CN102728331A - 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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- CN102728331A CN102728331A CN2012102529434A CN201210252943A CN102728331A CN 102728331 A CN102728331 A CN 102728331A CN 2012102529434 A CN2012102529434 A CN 2012102529434A CN 201210252943 A CN201210252943 A CN 201210252943A CN 102728331 A CN102728331 A CN 102728331A
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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 the biogas rubbish landfill gas except that methane the highest component of content, account for 30% ~ 40% of biogas composition.The existence of carbon dioxide greatly reduces the calorific value of biogas burning in the biogas, and the utilization ratio of its energy is reduced.Thereby in the marsh gas purifying technology, realize separating 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 had been the part Study scholar that biogas removal of impurities, purification and high-value-use technology are studied, all obtained a lot of significant achievements aspect adsorption/absorption agent exploitation, equipment for purifying and the technological design.For example; Chinese patent 200610096998.5 discloses a kind of marsh gas purifying, pressurization stores and the delivery technology method: the aqueous slkali that this invention mixes with quick lime and water; Or sodium hydroxide solution removes impurity such as carbon dioxide in the 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 also is one of effective technology of separating of gas, and its core is to select and the development high-efficiency adsorbent, and desirable sorbing material has that adsorption capacity is big, selectivity strong and regeneration is convenient.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 that is used for the methane and carbon dioxide separation and preparation method thereof: after using the cured fiber of polypropylene, viscose rayon, phenolic fibre, pitch fibers etc. to carry out charing as raw material; Carry out activation processing with steam and make the textile-like carbon molecular sieve; Be used for the methane and carbon dioxide separation process, separate the methane gas purity that obtains and surpass 96%.One Chinese patent application 201110295013.2 also discloses the method for carbon dioxide in a kind of transformation adsorbing separation and the purifying biogas.Used adsorbent is the compound adsorbent that active carbon, particulate iron oxide or calcium oxide, silica gel are formed, and adsorption capacity is not high enough, thereby eight adsorption towers need be set, and changes each adsorption column pressure that is made up circularly, and operating process is very loaded down with trivial details.
The metal-organic framework materials (MOFs) that obtained paying close attention in recent years is a kind of novel porous material; Form by metal ion and organic ligand self assembly; Have characteristics such as high porosity, bigger serface; Through selecting different metal ion, organic ligand molecule can realize that size, shape and surface characteristic to the hole regulate and control, thereby having a good application prospect aspect the gas separation in the preparation process.
One Chinese patent application 200780005157.1 discloses a kind of method for preparing the metal-organic framework material of porous; This method requires a kind of copper compound of the crystallization water and organic compound of at least a bidentate of not containing; Reaction in the presence of non-aqueous solvent is carried out with being higher than under 80 ℃ at atmospheric pressure.One Chinese patent application 201010145406.0 discloses a kind of carbon dioxide absorption and metal-organic framework materials that separates and preparation method thereof of being used for; This method elder generation is with nitrate, chloride or the carbonate and 1 of copper or zinc; 3, the equal benzene tricarbonic acid's prepared in reaction of 5-a kind of metal-organic framework materials, and then obtain a kind of adsorbent with the polymine solution reaction; The absorption that is used for carbon dioxide with separate, be used for the low pressure absorption of carbon dioxide in vacuum to a barometric pressure range.
One Chinese patent application 200680048735.5 discloses the application of a kind of MOF in pressure oscillating absorption; This method flows hydrogen under the elevated pressures of 2MPa ~ 5MPa (20-50 atmospheric pressure); To the absorption of methane, comprised a plurality of adsorbent beds and made pressure sequence ground through the complex process of bed circulation with the formation continuous process.
The preparation process that often requires above-mentioned preparation or gas separation process adopts nonaqueous solvents, perhaps will use virose aziridine modification, perhaps relates to the processing mist separation process of high pressure, complicated steps and improved the use cost of sorbing material.
Summary of the invention
Technical problem to be solved by this invention is: remedy the deficiency of above-mentioned 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 solves through following technical scheme:
A kind of preparation method of metal-organic framework materials of adsorbing separation carbon dioxide/methane comprises the steps:
(1) copper nitrate aqueous solution of 0.46 ~ 1.16 mol/L and the trimesic acid ethanolic solution of 0.23 ~ 0.58 mol/L are mixed; Fully stir the back and add in the band teflon-lined stainless steel cauldron and seal, the control crystallization temperature is that 60 ~ 150 ℃ and crystallization time are to carry out solvent thermal reaction in 12 ~ 24 hours;
(2) open stainless steel cauldron,, and, obtain blue colored crystal 80 ~ 105 ℃ of following dryings successively with methyl alcohol and deionized water washing through filtration;
(3) said blue colored crystal is vacuumized processing under 150 ~ 200 ℃ and obtain the copper-containing metal organic framework material.
The present invention adopts solvent-thermal method; With the aqueous solution of copper nitrate and the ethanolic solution of trimesic acid is initial feed, in having the teflon-lined stainless steel cauldron, in water and ethanol mixed solvent; Under certain crystallization temperature and crystallization time condition; To synthetic solid through methyl alcohol and deionized water washing and dry, control certain baking temperature, more 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 the said step (3) is 160-180 ℃.
A kind of metal-organic framework materials is made by above-mentioned any described preparation method, 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 ℃ ~ 85 ℃, and the volume fraction of carbon dioxide is 5% ~ 60% in methane and the carbon dioxide gas mixture.
During the application of above-mentioned metal-organic framework materials in adsorbing separation carbon dioxide/methane; The experiment proof; Under above adsorptive pressure, adsorption temp condition; One pack system adsorption capacity to methane, carbon dioxide is big, has high transformation adsorptive selectivity separating effect for the methane and the carbon dioxide gas mixture of certain gas concentration lwevel scope: for example, and the experiment proof; Under 25 ℃ and 0.4 MPa pressure, this material can reach 8.01mmol/g and 3.40mmol/g respectively to the one pack system adsorption capacity of carbon dioxide and methane; Under 25 ℃ 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 the above methane gas of 99% (volume fraction).
The present invention further has following advantage: for isolation of purified methane and carbon dioxide gas mixture provide effective a, technology easily; Advantage such as related adsorption technology has that pressure is low, energy consumption is low, sorbing material avirulence, environmental benefit are good and operating procedure are simple; The renewable repeated use of material, and have good use tolerance.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the embodiment of the invention one prepared copper-containing metal framework material that obtains.
The specific embodiment
Contrast accompanying drawing below and combine preferred embodiment that the present invention is carried out detailed elaboration.
The present invention provides a kind of preparation method of metal-organic framework materials of adsorbing separation carbon dioxide/methane, in one embodiment, comprises the steps:
(1) with the copper nitrate aqueous solution of 0.46 ~ 1.16 mol/L and the equal benzene of trimesic acid of 0.23 ~ 0.58 mol/L (1,3,5-Benzenetricarboxylic Acid, C
9H
6O
6, note by abridging and be H
3Btc) ethanolic solution mixes, and fully stirs the back and adds in the band teflon-lined stainless steel cauldron and seal, and the control crystallization temperature is that 60 ~ 150 ℃ and crystallization time are to carry out solvent thermal reaction in 12 ~ 24 hours;
(2) open stainless steel cauldron,, and, obtain blue colored crystal 80 ~ 105 ℃ of following dryings successively with methyl alcohol and deionized water washing through filtration;
(3) said blue colored crystal is vacuumized processing under 150 ~ 200 ℃ and obtain the copper-containing metal organic framework material.
Temperature in the preferred said step (3) is 160-180 ℃.
2-10h drying time in the preferred steps (2).
Pumpdown time in the 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 content of the present invention is described more specifically, below provide preferred embodiment.
Embodiment one
Take by weighing 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 the solution I; Compound concentration is the 25ml H of 0.58 mol/L
3The ethanolic solution of btc is labeled as the solution II; Solution I and solution II are mixed; The capacity of packing into after fully stirring is in the band teflon-lined stainless steel cauldron of 100ml, and 95 ℃ of crystallization 15 hours are washed three times with methyl alcohol and deionized water after the filtration successively; Each 50ml; Fully stir 10min, 105 ℃ of dryings 10 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 175 ℃ and handled 10 hours, and recording specific area is 1136m
2/ g, (XRD) is as shown in Figure 1 for X ray diffracting spectrum, and 2 θ angles are 6.72 °, 9.56 °, 11.70 °, 13.48 °, 14.70 °, 16.5 °, 17.54 ° and locate to occur characteristic peaks among the figure, show that this material has typical metal organic frame material structure.
Embodiment two
Be with the difference of embodiment one: in band teflon-lined stainless steel cauldron,, wash three times with methyl alcohol and deionized water successively after the filtration 60 ℃ of following crystallization 15 hours; Each 50ml; Fully stir 10min, 80 ℃ of dryings 2 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 150 ℃ and handled 3 hours, and recording specific area is 539m
2/ g.
Embodiment three
Be with the difference of embodiment one: in band teflon-lined stainless steel cauldron,, wash three times with methyl alcohol and deionized water successively after the filtration 150 ℃ of following crystallization 15 hours; Each 50ml; Fully stir 10min, 105 ℃ of dryings 10 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 200 ℃ and handled 15 hours, and recording specific area is 967m
2/ g.
Embodiment four
Be with the difference of embodiment one: in band teflon-lined stainless steel cauldron,, wash three times with methyl alcohol and deionized water successively after the filtration 95 ℃ of following crystallization 12 hours; Each 50ml; Fully stir 10min, 105 ℃ of dryings 10 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 160 ℃ and handled 10 hours, 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 the solution I; Compound concentration is the 25ml H of 0.58 mol/L
3The ethanolic solution of btc is labeled as the solution II; Solution I and solution II are mixed; Fully stirring the capacity of packing into behind the 45min is in the band teflon-lined stainless steel cauldron of 100ml, 95 ℃ of following crystallization 24 hours, washs three times with methyl alcohol and deionized water successively after the filtration; Each 50ml; Fully stir 10min, 105 ℃ of dryings 10 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 180 ℃ and handled 10 hours, and recording specific area is 1111m
2/ g.
Embodiment six
Be with the difference of embodiment one: in band teflon-lined stainless steel cauldron,, wash three times with methyl alcohol and deionized water successively after the filtration 95 ℃ of crystallization 15 hours; Each 50ml; Fully stir 10min, 105 ℃ of dryings 10 hours obtain blue colored crystal.The gained blue colored crystal vacuumizes at 175 ℃ and handled 10 hours, and recording specific area is 866m
2/ g.
The application of metal-organic framework materials in adsorbing separation carbon dioxide/methane that the present invention also provides a kind of above-mentioned any embodiment to prepare; Wherein, Adsorptive pressure is 0.1MPa ~ 0.4MPa; Adsorption temp is-15 ℃ ~ 85 ℃, and the volume fraction of carbon dioxide is 5% ~ 60% in methane and the carbon dioxide gas mixture.
The present invention is-15 ℃ ~ 85 ℃ with the metal-organic framework materials adsorption temp of packing into; Adsorptive pressure is in the pressure-swing absorption apparatus of 0.1MPa ~ 0.4MPa; Feed pure carbon dioxide or pure methane gas; Measure the variation of pressure in the adsorbent bed, thereby obtain under the different pressures condition adsorbent the adsorption capacity and the adsorption isotherm of pure gas; For admixture of gas; The present invention is-15 ℃ ~ 85 ℃ with the metal-organic framework materials adsorption temp of packing into; Adsorptive pressure is in the pressure-swing absorption apparatus of 0.1MPa ~ 0.4MPa, and as carrier gas, the feeding gas concentration lwevel is 5% ~ 60% methane/carbon dioxide gaseous mixture with helium; Utilize the composition of gas chromatographic measurement adsorbent bed exit gas, obtain the breakthrough curve and the adsorptive selectivity of gas.
Below describe through specific embodiment.
Embodiment seven
With the copper-containing metal framework material 0.6g that makes among the embodiment one; Vacuumize under 175 ℃ handle pack into after 10 hours variable-pressure adsorption bed in; Feed pure carbon dioxide or methane gas down at 85 ℃; 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
With the copper-containing metal framework material 0.6g that makes among the embodiment one; Vacuumize under 175 ℃ handle pack into after 10 hours variable-pressure adsorption bed in; Feed pure carbon dioxide or methane gas down at-15 ℃; 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
With the copper-containing metal framework material 14g that makes among the embodiment one; Vacuumize under 175 ℃ handle pack into after 10 hours variable-pressure adsorption bed in; With the helium is the operating pressure that carrier gas keeps 0.4MPa in the adsorbent bed; Feeding carbon dioxide volumetric concentration is 60% methane/carbon dioxide gaseous mixture, changes with the gas chromatographic detection gas componant in the adsorbent bed outlet; Selection methane or carbon dioxide exit concentration are that 50% o'clock of initial concentration is a breakthrough point, obtain methane and in the time of 7.3 minutes, penetrate, and carbon dioxide penetrated at 16.5 minutes, are 3.10 thereby calculate the adsorptive selectivity that can get carbon dioxide/methane blended gas.
Embodiment ten
With the copper-containing metal framework material 14g that makes among the embodiment one; Vacuumize under 175 ℃ handle pack into after 10 hours variable-pressure adsorption bed in; With the helium is the operating pressure that carrier gas keeps 0.4MPa in the adsorbent bed; The feeding gas concentration lwevel is 5% methane/carbon dioxide gaseous mixture, changes with the gas chromatographic detection gas componant in the adsorbent bed outlet, draws breakthrough curve; Selection methane or carbon dioxide exit concentration are that 50% o'clock of initial concentration is a breakthrough point, obtain methane and in the time of 5.7 minutes, penetrate, and carbon dioxide penetrated at 32.9 minutes, are 10.76 thereby calculate the adsorptive selectivity that can get carbon dioxide/methane blended gas.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, do not breaking away under the prerequisite of the present invention design, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be regarded as belonging to protection scope of the present invention.
Claims (4)
1. the preparation method of the metal-organic framework materials of an adsorbing separation carbon dioxide/methane is characterized in that, comprises the steps:
(1) copper nitrate aqueous solution of 0.46 ~ 1.16 mol/L and the trimesic acid ethanolic solution of 0.23 ~ 0.58 mol/L are mixed; Fully stir the back and add in the band teflon-lined stainless steel cauldron and seal, the control crystallization temperature is that 60 ~ 150 ℃ and crystallization time are to carry out solvent thermal reaction in 12 ~ 24 hours;
(2) open stainless steel cauldron,, and, obtain blue colored crystal 80 ~ 105 ℃ of following dryings successively with methyl alcohol and deionized water washing through filtration;
(3) said blue colored crystal is vacuumized processing under 150 ~ 200 ℃ and obtain the copper-containing metal organic framework material.
2. the preparation method of metal-organic framework materials as claimed in claim 1, it is characterized in that: the temperature in the said step (3) is 160-180 ℃.
3. metal-organic framework materials, it is characterized in that: made by any described preparation method of claim 1-2, its specific area is 500 ~ 1200 m
2/ g.
4. the application of the described metal-organic framework materials of claim 3 in adsorbing separation carbon dioxide/methane; It is characterized in that: adsorptive pressure is 0.1MPa ~ 0.4MPa; Adsorption temp is-15 ℃ ~ 85 ℃, and the volume fraction of carbon dioxide is 5% ~ 60% in methane and the carbon dioxide gas mixture.
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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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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691399A (en) * | 2013-12-18 | 2014-04-02 | 北京科技大学 | Preparation method of high-performance carbon molecular sieve for separating carbon dioxide/methane |
| CN105312026A (en) * | 2014-07-09 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal temperature methane high-efficiency adsorption material |
| CN105669593A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Barium base metal organic framework material preparation method |
| 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 |
| CN106693896A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院大连化学物理研究所 | Heterogeneous composite structure adsorption materials, and preparation method and application thereof |
| CN107376997A (en) * | 2017-07-04 | 2017-11-24 | 常州大学 | A kind of catalyst preparation and its application for Oxybenzene methyl alcohol producing benzaldehyde |
| 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 |
| CN112121652A (en) * | 2020-09-28 | 2020-12-25 | 郑州轻工业大学 | Preparation method of metal organic framework-ceramic membrane nanofiltration composite membrane |
| CN112619611A (en) * | 2020-12-11 | 2021-04-09 | 太原理工大学 | Acetylene efficient separation material |
| CN113426416A (en) * | 2021-05-25 | 2021-09-24 | 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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| CN103691399A (en) * | 2013-12-18 | 2014-04-02 | 北京科技大学 | Preparation method of high-performance carbon molecular sieve for separating carbon dioxide/methane |
| CN105312026A (en) * | 2014-07-09 | 2016-02-10 | 江苏瑞丰科技实业有限公司 | Normal temperature methane high-efficiency adsorption material |
| 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 |
| CN105669593A (en) * | 2014-11-19 | 2016-06-15 | 中国科学院大连化学物理研究所 | Barium base metal organic framework material preparation method |
| 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 |
| 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 |
| CN106693896A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院大连化学物理研究所 | Heterogeneous composite structure adsorption materials, and preparation method and application thereof |
| CN107376997B (en) * | 2017-07-04 | 2020-11-10 | 常州大学 | Preparation and application of catalyst for preparing benzaldehyde by oxidizing benzyl alcohol |
| CN107376997A (en) * | 2017-07-04 | 2017-11-24 | 常州大学 | A kind of catalyst preparation and its application for Oxybenzene methyl alcohol producing benzaldehyde |
| 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 |
| CN112121652A (en) * | 2020-09-28 | 2020-12-25 | 郑州轻工业大学 | Preparation method of metal organic framework-ceramic membrane nanofiltration composite membrane |
| 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 |
| CN112619611A (en) * | 2020-12-11 | 2021-04-09 | 太原理工大学 | Acetylene efficient separation material |
| CN112619611B (en) * | 2020-12-11 | 2022-06-07 | 太原理工大学 | Acetylene efficient separation material |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN102728331B (en) | 2014-10-29 |
| HK1171981A1 (en) | 2013-04-12 |
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