CN102728331B - Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane - Google Patents
Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane Download PDFInfo
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- CN102728331B CN102728331B CN201210252943.4A CN201210252943A CN102728331B CN 102728331 B CN102728331 B CN 102728331B CN 201210252943 A CN201210252943 A CN 201210252943A CN 102728331 B CN102728331 B CN 102728331B
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- 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
Abstract
The invention discloses a preparation method of a metal-organic framework material for adsorbing separation of carbon dioxide/ methane. The preparation method comprises the following steps of: (1) mixing 0.46-1.16mol/L cupric nitrate water solution and 0.23-0.58mol/L trimesic acid ethanol solution, fully stirring, then adding into a stainless steel reaction kettle provided with a polytetrafluoroethylene inner liner for sealing, and carrying out solvent thermal reaction while controlling the crystallization temperature to be 60-150 DEG C and the crystallization time at 12-24h; (2) opening the stainless steel reaction kettle, filtering, sequentially washing by methyl alcohol and deionized water, and drying at the temperature of 80-105 DEG C to obtain blue crystal; and (3) vacuumizing the blue crystal at the temperature of 150-200 DEG C to obtain the Cu-containing metal-organic framework material.
Description
Technical field
The invention belongs to environmental protection technical field, particularly a kind of preparation method of metal-organic framework materials of adsorbing separation carbon dioxide/methane.
Background technology
Carbon dioxide be in biogas rubbish landfill gas except methane the highest component of content, account for 30% ~ 40% of biogas composition.The existence of carbon dioxide in methane greatly reduces the calorific value of biogas combustion, can utilization ratio reduce.Thereby in marsh gas purifying technology, realize the separation of methane and carbon dioxide to obtain highly purified methane, and be to promote energy utilization efficiency, output high grade product, the demand of lifting biogas economic worth.
In the last few years, there is part Study scholar to be studied biogas removal of impurities, purification and high-value-use technology, aspect adsorption/absorption agent exploitation, equipment for purifying and technological design, all obtained a lot of significant achievements.For example, Chinese patent 200610096998.5 discloses a kind of marsh gas purifying, pressurized storage and delivery technology method: the aqueous slkali that this invention mixes with quick lime and water, or sodium hydroxide solution removes the impurity such as carbon dioxide in biogas, hydrogen sulfide, steam, can reach more than 70% thereby improve methane content.This liquid-like phase absorption process is often brought secondary pollution, and separative efficiency is also relatively low.
In addition, absorption method is also one of effective technology that gas separates, and its core is to select and development high-efficiency adsorbent, and it is large, selective strong and regeneration is convenient that desirable sorbing material has adsorption capacity.Be directed to the separation problem of methane and carbon dioxide gas mixture, Chinese patent 00104481.8 discloses a kind of molecular sieve carbon fabric and preparation method thereof separating for methane and carbon dioxide: carry out after charing for raw material with the cured fiber of polypropylene, viscose rayon, phenolic fibre, pitch fibers etc., carry out activation processing with steam and make textile-like carbon molecular sieve, for methane and carbon dioxide separation process, separate the methane gas purity obtaining and exceed 96%.Chinese patent application 201110295013.2 also discloses the method for carbon dioxide in a kind of pressure-variable adsorption separation and purifying biogas.Adsorbent used is the compound adsorbent of active carbon, particulate iron oxide or calcium oxide, silica gel composition, and adsorption capacity is not high enough, thereby eight adsorption towers need to be set, each adsorption column pressure that cyclically variation is combined, and operating process is very loaded down with trivial details.
The metal-organic framework materials (MOFs) that obtained in recent years paying close attention to is a kind of novel porous material, formed by metal ion and organic ligand self assembly, there is the feature such as high porosity, bigger serface, in preparation process, regulate and control by size, shape and the surface characteristic of selecting different metal ion, organic ligand molecule can realize hole, thereby having a good application prospect aspect gas separation.
Chinese patent application 200780005157.1 discloses a kind of method of the metal-organic framework materials of preparing porous, the method requires a kind of not containing the copper compound of the crystallization water and the organic compound of at least one bidentate, reaction under non-aqueous solvent exists, carries out at atmospheric pressure with at higher than 80 DEG C.Chinese patent application 201010145406.0 discloses a kind of for carbon dioxide absorption and metal-organic framework materials separating and preparation method thereof, the method first nitrate, chloride or carbonate and 1 with copper or zinc, 3, the equal benzene tricarbonic acid of 5-reacts and has prepared a kind of metal-organic framework materials, and then obtain a kind of adsorbent with polymine solution reaction, for the absorption of carbon dioxide with separate, for carbon dioxide from the low pressure absorption in vacuum to barometric pressure range.
Chinese patent application 200680048735.5 discloses the application of a kind of MOF in pressure oscillating absorption, the method flows hydrogen at 2MPa ~ 5MPa(20-50 atmospheric pressure) elevated pressures under, to the absorption of methane, comprise multiple adsorbent beds and made pressure sequence by bed and circulated to form the complex process of continuous process.
Above-mentioned preparation or gas separation process often require preparation process to adopt nonaqueous solvents, or will use virose aziridine modification, or relate to the processing mist separation process of high pressure, and step is complicated and improved the use cost of sorbing material.
Summary of the invention
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, propose a kind of preparation method of metal-organic framework materials of adsorbing separation carbon dioxide/methane.
Technical problem of the present invention is solved by following technical scheme:
A preparation method for the metal-organic framework materials of adsorbing separation carbon dioxide/methane, comprises the steps:
(1) the trimesic acid ethanolic solution of the copper nitrate aqueous solution of 0.46 ~ 1.16 mol/L and 0.23 ~ 0.58 mol/L is mixed, after fully stirring, add in band teflon-lined stainless steel cauldron and seal, controlling crystallizing temperature is that 60 ~ 150 DEG C and crystallization time are within 12 ~ 24 hours, to carry out solvent thermal reaction;
(2) open stainless steel cauldron, after filtration, and successively with methyl alcohol and deionized water washing, the dry blue colored crystal that obtains at 80 ~ 105 DEG C;
(3) described blue colored crystal is vacuumized at 150 ~ 200 DEG C to processing and obtain copper-containing metal organic framework material.
The present invention adopts solvent-thermal method, taking the aqueous solution of copper nitrate and the ethanolic solution of trimesic acid as initial feed, having in teflon-lined stainless steel cauldron, in the mixed solvent of water and ethanol, under certain crystallization temperature and crystallization time condition, synthetic solid is washed and is dried through methyl alcohol and deionized water, control certain baking temperature, again at a certain temperature through vacuumizing, under the acting in conjunction of a series of conditions of above each step, finally obtain having the copper-containing metal organic framework material of high-specific surface area, it is blue colored crystal sprills shape.
Preferably, the temperature in described step (3) is 160-180 DEG C.
A kind of metal-organic framework materials, is made by the preparation method described in above-mentioned any one, and its specific area is 500 ~ 1200 m
2/ g.
The application of above-mentioned metal-organic framework materials in adsorbing separation carbon dioxide/methane, wherein, adsorptive pressure is 0.1MPa ~ 0.4MPa, and adsorption temp is-15 DEG C ~ 85 DEG C, and the volume fraction of methane and carbon dioxide carbon dioxide in gas mixture is 5% ~ 60%.
When the application of above-mentioned metal-organic framework materials in adsorbing separation carbon dioxide/methane, experimental results show that, under above adsorptive pressure, adsorption temp condition, one pack system adsorption capacity to methane, carbon dioxide is large, methane and carbon dioxide gas mixture for certain gas concentration lwevel scope have high pressure-variable adsorption Selective Separation effect: for example, experimental results show that, under 25 DEG C and 0.4 MPa pressure, this material can reach respectively 8.01mmol/g and 3.40mmol/g to the one pack system adsorption capacity of carbon dioxide and methane; Under 25 DEG C and 0.4 MPa pressure, this material has good separating power to the methane/carbon dioxide gaseous mixture of different proportionings, and can obtain purity is 99%(volume fraction) above methane gas.
The further tool of the present invention has the following advantages: for isolation of purified methane and carbon dioxide gas mixture provide effective a, technology easily, related adsorption technology there is the advantages such as pressure is low, energy consumption is low, sorbing material is non-toxic, environmental benefit is good and operating procedure simple, material is renewable to be reused, and has good use tolerance.
Brief description of the drawings
Fig. 1 is the X-ray diffraction spectrogram of the preparation-obtained copper-containing metal framework material of the embodiment of the present invention one.
Detailed description of the invention
Contrast accompanying drawing below and in conjunction with preferred embodiment, the present invention be explained in detail.
The invention provides a kind of preparation method of metal-organic framework materials of adsorbing separation carbon dioxide/methane, in one embodiment, comprise the steps:
(1) by the equal benzene of trimesic acid (1,3,5-Benzenetricarboxylic Acid, the C of the copper nitrate aqueous solution of 0.46 ~ 1.16 mol/L and 0.23 ~ 0.58 mol/L
9h
6o
6, note by abridging as H
3btc) ethanolic solution mixes, and adds in band teflon-lined stainless steel cauldron and seal after fully stirring, and controlling crystallizing temperature is that 60 ~ 150 DEG C and crystallization time are within 12 ~ 24 hours, to carry out solvent thermal reaction;
(2) open stainless steel cauldron, after filtration, and successively with methyl alcohol and deionized water washing, the dry blue colored crystal that obtains at 80 ~ 105 DEG C;
(3) described blue colored crystal is vacuumized at 150 ~ 200 DEG C to processing and obtain copper-containing metal organic framework material.
Temperature in preferred described step (3) is 160-180 DEG C.
2-10h drying time in preferred steps (2).
Pumpdown time in preferred steps (3) is 3-15h.
The present invention also provides a kind of metal-organic framework materials, is made by above-mentioned preparation method, and its specific area is 500 ~ 1200 m
2/ g.
For more specific description content of the present invention, below provide preferred embodiment.
embodiment mono-
Take a certain amount of Cu (NO
3)
23H
2o, is dissolved in a certain amount of deionized water, and being mixed with concentration is the 25ml Cu (NO of 1.16 mol/L
3)
23H
2the O aqueous solution, is labeled as solution I; Compound concentration is the 25ml H of 0.58 mol/L
3the ethanolic solution of btc, is labeled as solution II; Solution I and solution II are mixed, after fully stirring, pack in the band teflon-lined stainless steel cauldron that capacity is 100ml, 95 DEG C of crystallization 15 hours, after filtration, wash three times by methyl alcohol and deionized water successively, each 50ml, fully stir 10min, 105 DEG C are dried 10 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 10 hours at 175 DEG C, and recording specific area is 1136m
2/ g, as shown in Figure 1, in figure, 2 θ angles are 6.72 °, 9.56 °, 11.70 °, 13.48 °, 14.70 °, 16.5 °, 17.54 ° and locate to occur characteristic peaks X ray diffracting spectrum (XRD), show that this material has typical metal organic frame material structure.
embodiment bis-
Be with the difference of embodiment mono-: in band teflon-lined stainless steel cauldron, crystallization 15 hours at 60 DEG C, washs three times by methyl alcohol and deionized water after filtration successively, each 50ml, fully stir 10min, 80 DEG C are dried 2 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 3 hours at 150 DEG C, and recording specific area is 539m
2/ g.
embodiment tri-
Be with the difference of embodiment mono-: in band teflon-lined stainless steel cauldron, crystallization 15 hours at 150 DEG C, washs three times by methyl alcohol and deionized water after filtration successively, each 50ml, fully stir 10min, 105 DEG C are dried 10 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 15 hours at 200 DEG C, and recording specific area is 967m
2/ g.
embodiment tetra-
Be with the difference of embodiment mono-: in band teflon-lined stainless steel cauldron, crystallization 12 hours at 95 DEG C, washs three times by methyl alcohol and deionized water after filtration successively, each 50ml, fully stir 10min, 105 DEG C are dried 10 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 10 hours at 160 DEG C, and recording specific area is 1025m
2/ g.
embodiment five
Compound concentration is the 25ml Cu (NO of 1.16 mol/L
3)
23H
2the O aqueous solution, is labeled as solution I; Compound concentration is the 25ml H of 0.58 mol/L
3the ethanolic solution of btc, is labeled as solution II; Solution I and solution II are mixed, after fully stirring 45min, pack in the band teflon-lined stainless steel cauldron that capacity is 100ml, crystallization 24 hours at 95 DEG C, after filtration, wash three times by methyl alcohol and deionized water successively, each 50ml, fully stir 10min, 105 DEG C are dried 10 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 10 hours at 180 DEG C, and recording specific area is 1111m
2/ g.
embodiment six
Be with the difference of embodiment mono-: in band teflon-lined stainless steel cauldron, 95 DEG C of crystallization 15 hours, after filtration successively with methyl alcohol and deionized water washing three times, each 50ml, fully stir 10min, 105 DEG C are dried 10 hours, obtain blue colored crystal.Gained blue colored crystal vacuumizes and processes 10 hours at 175 DEG C, and recording specific area is 866m
2/ g.
The present invention also provides the application in adsorbing separation carbon dioxide/methane of metal-organic framework materials that a kind of above-mentioned any one embodiment prepares, wherein, adsorptive pressure is 0.1MPa ~ 0.4MPa, adsorption temp is-15 DEG C ~ 85 DEG C, and the volume fraction of methane and carbon dioxide carbon dioxide in gas mixture is 5% ~ 60%.
It is-15 DEG C ~ 85 DEG C that the present invention packs metal-organic framework materials into adsorption temp; adsorptive pressure is in the pressure-swing absorption apparatus of 0.1MPa ~ 0.4MPa; pass into pure carbon dioxide or pure methane gas; measure the variation of pressure in adsorbent bed, thereby obtain adsorption capacity and the adsorption isotherm of adsorbent to pure gas under different pressures condition; For admixture of gas, it is-15 DEG C ~ 85 DEG C that the present invention packs metal-organic framework materials into adsorption temp, adsorptive pressure is in the pressure-swing absorption apparatus of 0.1MPa ~ 0.4MPa, using helium as carrier gas, pass into gas concentration lwevel and be 5% ~ 60% methane/carbon dioxide gaseous mixture, utilize the composition of gas chromatographic measurement adsorbent bed exit gas, obtain breakthrough curve and the adsorptive selectivity of gas.
Describe by specific embodiment below.
embodiment seven
By the copper-containing metal framework material 0.6g making in embodiment mono-, at 175 DEG C, vacuumize process pack into after 10 hours variable-pressure adsorption bed in, at 85 DEG C, pass into pure carbon dioxide or methane gas, under 0.4MPa pressure, this material up to 6.40mmol/g, is 2.55mmol/g to the adsorption capacity of methane to the adsorption capacity of carbon dioxide.
embodiment eight
By the copper-containing metal framework material 0.6g making in embodiment mono-, at 175 DEG C, vacuumize process pack into after 10 hours variable-pressure adsorption bed in, at-15 DEG C, pass into pure carbon dioxide or methane gas, under 0.4MPa pressure, this material up to 9.40mmol/g, is 3.90mmol/g to the adsorption capacity of methane to the adsorption capacity of carbon dioxide.
embodiment nine
By the copper-containing metal framework material 14g making in embodiment mono-, at 175 DEG C, vacuumize process pack into after 10 hours variable-pressure adsorption bed in, keep the operating pressure of 0.4MPa in adsorbent bed taking helium as carrier gas, pass into carbon dioxide volumetric concentration and be 60% methane/carbon dioxide gaseous mixture, change with gas chromatographic detection gas componant in adsorbent bed outlet; To select methane or carbon dioxide exit concentration be initial concentration 50% time is breakthrough point, obtains methane and penetrates in the time of 7.3 minutes, and carbon dioxide penetrated at 16.5 minutes, thereby the adsorptive selectivity that can be calculated carbon dioxide/methane blended gas is 3.10.
embodiment ten
By the copper-containing metal framework material 14g making in embodiment mono-, at 175 DEG C, vacuumize process pack into after 10 hours variable-pressure adsorption bed in, keep the operating pressure of 0.4MPa in adsorbent bed taking helium as carrier gas, pass into gas concentration lwevel and be 5% methane/carbon dioxide gaseous mixture, change with gas chromatographic detection gas componant in adsorbent bed outlet, draw breakthrough curve; To select methane or carbon dioxide exit concentration be initial concentration 50% time is breakthrough point, obtains methane and penetrates in the time of 5.7 minutes, and carbon dioxide penetrated at 32.9 minutes, thereby the adsorptive selectivity that can be calculated carbon dioxide/methane blended gas is 10.76.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make some being equal to substitute or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (3)
1. a preparation method for the metal-organic framework materials of adsorbing separation carbon dioxide/methane, is characterized in that, comprises the steps:
(1) the trimesic acid ethanolic solution of the copper nitrate aqueous solution of 0.46～1.16mol/L and 0.23～0.58mol/L is mixed, after fully stirring, add in band teflon-lined stainless steel cauldron and seal, controlling crystallizing temperature is that 60～150 DEG C and crystallization time are within 12～24 hours, to carry out solvent thermal reaction;
(2) open stainless steel cauldron, after filtration, and successively with methyl alcohol and deionized water washing, the dry blue colored crystal that obtains at 80～105 DEG C;
(3) described blue colored crystal is vacuumized at 160-180 DEG C to processing and obtain copper-containing metal organic framework material, the specific area of described copper-containing metal organic framework material is 500～1200m
2/ g.
2. a metal-organic framework materials, is characterized in that: made by preparation method claimed in claim 1, its specific area is 500～1200m
2/ g.
3. the application of metal-organic framework materials claimed in claim 2 in adsorbing separation carbon dioxide/methane, it is characterized in that: adsorptive pressure is 0.4MPa, adsorption temp is-15 DEG C～85 DEG C, and the volume fraction of methane and carbon dioxide carbon dioxide in gas mixture is 5%～60%.
Priority Applications (2)
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| CN201210252943.4A CN102728331B (en) | 2012-07-20 | 2012-07-20 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
| HK12112979.6A HK1171981A1 (en) | 2012-07-20 | 2012-12-14 | Preparation method of metal organic skeleton material |
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|---|---|---|---|
| CN201210252943.4A CN102728331B (en) | 2012-07-20 | 2012-07-20 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
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| Publication Number | Publication Date |
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| CN102728331A CN102728331A (en) | 2012-10-17 |
| CN102728331B true CN102728331B (en) | 2014-10-29 |
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| HK (1) | HK1171981A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622139A (en) * | 2015-11-03 | 2017-05-10 | 中国石油化工股份有限公司 | Metal organic framework material and preparation method and application thereof |
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| CN103691399B (en) * | 2013-12-18 | 2016-01-20 | 北京科技大学 | For separating of the preparation method of the high-performance carbon molecular sieve of carbon dioxide/methane |
| CN105312026B (en) * | 2014-07-09 | 2017-10-31 | 江苏瑞丰科技实业有限公司 | Normal temperature methane efficient absorption material |
| CN105669593B (en) * | 2014-11-19 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of preparation method of barium Base Metal organic framework material |
| CN106693896B (en) * | 2015-11-12 | 2019-11-08 | 中国科学院大连化学物理研究所 | Heterogeneous Composite structure adsorbent material and its preparation and application |
| CN107376997B (en) * | 2017-07-04 | 2020-11-10 | 常州大学 | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol |
| CN108163936A (en) * | 2017-12-26 | 2018-06-15 | 南开大学 | A kind of electrode based on metal-organic framework materials and preparation method thereof |
| CN112121652B (en) * | 2020-09-28 | 2022-03-11 | 郑州轻工业大学 | Preparation method of metal organic framework-ceramic membrane nanofiltration composite membrane |
| CN112619611B (en) * | 2020-12-11 | 2022-06-07 | 太原理工大学 | Acetylene efficient separation material |
| CN113426416B (en) * | 2021-05-25 | 2022-08-26 | 浙江大学 | MOFs material with efficient water collection performance, preparation method thereof and application of MOFs material in water taking from air |
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| CN106622139A (en) * | 2015-11-03 | 2017-05-10 | 中国石油化工股份有限公司 | Metal organic framework material and preparation method and application thereof |
| CN106622139B (en) * | 2015-11-03 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of metal-organic framework materials and the preparation method and application thereof |
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|---|---|
| CN102728331A (en) | 2012-10-17 |
| HK1171981A1 (en) | 2013-04-12 |
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