CN106732390A - CO high2Modified ZIFs materials of absorption property and preparation method thereof - Google Patents
CO high2Modified ZIFs materials of absorption property and preparation method thereof Download PDFInfo
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- 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]
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- 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
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Abstract
The invention discloses a kind of CO high2The modified zeolite imidazate frame structure material of absorption property（ZIFs）Preparation method.It is during ZIF 8 is synthesized, to introduce large scale Ligands（1, n double (base of imidazoles 1) alkane, n=6,8,10）Reaming is carried out to ZIF 8, the narrow ducts of ZIF 8 is on the one hand effectively improved to CO2The diffusion limitation of molecule, on the other hand can also keep the skeleton structure and bigger serface of the stabilizations of ZIF 8, so as to significantly improve to CO2Absorption property.The adsorbent of present invention design synthesis is to CO2With excellent absorption property, CO under normal pressure2Adsorbance can reach 7.3mmol/g, the remote adsorbances of ultrapure ZIF 8（1.9 mmol/g）, and can keep efficient absorption, absorption property that leading position is also in the adsorbent of hitherto reported in low-temperature space and high-temperature region.
Description
Technical field
The present invention relates to the modified field of sorbing material, specially a kind of CO high2The modified zeolite imidazate bone of absorption property
Frame structural material（ZIFs）, and the adsorbent preparation method.
Background technology
Global warming has turned into the environmental problem for receiving much concern, with CO2Based on greenhouse gases largely discharge, be to lead
Cause the main cause of greenhouse effects aggravation.CO2Capture and storage（CCS）It is still the current main skill for reducing CO2 emission
Art means.CO2Primary discharge also come from the discharge of industrial waste gas, directly by the carbon dioxide capture in flue gas and storage
Deposit, CCS costs can be greatly reduced.But because industrial waste gas complicated component, temperature are high, therefore, directly adsorb and catch
Obtain the CO in flue gas2As the hot spot technology for currently urgently developing.
Metal-organic framework materials（MOFs）It is that the class generated by self assembly by metal ion and organic ligand is new
Type porous material, with specific surface area it is big, pore passage structure is regular, duct and surface chemical property can the feature such as modulation, absorption,
The aspect such as separation and catalysis shows wide application prospect.Zeolitic imidazolate framework material（ZIFs）In being MOFs materials
One kind, it be by transition metal atoms Zn or Co it is new with the class that imidazoles or imdazole derivatives are connected and generate, have
The nano-porous materials of zeolite topological.ZIFs not only has the advantages that MOFs materials, and compared with MOFs materials, has
More excellent heat and hydrothermal stability.ZIF-8 is most representational one kind in ZIFs materials, its cage mouthful diameter 0.34nm, with
CO2The kinetic diameter of molecule（0.33nm）It is close, therefore to CO2With good selectivity.ZIF-8 is in absorption, separation, storage
The multiple fields such as gas and catalysis all show excellent performance.
But, although ZIF-8 is to CO2The excellent but narrow duct of selectivity seriously limits CO2Effective diffusion of molecule,
So that CO2Absorption cracking pressure is larger.Reaming, can not only promote expansion of the gas molecule in MOFs cages between surface
Dissipate, can also effectively prevent duct from blocking, promote CO2Desorption, extends adsorbent service life.Research finds, in synthesis MOFs
During introduce large scale organic ligand, not only reaming effectively can be carried out to MOFs, can also keep the bone of original material settling out
Frame structure and bigger serface, so as to show the advantage of uniqueness in adsoption catalysis field.Therefore, this invention address that by drawing
Enter large scale Ligands, increase the macroporous structure in ZIF-8 skeletons, reduce CO2Resistance to mass tranfer, so as to significantly improve adsorbent
Absorption property.
The content of the invention
It is an object of the invention to provide a kind of CO high2The preparation method of the modified ZIFs materials of absorption property, to realize CO2
Efficient absorption, reduce CCS technical costs.
The present invention adopts the following technical scheme that realization：
A kind of CO high2The modified ZIFs materials of absorption property, are based on metal-organic framework materials ZIF-8, to synthesize ZIF-8
During, large scale Ligands are introduced, reaming is carried out to ZIF-8, synthesis has the compound ZIFs materials for mixing part.I.e.
It is the first part with 2-methylimidazole, imidazoles organic ligand 1, double (imidazoles -1- bases) hexanes of 6-, 1,8- are double (imidazoles -1- bases)
Double (imidazoles -1- bases) decane of octane or 1,10- are Ligands, prepare modified ZIFs materials, wherein, Ligands and the
The mole dosage ratio of one part is 1:1~20.
Above-mentioned CO high2The preparation method of the ZIFs material catalysts of absorption property is as follows：
S1：Dimethyl sulfoxide (DMSO) under nitrogen protection（DMSO）In dicyandiamide solution, 1,6- dibromo-hexane, the bromooctanes of 1,8- bis- or 1,
10- dibromo-decanes and dimethyl sulfoxide (DMSO) of the imidazoles at 160~180 DEG C（DMSO）Reaction 24~48 hours in dicyandiamide solution, 1,
6- dibromo-hexanes（Or the bromooctanes of 1,8- bis-, 1,10- dibromo-decanes）It is 1 with the mole dosage ratio of imidazoles：2~3.Product is removed
Go with chloroform, drying after DMSO, then washed with deionized water, finally recrystallized in water, wash and dry the heavy of precipitation
Shallow lake obtains double (imidazoles -1- bases) hexanes of imidazoles organic ligand 1,6-, double (imidazoles -1- bases) octanes of 1,8- and the double (miaows of 1,10-
Azoles -1- bases) decane.
S2：By double (imidazoles -1- bases) hexanes of 1,6-（Or double (imidazoles -1- bases) octanes of 1,8-, 1,10- are double (imidazoles -1- bases)
Decane）It is scattered in absolute methanol according to mol ratio with 2-methylimidazole, zinc nitrate hexahydrate absolute methanol solution is instilled, 20
Reacted 24~72 hours at~30 DEG C, prepare the ZIFs materials of the high absorption property.
In above-mentioned preparation method, zinc nitrate hexahydrate and organic ligand（First coordinates and Ligands）Mole dosage ratio
It is 1:8~10.
The present invention introduces large scale Ligands during ZIF-8 is synthesized, and has on the one hand carried out reaming to ZIF-8, has
Effect improves the narrow ducts of ZIF-8 to CO2The diffusion limitation of molecule, on the other hand can also keep the skeleton knot of ZIF-8 stabilizations
Structure and bigger serface, so as to significantly improve to CO2Absorption property.
The modified ZIFs materials of the high absorption property prepared by the present invention can be applied to absorption capture CO2, particularly it is used for
CO in flue gas2Absorption with storage.
CO in flue gas of the present invention2Volumn concentration be 15%.
CO of the present invention2Adsorption temp is 25~120 DEG C.
CO of the present invention2Adsorptive pressure is normal pressure.
The adsorbent of present invention design synthesis is to CO2With excellent absorption property, CO under normal pressure2Adsorbance is reached as high as
To 7.3mmol/g, remote ultrapure ZIF-8 adsorbances（1.9 mmol/g）, and efficient absorption can be kept in low-temperature space and high-temperature region,
Absorption property is also at leading position in the adsorbent of hitherto reported.
Specific embodiment
Specific embodiment of the invention is described in detail below.
Embodiment 1
Weigh 20.4 g（300 mmol）Imidazoles, 12.0 g（300 mmol）NaOH, is added in 20mL DMSO, leads to nitrogen and protects
Shield, is heated to 65 DEG C, back flow reaction 4 hours under stirring.It is then slowly added into 1,6- dibromo-hexanes（100 mmol）, reaction terminates
Afterwards, revolving removes solvent DMSO, is extracted 3 times with chloroform, then with saturated common salt water washing 3 times, washes with water 3 times, rotates dense
Contracting, vacuum drying obtains double (imidazoles -1- bases) hexanes of 1,6-.
Weigh 25mmol 2-methylimidazoles and double (imidazoles -1- bases) hexanes of 1,6-（Wherein, 2-methylimidazole and 1,6- are double
(imidazoles -1- bases) hexane mol ratio is 2:1）, it is dissolved in 62.5 mL absolute methanols, above-mentioned solution then is placed in into hydro-thermal closes
Into in kettle, 50 DEG C of 2 h of holding.1.89 g zinc nitrate hexahydrates are weighed, is dissolved in 62.5mL absolute methanols.Before after cooling
Person is slowly dropped in zinc nitrate methanol solution, and 24 h are stirred vigorously at room temperature.Centrifugation, the solid that will be obtained is with without water beetle
After alcohol washing, vacuum drying, the powdered ZIFs materials 0.80g of high absorption property is obtained, labeled as 6-2-ZIF-8.
Embodiment 2-5
With embodiment 1, change 2-methylimidazole and double (imidazoles -1- bases) the hexane mol ratio x of 1,6-, obtain a series of ZIFs materials
Material, labeled as 6-x-ZIF-8, wherein x is respectively 5,10,15,20.
Embodiment 6
Weigh 20.4 g（300 mmol）Imidazoles, 12.0 g（300 mmol）NaOH, is added in 20mL DMSO, leads to nitrogen and protects
Shield, is heated to 65 DEG C, back flow reaction 4 hours under stirring.It is then slowly added into the bromooctanes of 1,8- bis-（100 mmol）, reaction terminates
Afterwards, revolving removes solvent DMSO, is extracted 3 times with chloroform, then with saturated common salt water washing 3 times, washes with water 3 times, rotates dense
Contracting, vacuum drying obtains double (imidazoles -1- bases) octanes of 1,8-.
Weigh 25mmol 2-methylimidazoles and double (imidazoles -1- bases) octanes of 1,8-（Wherein, 2-methylimidazole and 1,8- are double
(imidazoles -1- bases) octane mol ratio is 1:1）It is dissolved in 62.5 mL absolute methanols, above-mentioned solution is then placed in Hydrothermal Synthesiss
In kettle, 50 DEG C of 2 h of holding.1.89 g zinc nitrate hexahydrates are weighed, is dissolved in 62.5mL absolute methanols.The former is slowly added dropwise
To in zinc nitrate methanol solution, 24 h are stirred vigorously at room temperature.Centrifugation, the solid that will be obtained washs with absolute methanol, true
After sky is dried, the ZIFs materials of high absorption property, powdered 0.80g, labeled as 8-1-ZIF-8 are obtained.
Embodiment 7-10
With embodiment 1, change 2-methylimidazole and double (imidazoles -1- bases) the octane mol ratio x of 1,8-, obtain a series of ZIFs materials
Material, labeled as 8-x-ZIF-8, wherein x is respectively 2,5,10,15,20.
Embodiment 11
Weigh 20.4 g（300 mmol）Imidazoles, 12.0 g（300 mmol）NaOH, is added in 20mL DMSO, leads to nitrogen and protects
Shield, is heated to 65 DEG C, the h of back flow reaction 4 under stirring.It is then slowly added into 1,10- dibromo-decanes（100 mmol）, reaction terminates
Afterwards, revolving removes solvent DMSO, is extracted 3 times with chloroform, then with saturated common salt water washing 3 times, washes with water 3 times, rotates dense
Contracting, vacuum drying obtains double (imidazoles -1- bases) decane of 1,10-.
Weigh 25mmol 2-methylimidazoles and double (imidazoles -1- bases) decane of 1,10-（Wherein, 2-methylimidazole and 1,10-
Double (imidazoles -1- bases) decane mol ratios are 2:1）It is dissolved in 62.5 mL absolute methanols, above-mentioned solution then is placed in into hydro-thermal closes
Into in kettle, 50 DEG C of 2 h of holding.1.89 g zinc nitrate hexahydrates are weighed, is dissolved in 62.5mL absolute methanols.The former is slowly dripped
It is added in zinc nitrate methanol solution, 24 h is stirred vigorously at room temperature.Centrifugation, the solid that will be obtained with absolute methanol wash,
After vacuum drying, the ZIFs materials of high absorption property, powdered 0.80g, labeled as 10-2-ZIF-8 are obtained.
Embodiment 12-15
With embodiment 1, change 2-methylimidazole and double (imidazoles -1- bases) the decane mol ratio x of 1,10-, obtain a series of ZIFs materials
Material, labeled as 8-x-ZIF-8, wherein x is respectively 5,10,15,20.
Comparative example 1
Weigh 1.5 g zinc nitrate hexahydrates to be scattered in 70 mL absolute methanols, be slowly added dropwise 70 mL and be dissolved with 3.3 g 2- first
The absolute methanol of base imidazoles, is stirred vigorously 48 h at room temperature.Centrifugation, the solid that will be obtained is washed with absolute methanol, vacuum
After drying, the pure g of metal organic framework ZIF-8 white powders 1.3 is obtained.
Following application examples uses CO2Infrared spectrum analyser, the ZIF-8 using the preparation of comparative example 1 is determined under normal pressure as control
The ZIFs materials of embodiment preparation are stated to CO2Adsorption selectivity.
Application examples 1
Weigh about 1.0 g 6-2-ZIF-8 to be filled in adsorptive reactor, in 98.5 cm3Under the nitrogen stream of/min, opened from room temperature
Begin to be warming up to 140 DEG C of holding constant temperature with the heating rate of 1 DEG C/min, purge 60 min；Then absorption is cooled in nitrogen atmosphere
25 DEG C of temperature, is passed through with the gas flow rate of 115 mL/min and contains 85% N2With 15% CO2Gaseous mixture, and real-time recorded data.
The CO of sample2Selection adsorbance is according to CO2Infrared spectrum analyser measurement data is calculated, and selection adsorbance is 1.8 mmol/g.
Application examples 2-5
With application examples 1,2-methylimidazole in adsorbent and double (imidazoles -1- bases) the hexane mol ratios of 1,6- are carried out preferably, no
The adsorbent obtained under double (imidazoles -1- bases) the hexane mol ratios of same 2-methylimidazole/1,6- is to CO2Adsorbance be shown in Table 1.Thus
It can be seen that, with the continuous increase of double (imidazoles -1- bases) the hexane contents in adsorbent of 1,6-, CO2Adsorbance is presented after first increasing
The trend of reduction, 2-methylimidazole/1, double (imidazoles -1- bases) the hexane mol ratios of 6- are 15:When 1, CO2Adsorbance highest, it is reachable
4.9 mmol/g。
The CO of the 6-x-ZIF-8 of table 12Adsorbance
Application examples 6-10
With application examples 1, to the CO under optimum absorbent 6-15-ZIF-8 different temperatures2Adsorbance is determined, and is shown in table 2.
As can be seen here, 6-15-ZIF-8 can keep CO higher in low temperature and high-temperature region2Adsorbance.
The CO of the 6-15-ZIF-8 of table 22Adsorbance
Application examples 11-16
With application examples 1,8-x-ZIF-8 at testing 25 DEG C（X=1,2,5,10,15,20）To CO2Absorption property, to 2- first
Base imidazoles and double (imidazoles -1- bases) the octane mol ratios of 1,8- have been carried out preferably, different 2-methylimidazole/1, the double (imidazoles -1- of 8-
Base) adsorbent that obtains under octane mol ratio is to CO2Adsorbance be shown in Table 3.As can be seen here, it is similar to 6-x-ZIF-8 series, with
The continuous increase of double (imidazoles -1- bases) the octane contents in adsorbent of 1,8-, CO2Adsorbance is presented first increases becoming of reducing afterwards
Gesture, when 2-methylimidazole/1, double (imidazoles -1- bases) the octane mol ratios of 8- are 2:When 1, CO2Adsorbance highest, up to 6.0
mmol/g。
The CO of the 8-x-ZIF-8 of table 32Adsorbance
Application examples 17-21
With application examples 1, to optimum absorbent 8-2-ZIF-8 CO at different temperatures2Adsorbance is determined, and is shown in table
4.As can be seen here, 8-2-ZIF-8 can keep CO higher in low temperature and high-temperature region2Adsorbance, can reach at 75 DEG C
7.3 mmol/g。
The CO of the 8-2-ZIF-8 of table 42Adsorbance
Application examples 22-27
With application examples 1,10-x-ZIF-8 at testing 25 DEG C（X=1,2,5,10,15,20）To CO2Absorption property, to 2-
Methylimidazole and double (imidazoles -1- bases) the decane mol ratios of 1,10- have been carried out preferably, different 2-methylimidazole/1,10- pairs (imidazoles -
1- yls) adsorbent that obtains under decane mol ratio is to CO2Adsorbance be shown in Table 5.It can be seen that, with 1,10- double (imidazoles -1- bases) last of the ten Heavenly stems
The continuous increase of alkane content in adsorbent, CO2Adsorbance is equally presented first increases the trend that reduces afterwards, when 2-methylimidazole/
Double (imidazoles -1- bases) the decane mol ratios of 1,10- are 2:When 1, CO2Adsorbance highest, up to 3.4 mmol/g.
The CO of the 10-x-ZIF-8 of table 52Adsorbance
Application examples 28-32
With application examples 1, to optimum absorbent 10-2-ZIF-8 CO at different temperatures2Adsorbance is determined, and is shown in table
6.As can be seen here, 10-2-ZIF-8 equally can keep CO higher in low temperature and high-temperature region2Adsorbance, at 75 DEG C, highest can
Reach 3.9 mmol/g.
The CO of the 10-2-ZIF-8 of table 62Adsorbance
Comparative example 1
Weigh about 1.0 g ZIF-8 to be filled in adsorptive reactor, in 98.5 cm3Under the nitrogen stream of/min, since room temperature with
The heating rate of 1 DEG C/min is warming up to 140 DEG C of holding constant temperature, purges 60min；Then adsorption temp 25 is cooled in nitrogen atmosphere
DEG C, it is passed through with the gas flow rate of 115 ml/min and contains 85 % N2With 15 % CO2Gaseous mixture, adsorption reaction 10min, and in fact
When record data.The CO of sample2Selection adsorbance is according to CO2Infrared spectrum analyser measurement data is calculated, and selection adsorbance is
2.0 mmol/g。
Comparative example 2-6
Respectively in 50 DEG C, 75 DEG C, 90 DEG C, 100 DEG C, 120 DEG C of CO2Adsorbent ZIF-8 is determined under adsorption reaction temperature conditionss, its
His condition is with comparative example 1, CO2Selection adsorbance be shown in Table 7.
The CO of the metal organic framework ZIF-8 of table 72Adsorbance
As can be seen here, after being modified to ZIF-8 by introducing large scale Ligands, it is remarkably improved the CO of ZIF-82Absorption
Performance.Modified ZIFs adsorption capacities of materials can reach 7.3mmol/g, and can keep efficient in low-temperature space and high-temperature region
Absorption, absorption property is also at leading position in the adsorbent of hitherto reported.
Several efficient CO have been prepared in above-described embodiment2Adsorbent, realizes to CO2High selectivity, Large Copacity,
Low energy consumption is trapped, and is CO2Fixed conversion particularly flue gas in CO2Fixed conversion provide effective ways.
It should be noted last that, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although ginseng
It has been described in detail according to the embodiment of the present invention, it will be understood by those within the art that, to technical scheme
Modify or equivalent, without departure from the spirit and scope of technical scheme, it all should cover claim
In protection domain.
Claims (10)
1. a kind of CO high2The modified ZIFs materials of absorption property, it is characterised in that：It is with metal-organic framework materials ZIF-8 as base
Plinth introduces Ligands, the Ligands be double (imidazoles -1- bases) hexanes of 1,6-, double (imidazoles -1- bases) octanes of 1,8- or
Double (imidazoles -1- bases) decane of 1,10-.
2. CO high according to claim 12The modified ZIFs materials of absorption property, it is characterised in that：The Ligands and
The mol ratio of the first part 2-methylimidazole in metal-organic framework materials ZIF-8 is 1:1~20.
3. a kind of CO high2The preparation method of the modified ZIFs materials of absorption property, it is characterised in that：Comprise the following steps：
（1）, in dimethyl sulfoxide solvent system under nitrogen protection, by imidazoles and 1,6- dibromo-hexane, the bromooctanes of 1,8- bis-
Or 1,10- dibromo-decanes heating reflux reaction under alkaline environment prepare imidazoles Ligands 1,6- double (imidazoles -1- bases) oneself
Double (imidazoles -1- bases) octanes of alkane, 1,8- and double (imidazoles -1- bases) decane of 1,10-；
（2）, one of above-mentioned Ligands are scattered in absolute methanol with the first part 2-methylimidazole, instill six nitric hydrates
Zinc absolute methanol solution, reaction prepares the modified ZIFs materials of the high absorption property.
4. CO high according to claim 32The preparation method of the modified ZIFs materials of absorption property, it is characterised in that：Step
（1）In, 1, the 6- dibromo-hexanes or the bromooctane of 1,8- bis-, 1,10- dibromo-decanes and diformazan of the imidazoles at 160~180 DEG C
Reaction 24~48 hours, 1,6- dibromo-hexane or the bromooctane of 1,8- bis-, 1,10- dibromo-decanes and imidazoles in base sulfoxide solvent system
Mole dosage ratio be 1：2~3；With chloroform, drying after product removing dimethyl sulfoxide (DMSO), then washed with deionization
Wash, finally recrystallized in water, wash and dry the precipitation for separating out and obtain imidazoles Ligands 1,6- double (imidazoles -1- bases) oneself
Double (imidazoles -1- bases) octanes of alkane, 1,8- and double (imidazoles -1- bases) decane of 1,10-.
5. CO high according to claim 32The preparation method of the modified ZIFs materials of absorption property, it is characterised in that：Step
（2）In, reacted in the absolute methanol dicyandiamide solution of the Ligands, the first part and zinc nitrate hexahydrate at 20~30 DEG C
24~72 hours.
6. CO high according to claim 52The preparation method of the modified ZIFs materials of absorption property, it is characterised in that：Step
（2）In, the zinc nitrate hexahydrate and two kinds of mole dosage ratios of organic ligand are 1:8~10.
7. a kind of CO high2The modified ZIFs materials of absorption property CO in absorption capture flue gas2On application.
8. application according to claim 7, it is characterised in that：CO high2The modified ZIFs materials of absorption property are 25~120
DEG C adsorption temp under adsorb capture CO2。
9. the application according to claim 7 or 8, it is characterised in that：CO in flue gas2Volumn concentration be 15%.
10. application according to claim 8, it is characterised in that：
CO high2The modified ZIFs materials 6-15-ZIF-8 of absorption property adsorbs capture CO under 50~120 DEG C of adsorption temp2；
CO high2The modified ZIFs materials 8-2-ZIF-8 of absorption property adsorbs capture CO under 25~120 DEG C of adsorption temp2；
CO high2The modified ZIFs materials 10-2-ZIF-8 of absorption property adsorbs capture CO under 50~120 DEG C of adsorption temp2。
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| CN114685804A (en) * | 2022-04-06 | 2022-07-01 | 中国药科大学 | Core-shell type dual-ligand coordination polymer and preparation method and application thereof |
| CN114685804B (en) * | 2022-04-06 | 2023-03-07 | 中国药科大学 | Core-shell type dual-ligand coordination polymer and preparation method and application thereof |
| CN114958752A (en) * | 2022-05-17 | 2022-08-30 | 西南交通大学 | Multifunctional magnetic nano composite material and preparation method and application thereof |
| CN114958752B (en) * | 2022-05-17 | 2023-10-24 | 西南交通大学 | Multifunctional magnetic nanocomposite and preparation method and application thereof |
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