CN106475059A - A kind of to C6Isomer has ferrous metals organic framework material of high adsorptive selectivity and preparation method and application - Google Patents
A kind of to C6Isomer has ferrous metals organic framework material of high adsorptive selectivity and preparation method and application Download PDFInfo
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- CN106475059A CN106475059A CN201610939912.4A CN201610939912A CN106475059A CN 106475059 A CN106475059 A CN 106475059A CN 201610939912 A CN201610939912 A CN 201610939912A CN 106475059 A CN106475059 A CN 106475059A
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- 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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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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Abstract
The invention discloses a kind of to C6Isomer has ferrous metals organic framework material of high adsorptive selectivity and preparation method and application, and the method comprises the steps：（1）By 2,2 pairs（4 carboxyl phenyls）HFC-236fa and iron cluster are dissolved separately in DMF；（2）By 2,2 pairs（4 carboxyl phenyls）The DMF solution of HFC-236fa is added dropwise in the DMF solution of iron cluster, drips glacial acetic acid, stirring；（3）Load stainless steel autoclave, carry out temperature programmed control hydrothermal synthesis reaction；（4）Washing, centrifugation, dry, obtain ferrous metals organic framework material.Resulting materials of the present invention are to C6Alkane Isomers have high adsorptive selectivity, and under equal conditions, which is more than 3 times of the conventional adsorbent such as 5A molecular sieve to n-hexane adsorptive selectivity, and with good chemical stability and hydrophobicity.The material can separate C from direct steaming gasoline6Isomer, with good potential application foreground.
Description
Technical field
The present invention relates to C6Alkane Isomers adsorption separation technology field, more particularly to a kind of to C6 isomer
Ferrous metals organic framework material with high adsorptive selectivity and preparation method and application.
Background technology
N-hexane is one of industrial broad-spectrum varsol, and most representational non-polar solven, may be used also
As essential oil diluent and for extracting essence in fragrance material etc..At present, rectifying typically used from direct steaming gasoline by n-hexane
Separation method is obtained.But in these raw materials, containing the component very close with n-hexane boiling point, such as 3- methylpentane and 2,2-
The isomer of the n-hexanes such as dimethylbutane, therefore, efficiently separates n-hexane, 3- methylpentane and 2,2- dimethylbutane
Deng C6Isomer has significant application value and Research Significance.
At present, domestic and international C6The isolation technics of Alkane Isomers mainly has conventional distillation method, azeotropic distillation, extraction
Rectification method and adsorption method of separation etc..Wherein, adsorption method of separation due to technological equipment investment low, energy consumption is low, simple operation and other advantages,
It is considered as a kind of C of great potential6The isolation technics of Alkane Isomers.Sorbing material is the core of adsorption separation technology
The heart, develops to C6Alkane Isomers adsorption capacity is big, and selective higher sorbing material has become one of study hotspot.
Molecular sieve is widely used in C as a kind of common conventional adsorbent6The adsorbing separation of Alkane Isomers.Patrick
The BETA molecular sieve such as S.Ba ' rcia is to C6Alkane Isomers research discovery, 423K, during 0.3bar, BETA molecular sieve is to C6
Alkane Isomers adsorbance can reach 0.07g/g, and adsorbance size order is n-hexane>3- methylpentane>2,3- diformazans
Base butane>2,2- dimethylbutanes.The Beta (H, Na) such as K.Huddersman, mordenite (Na), silicalite
(Na), a series of molecular sieves such as EU-1 (Na), ZSM-12 (Na), SAPO-5 are to C6Alkane Isomers adsorption separation performance enters
Row research, when research finds 325 DEG C, Beta (H, Na) has excellent adsorptivity to 3- methylpentane and 2,3- dimethylbutane
Can, adsorbance is respectively 0.104g/g and 0.099g/g.The research such as R.Krishna finds, during 433K, is separated with molecular sieve MFI
N-hexane/dimethyl pentane, adsorptive selectivity are 4.Above research shows molecular sieve to C6The absorption of Alkane Isomers is held
Amount is relatively low.Additionally, adsorbent of molecular sieve is to C6Alkane Isomers adsorptive selectivity is poor, it is impossible to efficiently separated, limit
Its application is industrially made.Therefore, research and development are to C6Alkane Isomers adsorption capacity is big, and selectively higher is new
Type sorbing material has extremely important realistic meaning.
In recent years, emerging family's porous functional material, i.e. metal-organic framework materials（Metal Organic
Frameworks, abbreviation MOFs）Appearance, cause great interest and the concern of people.Patrick S.Ba ' rcia etc. is first
Using Zn (BDC) (Dabco)0.5(MOF 1) is used for C6Alkane Isomers adsorbing separation, finds 1 material Preferential adsorption of MOF
Straight chain C6Alkane.The research of Na Chang research group finds ZIF-8 material to straight chain C6Alkane and side chain C6Alkane has separation property
Can, and Preferential adsorption straight chain C6Alkane；Patrick S.Ba ' rcia etc. has found that UiO-66 can also be used for C6Alkane isomerism
Body adsorbing separation and Preferential adsorption side chain C6Alkane, it is longer that reason is that the tetrahedroid duct of UiO-66 can not accommodate carbochain
N-hexane；0.6Kpa, when 430 DEG C, the selection of 2,2- dimethylbutanes/n-hexane and 2,2- dimethylbutane/3- methylpentane
Property may each be about 6.5.Zoey R.Herm etc. reports Fe2(BDP)3For C6Alkane Isomers adsorbing separation, and find Fe2
(BDP)3To different C6Alkane adsorptive selectivity order be：N-hexane>2- methylpentane>3- methylpentane>2,3- dimethylbutane
≈ 2,2- dimethylbutane, but there is adsorbing separation C6The selectively relatively low problem of isomer.
Content of the invention
In order to overcome problem above, the invention provides a kind of to C6Isomer has the iron-based of high adsorptive selectivity
Metal-organic framework materials and preparation method and application.
The ferrous metals organic framework material of the present invention（Fe-hifpbb）, be by iron cluster Fe3(CH3COO)6And organic ligand
2,2- is double（4- carboxyl phenyl）HFC-236fa is through the three-dimensional porous framework material of self assembly.Fe-hifpbb is to C6Alkane
Isomer has excellent adsorption separation performance, and it is closer with the kinetic diameter of n-hexane to be mainly its aperture, causes
Its Preferential adsorption n-hexane.What is particularly worth mentioning is that, due to the strong coordination of ferric iron and part, make the materials chemistry stability
Good, can acid and alkali-resistance immersion.Additionally, containing substantial amounts of fluorine atom on organic ligand so as to stronger hydrophobic performance.Material dredge
Aqueous can ensure that when carrying out adsorbing separation in wet condition, the duct of material and adsorption site are not occupied by hydrone, are kept away
Exempt to occur material and reduce the problem of its adsorption capacity because adsorbing steam and forming competitive Adsorption.The material is in C6Isomer divides
There is good potential application foreground from aspect.
The purpose of the present invention is achieved through the following technical solutions.
A kind of to C6Isomer has the preparation method of the ferrous metals organic framework material of high adsorptive selectivity, bag
Include following steps：
（1）2,2- is double（4- carboxyl phenyl）HFC-236fa and iron cluster are dissolved separately in DMF, obtain 2,2- double（4- carboxyl
Phenyl）The DMF solution of HFC-236fa and the DMF solution of iron cluster；
（2）2,2- is double（4- carboxyl phenyl）The DMF solution of HFC-236fa is added dropwise in the DMF solution of iron cluster, then by
Drop adds glacial acetic acid, and stirs, and obtains mixed liquor；
（3）Mixed liquor is loaded stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；
（4）Reaction is washed with DMF and dichloromethane after terminating successively, and centrifugal filtration is extracted, and is put in baking oven and is dry, obtains iron
Base Metal organic framework material, is labeled as Fe-hifpbb.
Preferably, step（1）The preparation of the iron cluster is comprised the following steps：First by anhydrous sodium acetate and Fe (NO3)3·
9H2O is dissolved in water, and obtains sodium acetate solution and iron nitrate solution；Then sodium acetate solution is dropwise instilled ferric nitrate molten
In liquid, stirring, form mixed solution；Again mixed solution is carried out suction filtration, and deionized water and ethanol washing successively, be put into baking
Dry in case, obtain iron cluster.
It is further preferred that the anhydrous sodium acetate and Fe (NO3)3·9H2The mass ratio of O is（3.147～4）：1.
It is further preferred that the time of the stirring is 8～24h.
Preferably, 2, the 2- are double（4- carboxyl phenyl）The mass ratio of HFC-236fa/iron cluster/glacial acetic acid/DMF is 1:(1～
2):(11.6～20):(126.4～150).
Preferably, step（3）The temperature programmed control process of the hydrothermal synthesis reaction is：
The temperature programming stage：Heating rate is set as 5～10 DEG C/min, mixed liquor is risen to 140～150 DEG C from room temperature；
The constant temperature stage：The temperature of mixed liquor keeps 12～24h at 140～150 DEG C;
The programmed cooling stage：If rate of temperature fall is 0.4～1 DEG C/min, reaction solution is down to 25 from 140～150 DEG C～
50℃.
It is further preferred that step（3）The temperature programmed control process of the hydrothermal synthesis reaction is：
The temperature programming stage：Heating rate is set as 5～10 DEG C/min, mixed liquor is risen to 150 DEG C from room temperature；
The constant temperature stage：The temperature of mixed liquor keeps 12～24h at 150 DEG C;
The programmed cooling stage：If rate of temperature fall is 0.4～1 DEG C/min, reaction solution is down to 35 DEG C from 150 DEG C.
Preferably, step（4）The rotating speed of the centrifugation is 6000～9000r/min.
Preferably, step（4）The temperature of the drying is 80～150 DEG C.
A kind of to C obtained in above-described preparation method6Isomer has the iron-based gold of high adsorptive selectivity
Category organic framework material；The ferrous metals organic framework material is applied to C6In the separation of isomer.
Compared with prior art, the invention has the advantages that and technique effect：
1. chemical stability is good, soaking-resistant, acid and alkali-resistance, soaks skeleton structure basic in pH=2 and pH=10 solution
Keep constant.
2., with good hydrophobicity, hydrophobicity test contact angle is 110 °.
3.Fe-hifpbb is to C6Alkane Isomers have good adsorptive selectivity, can efficiently separate straight chain and prop up
Chain C6Alkane.
Description of the drawings
Fig. 1 is Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and the Fe- prepared by the embodiment of the present invention 1～4
The XRD of hifpbb-4.
Fig. 2 is Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and the Fe- prepared by the embodiment of the present invention 1～4
The heat stability testing of hifpbb-4.
Fig. 3 is n-hexane, 3- methylpentane, and 2,2- dimethylbutanes are in the Fe- prepared by the embodiment of the present invention 1
Adsorbance on hifpbb-1 changes over curve.
Fig. 4 is the XRD after the Fe-hifpbb-1 prepared by the embodiment of the present invention 1 is soaked in different pH solution.
Fig. 5 is the contact angle test chart of the Fe-hifpbb-1 prepared by the embodiment of the present invention 1.
Fig. 6 is n-hexane/absorption of the 2,2- dimethylbutane on the Fe-hifpbb-1 prepared by the embodiment of the present invention 1
H103 resin figure.
Fig. 7 is that absorption of the n-hexane/3- methylpentane on the Fe-hifpbb-1 prepared by the embodiment of the present invention 1 is passed through
Curve map.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
（1）The synthesis of iron cluster：1. by 25.4293g anhydrous sodium acetate and 8.08g Fe (NO3)3·9H2O is dissolved separately in
In 50ml water；2. aqueous sodium acetate solution is dropwise instilled in iron nitrate aqueous solution, and 8h is stirred, obtain mixed liquor；3. will mixing
Liquid carries out suction filtration and obtains brown solid, and deionized water and ethanol washed product successively, and product is put under 70 DEG C of vacuum drying chambers
Freeze-day with constant temperature 7 hours, is obtained iron cluster [Fe3(CH3COO)6].
（2）The synthesis of Fe-hifpbb：1. 450mg part 2,2- is double（4- carboxyl phenyl）HFC-236fa and 450mg iron cluster
It is dissolved separately in 30ml (28.44g) DMF (DMF)；2. 2,2- is double（4- carboxyl phenyl）HFC-236fa
DMF solution be added dropwise in the DMF solution of iron cluster, then be added dropwise over 5.0ml (5.25g) glacial acetic acid, and stir 30min to mixed
Close liquid uniform；3. mixed liquor is loaded 100ml stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；Set and rise
Warm program is：Reaction solution is heated to 140 DEG C with the heating rate of 5 DEG C/min, heats 12h at a temperature of 140 DEG C, then with
Reaction solution is down to 25 DEG C by the rate of temperature fall of 0.4 DEG C/min；4. product carries out DMF successively and dichloromethane washing is each twice,
Centrifuge speed is 6000r/min centrifugation, the product after washing is put into 80 DEG C of oven for drying standby, and marks this sample for Fe-
hifpbb-1.
Embodiment 2
（1）The synthesis of iron cluster：1. by 32.32g anhydrous sodium acetate and 8.08g Fe (NO3)3·9H2O is dissolved separately in 50ml
In water；2. aqueous sodium acetate solution is dropwise instilled in iron nitrate aqueous solution, and 24h is stirred, obtain mixed liquor；3. mixed liquor is entered
Row suction filtration obtains brown solid, and deionized water and ethanol washed product successively, and product is put into constant temperature under 70 DEG C of vacuum drying chambers
Dry 7 hours, iron cluster [Fe is obtained3(CH3COO)6].
（2）The synthesis of Fe-hifpbb：1. 450mg part 2,2- is double（4- carboxyl phenyl）HFC-236fa and 900mg iron cluster
It is dissolved separately in 35.6ml (33.75g) DMF (DMF)；2. 2,2- is double（4- carboxyl phenyl）Hexafluoro third
The DMF solution of alkane is added dropwise in the DMF solution of iron cluster, then is added dropwise over 8.57ml (9.0g) glacial acetic acid, and stirs 30min extremely
Mixed liquor is uniform；3. mixed liquor is loaded 100ml stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；Set
Heating schedule is：Reaction solution is heated to 150 DEG C with the heating rate of 10 DEG C/min, 24h is heated at a temperature of 150 DEG C, so
Reaction solution is down to 50 DEG C with the rate of temperature fall of 1 DEG C/min afterwards；4. product carries out DMF and dichloromethane washing each two successively
Secondary, centrifuge speed is 9000r/min centrifugation, the product after washing is put into 80 DEG C of oven for drying standby, and marks this sample to be
Fe-hifpbb-2.
Embodiment 3
（1）The synthesis of iron cluster：1. by 28.87g anhydrous sodium acetate and 8.08g Fe (NO3)3·9H2O is dissolved separately in 50ml
In water；2. aqueous sodium acetate solution is dropwise instilled in iron nitrate aqueous solution, and 16h is stirred, obtain mixed liquor；3. mixed liquor is entered
Row suction filtration obtains brown solid, and deionized water and ethanol washed product successively, and product is put into constant temperature under 70 DEG C of vacuum drying chambers
Dry 7 hours, iron cluster [Fe is obtained3(CH3COO)6].
（2）The synthesis of Fe-hifpbb：1. 450mg part 2,2- is double（4- carboxyl phenyl）HFC-236fa and 675mg iron cluster
It is dissolved separately in 32.8ml (31.1g) DMF (DMF)；2. 2,2- is double（4- carboxyl phenyl）HFC-236fa
DMF solution be added dropwise in the DMF solution of iron cluster, then be added dropwise over 6.785ml (7.125g) glacial acetic acid, and stir 30min
Uniform to mixed liquor；3. mixed liquor is loaded 100ml stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；If
Determining heating schedule is：Reaction solution is heated to 145 DEG C with the heating rate of 7.5 DEG C/min, at a temperature of 145 DEG C, 24h is heated,
Then 37.5 DEG C are down to reaction solution with the rate of temperature fall of 0.7 DEG C/min；4. product carries out DMF and dichloromethane washing successively
Each centrifuge speed is 7500r/min centrifugation twice, the product after washing is put into 115 DEG C of oven for drying standby, and marks this
Sample is Fe-hifpbb-3.
Embodiment 4
（1）The synthesis of iron cluster：1. by 25.4293g anhydrous sodium acetate and 8.08g Fe (NO3)3·9H2O is dissolved separately in
In 50ml water；2. aqueous sodium acetate solution is dropwise instilled in iron nitrate aqueous solution, and 8h is stirred, obtain mixed liquor；3. will mixing
Liquid carries out suction filtration and obtains brown solid, and deionized water and ethanol washed product successively, and product is put under 70 DEG C of vacuum drying chambers
Freeze-day with constant temperature 7 hours, is obtained iron cluster [Fe3(CH3COO)6].
（2）The synthesis of Fe-hifpbb：1. 450mg part 2,2- is double（4- carboxyl phenyl）HFC-236fa and 675mg iron cluster
It is dissolved separately in 32.8ml (31.1g) DMF (DMF)；2. 2,2- is double（4- carboxyl phenyl）HFC-236fa
DMF solution be added dropwise in the DMF solution of iron cluster, then be added dropwise over 6.785ml (7.125g) glacial acetic acid, and stir 30min
Uniform to mixed liquor；3. mixed liquor is loaded 100ml stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；If
Determining heating schedule is：Reaction solution is heated to 145 DEG C with the heating rate of 7.5 DEG C/min, at a temperature of 145 DEG C, 24h is heated,
Then 37.5 DEG C are down to reaction solution with the rate of temperature fall of 0.7 DEG C/min；4. product carries out DMF and dichloromethane washing successively
Each centrifuge speed is 7500r/min centrifugation twice, the product after washing is put into 115 DEG C of oven for drying standby, and marks this
Sample is Fe-hifpbb-4.
(1) the pore structure property of Fe-hifpbb ferrous metals organic framework material
Using U.S. Micro company ASAP-2020 specific surface pore-size distribution instrument to prepared by embodiment of the present invention 1-4
The pore structure of Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 is characterized, as a result as table 1,
Shown in table 2.
Table 1
Table 2
By table 1, table 2 is as can be seen that the BET of Fe-hifpbb ferrous metals organic framework material prepared by the present invention compares table
Area is about in 136-272m2/ g, total pore volume are 0.088cm to the maximum3/ g, wherein mesopore pore size is about in 8-13nm or so；This explanation is originally
Four kinds of embodiments of invention are respectively provided with relatively-stationary micropore and mesopore pore size skeleton structure；Fe-hifpbb ferrous metals is organic
Framework material has middle micro-diplopore skeleton structure, is conducive to low-pressure state to form the strong suction-operated to small-molecule substance, and
The aperture of its micropore is more nearly with the kinetic diameter of n-hexane, causes which to have higher adsorptive selectivity to n-hexane.
(2) crystal structure properties of Fe-hifpbb ferrous metals organic framework material
Using German Bruker company D8-ADVANCE type X-ray diffractometer to the Fe- prepared by embodiment of the present invention 1-4
The crystal structure of hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 is characterized respectively, is wherein operated
Condition is：Cu target KαLight source, radiates intraductal electric current 40mA, voltage 40kv, and continuous scan mode, scanning angle scope are 5-45 °,
Sweep speed is 0.1 second/step, and scanning step is 0.02 °.
Fe-hifpbb-1, Fe-hifpbb-2, the Fe-hifpbb-3 prepared by embodiment of the present invention 1-4 is shown in Fig. 1
With the XRD spectra of Fe-hifpbb-4, it will be seen from figure 1 that four kinds of Fe-hifpbb samples are respectively provided with identical XRD spectra, its
Principal character peak position is identical, and under the conditions of this four kinds of explanation, synthesized material has identical crystal structure.
(3) Fe-hifpbb ferrous metals organic framework material heat endurance
Thermogravimetric analyzer using HTG-1/2 is to Fe-hifpbb-1, the Fe- prepared by embodiment of the present invention 1-4
Hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 carry out heat endurance sign, and its operating condition is：30 DEG C of initial temperature,
500 DEG C of final temperature, 5 DEG C/min of heating rate, nitrogen flow 30mL/min.
Illustrate in Fig. 2 Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 prepared by embodiment of the present invention 1-4 and
The thermogravimetric curve of Fe-hifpbb-4, from figure 2 it can be seen that four kinds of Fe-hifpbb samples all occur in that three weightlessness：First
Before step weight loss temperature range is 100 DEG C, this stage is mainly the guest molecule such as the water of residual, acetic acid in material pore structure
Lose, weight loss is the 5% of gross weight, belongs to physical change process；Second stage weightless temperature scope is 200 DEG C～300 DEG C,
The stage is mainly losing for double (4- carboxyl phenyl) HFC-236fas of 2,2-, and weight loss is the 15% of gross weight, illustrates in the stage
Its skeleton structure starts to cave in；Phase III weightless temperature scope is 390 DEG C～495 DEG C, mainly the losing of iron cluster, weight loss
For the 60% of gross weight, the phase material skeleton structure is caved in completely.
(4) curve of adsorption kinetics of the Fe-hifpbb ferrous metals organic framework material to C6
Curve of adsorption kinetics adopts Britain's Hiden IGA-003 weight adsorption analysis-e/or determining.Fig. 3 be 373K under, just
Hexane, 3- methylpentane, absorption power of 2, the 2- dimethylbutanes on the Fe-hifpbb-1 prepared by the embodiment of the present invention 1
Learn curve.Pretreatment condition before sample test is：Sample is vacuumized at 150 DEG C and 10h is dry, vacuum is up to 4-8Pa.
As seen from Figure 3, n-hexane under 298K, 80Torr, 3- methylpentane, 2,2- dimethylbutanes are in Fe-hifpbb-1 material
Adsorption capacity on material is respectively about 65mg/g, 55mg/g and 5mg/g, therefore for C6Alkane Isomers, Fe-
Hifpbb-1 has higher adsorptive selectivity to n-hexane.In addition as shown in Figure 3 the material to C6Alkane Isomers have
There is good separating property, for n-hexane/2,2- dimethylbutane system, adsorption capacity ratio are 13；For 3- methylpent
Alkane/2,2- dimethylbutane system, adsorption capacity ratio are 11.
(5) Fe-hifpbb ferrous metals organic framework material chemical stability
Using German Bruker company D8-ADVANCE X-ray diffractometer to the Fe- prepared by the embodiment of the present invention 1
Hifpbb-1 chemical stability is characterized, and wherein operating condition is：Cu target KαLight source, radiates intraductal electric current 40mA, voltage
40kv, continuous scan mode, scanning angle scope are 5-40 °, and sweep speed is 0.1 second/step, and scanning step is 0.02 °.
As seen from Figure 4, solution of the Fe-hifpbb-1 prepared by embodiment 1 in water immersion two weeks or in pH=2-10
Middle soak 24 hours afterwards, the XRD that obtains with do not soak before XRD basically identical, material in 2 θ=3.5 °, 11 °, 14 °,
15.2 ° etc. of characteristic diffraction peak is still present, and before and after illustrating to soak, the crystal framework structure of material is not changed substantially,
Keep original pore structure.Fe-hifpbb-1 soaking-resistant prepared by embodiment 1 is described, acid and alkali-resistance, chemical stability are good
Good.
(6) Fe-hifpbb ferrous metals organic framework material hydrophilicity and hydrophobicity test
Using German dataphysics company OCA40Micro type Surface Tension Surface contact angle tester to reality of the present invention
The hydrophobic performance for applying the Fe-hifpbb-1 prepared by example 1 is characterized, and wherein operating condition is：Brightness-adjustable monochrome cold light LED
Back light, method of testing are sessile drop method, sample diameter 13mm, and thickness is 0.5mm, and measuring resolution is 0.01 °, measuring accuracy
For 0.1 °, sample stage size is 120*120*30mm.
As seen from Figure 5, the Fe-hifpbb-1 prepared by embodiment 1 is 110 ° with the contact angle of water, and the material is described
For strong hydrophobic material.The strong-hydrophobicity of material can ensure that in wet condition carries out C6During isomer adsorbing separation, material
The duct of material and adsorption site are not occupied by hydrone, it is to avoid material occurred and reduced to C because adsorbing steam formation competitive Adsorption6
The situation of the adsorption capacity of isomer.
(7) Fe-hifpbb is tested to the absorption H103 resin of C6 isomer
Using GC9560 type gas chromatograph, flame ionization ditector (FID) detection outlet C6Alkane concentration.Chromatogram
Post is GDX5023DX502 type stainless stee l packed column, filler 149mg, a length of 2cm of filled column.Nitrogen buffer gas, adopt six
Port valve sample introduction, sample introduction gas be each concentration of component be all 1500ppm n-hexane/3- methylpentane gaseous mixture or n-hexane/2,2-
Dimethylbutane gaseous mixture, carrier gas flux are 18.5ml/min, and chromatogram column temperature is 363K, and detector temperature is 473K.
As seen from Figure 6, for concentration ratio be 1：1 n-hexane/2,2- dimethylbutane gaseous mixture, in embodiment 1
The time that H103 resin on prepared Fe-hifpbb-1 occurs through point is respectively about 51min and 5min, illustrates to implement
, for n-hexane/2,2- dimethylbutane mixed system, with Preferential adsorption n-hexane for Fe-hifpbb-1 prepared by example 1
Performance.
As seen from Figure 7, for concentration ratio be 1：1 n-hexane/3- methylpentane gaseous mixture, made in embodiment 1
The time that H103 resin on standby Fe-hifpbb-1 occurs through point is respectively about 15min and 1min, and embodiment 1 is described
Prepared Fe-hifpbb-1 has higher absorption to n-hexane and selects for n-hexane/3- methylpentane mixed system
Property.
It is possible thereby to illustrate 1 material of embodiment to n-hexane, the adsorbing separation of 3- methylpentane and 2,2- dimethylbutane
Performance has larger difference, therefore can be with the effective adsorbing separation n-hexane of Fe-hifpbb1,3- methylpentane and 2,2- diformazan
Base butane, Fe-hifpbb prepared by other embodiments and Fe-hifpbb1 have identical effect.
Claims (10)
1. a kind of to C6Isomer has the preparation method of the ferrous metals organic framework material of high adsorptive selectivity, and which is special
Levy and be, comprise the following steps：
（1）2,2- is double（4- carboxyl phenyl）HFC-236fa and iron cluster are dissolved separately in DMF, obtain 2,2- double（4- carboxyl phenyl）
The DMF solution of HFC-236fa and the DMF solution of iron cluster；
（2）2,2- is double（4- carboxyl phenyl）The DMF solution of HFC-236fa is added dropwise in the DMF solution of iron cluster, then is dropwise added
Acetic acid on the rocks, and stir, obtain mixed liquor；
（3）Mixed liquor is loaded stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；
（4）Reaction is washed with DMF and dichloromethane after terminating successively, and centrifugal filtration is extracted, and is put in baking oven and is dry, and obtains iron-based gold
Category organic framework material, is labeled as Fe-hifpbb.
2. preparation method according to claim 1, it is characterised in that step（1）The preparation of the iron cluster includes following step
Suddenly：First by anhydrous sodium acetate and Fe (NO3)3·9H2O is dissolved in water, and obtains sodium acetate solution and iron nitrate solution；Then
Sodium acetate solution is dropwise instilled in iron nitrate solution, stirring, form mixed solution；Again mixed solution is carried out suction filtration, and according to
Secondary deionized water and ethanol washing, are put in baking oven and dry, obtain iron cluster.
3. preparation method according to claim 2, it is characterised in that the anhydrous sodium acetate and Fe (NO3)3·9H2O's
Mass ratio is（3.147~4）：1.
4. preparation method according to claim 2, it is characterised in that the time of the stirring is 8 ~ 24 h.
5. preparation method according to claim 1, it is characterised in that 2, the 2- are double（4- carboxyl phenyl）HFC-236fa/
The mass ratio of iron cluster/glacial acetic acid/DMF is 1:(1~2):(11.6~20):(126.4~150).
6. preparation method according to claim 1, it is characterised in that step（3）The program control of the hydrothermal synthesis reaction
Warm process is：
The temperature programming stage：Heating rate is set as 5 ~ 10 DEG C/min, mixed liquor is risen to 140 ~ 150 DEG C from room temperature；
The constant temperature stage：The temperature of mixed liquor keeps 12 ~ 24h at 140 ~ 150 DEG C;
The programmed cooling stage：If rate of temperature fall is 0.4 ~ 1 DEG C/min, reaction solution is down to 25 ~ 50 DEG C from 140 ~ 150 DEG C.
7. preparation method according to claim 1, it is characterised in that step（4）The rotating speed of the centrifugation is 6000 ~ 9000
r/min.
8. preparation method according to claim 1, it is characterised in that step（4）The temperature of the drying is 80 ~ 150 DEG C.
9. a kind of to C obtained in preparation method described in any one of claim 1-86Isomer has high absorption and selects
The ferrous metals organic framework material of property.
10. a kind of to C described in claims 96Isomer has the ferrous metals organic backbone material of high adsorptive selectivity
Material is applied to C6In the separation of isomer.
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| CN108329484A (en) * | 2018-03-01 | 2018-07-27 | 华南理工大学 | Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof |
| CN108794754A (en) * | 2018-06-05 | 2018-11-13 | 安徽师范大学 | New copper-metal-organic framework material and its preparation method and application |
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| CN107732248A (en) * | 2017-11-21 | 2018-02-23 | 盐城工学院 | The MOF materials of negative electrode of lithium ion battery and its application |
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| CN108329484A (en) * | 2018-03-01 | 2018-07-27 | 华南理工大学 | Double ligand metal organic framework materials of a kind of iron-based of Preferential adsorption ethane and the preparation method and application thereof |
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| CN112645788B (en) * | 2020-05-08 | 2021-09-21 | 浙江大学 | Method for separating 2, 2-dimethylbutane and 2, 3-dimethylbutane |
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| CN113117648A (en) * | 2021-03-04 | 2021-07-16 | 浙江大学 | Separation method of hexane isomers |
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