 adsorption and preparation method thereof | |
| CN106268652B (en) | A kind of preparation method of the heavy metal chelating agent based on MOFs | |
| CN105233802A (en) | Copper-based metal organic framework material doped with L-arginine and preparation method of copper-based metal organic framework material | |
| CN109420479B (en) | Ion hybrid porous material and preparation method and application thereof | |
| CN103435620B (en) | Porous copper organic framework material for CO2 adsorption and separation and preparation method of porous copper organic framework material | |
| Shan et al. | A cobalt metal‐organic framework with small pore size for adsorptive separation of CO2 over N2 and CH4 | |
| CN103203159A (en) | Method for separating nitrous oxide and carbon dioxide by using zeolite-like molecular sieve skeleton material | |
| CN104226260A (en) | Preparation and modification methods of metal-organic frame material Bi-BTC for adsorbing CO2 | |
| Ahmad et al. | Porous liquids–Future for CO2 capture and separation? | |
| CN115536857A (en) | Zinc-organic framework material for selectively adsorbing carbon dioxide and synthesis method | |
| EP2907569B1 (en) | Regeneration method for cu-btc material | |
| Gan et al. | Adsorptive Separation of CO2 by a Hydrophobic Carborane-Based Metal–Organic Framework under Humid Conditions | |
| Yu et al. | Review and Perspectives of Monolithic Metal–Organic Frameworks: Toward Industrial Applications | |
| WO2014122105A1 (en) | Ultraporous metal organic framework materials and method for their production | |
| KR20230019445A (en) | How to purify hydrogen used in fuel cells | |
| Ding et al. | Pore engineering of metal–organic frameworks for boosting low-pressure CO 2 capture | |
| KR102075341B1 (en) | Isoreticular series of metal-organic polyhedra and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100901 |