CN106475059B - A kind of couple of C6Isomer has the ferrous metals organic framework material and the preparation method and application thereof of high adsorptive selectivity - Google Patents
A kind of couple of C6Isomer has the ferrous metals organic framework material and the preparation method and application thereof of high adsorptive selectivity Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
Abstract
The invention discloses a kind of couple of C6Isomer has the ferrous metals organic framework material and the preparation method and application thereof of high adsorptive selectivity, and this method comprises the following steps: (1) bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- and iron cluster being dissolved separately in DMF；(2) DMF solution of bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- is added dropwise in the DMF solution of iron cluster, glacial acetic acid, stirring is added dropwise；(3) it is packed into stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；(4) it washs, is centrifuged, it is dry, obtain ferrous metals organic framework material.Resulting materials of the present invention are to C6It is under equal conditions 3 times or more of the conventional adsorbents such as 5A molecular sieve to n-hexane adsorptive selectivity that Alkane Isomers, which have high adsorptive selectivity, and has good chemical stability and hydrophobicity.The material can separate C from direct steaming gasoline6Isomer has good potential application foreground.
Description
Technical field
The present invention relates to C6Alkane Isomers adsorption separation technology field, in particular to a kind of pair of C6 isomer
Ferrous metals organic framework material and the preparation method and application thereof with high adsorptive selectivity.
Background technique
N-hexane is industrial widely used one of hydrocarbon solvent, and most representative nonpolar solvent, may be used also
As essential oil diluent and for extracting essence in fragrance material etc..Currently, n-hexane generally uses rectifying from direct steaming gasoline
Separation method obtains.But in these raw materials, containing with the very similar component of n-hexane boiling point, such as 3- methylpentane and 2,2-
Therefore the isomer of the n-hexanes such as dimethylbutane efficiently separates n-hexane, 3- methylpentane and 2,2- dimethylbutane
Equal C6Isomer has significant application value and research significance.
Currently, domestic and international C6The isolation technics of Alkane Isomers mainly has conventional distillation method, azeotropic distillation, extraction
Rectification method and adsorption separation method etc..Wherein, adsorption separation method due to technological equipment investment it is low, low energy consumption, simple operation and other advantages,
It is considered as a kind of C of great potential6The isolation technics of Alkane Isomers.Adsorbent material is the core of adsorption separation technology
The heart is developed to C6Alkane Isomers adsorption capacity is big, and the higher adsorbent material of selectivity has become one of research hotspot.
Molecular sieve is widely used in C as a kind of common conventional adsorbent6The adsorbing separation of Alkane Isomers.Patrick
S.Ba ' rcia etc. is with BETA molecular sieve to C6Alkane Isomers are the study found that when 423K, 0.3bar, BETA molecular sieve pair
C6Alkane Isomers adsorbance can reach 0.07g/g, and adsorbance size order is n-hexane > 3- methylpentane > 2,3- bis-
Methybutane > 2,2- dimethylbutane.K.Huddersman etc. uses Beta (H, Na), mordenite (Na), silicalite
(Na), EU-1 (Na), ZSM-12 (Na), a series of molecular sieves such as SAPO-5 are to C6Alkane Isomers adsorption separation performance into
Row research, research find that Beta (H, Na) has excellent adsorptivity to 3- methylpentane and 2,3- dimethylbutane at 325 DEG C
Can, adsorbance is respectively 0.104g/g and 0.099 g/g.R.Krishna etc. is separated the study found that when 433K with molecular sieve MFI
N-hexane/dimethyl pentane, adsorptive selectivity 4.Above research shows that molecular sieve is to C6The absorption of Alkane Isomers is held
It measures lower.In addition, adsorbent of molecular sieve is to C6Alkane Isomers adsorptive selectivity is poor, can not be efficiently separated, limit
Its application industrially is made.Therefore, research and development are to C6Alkane Isomers adsorption capacity is big, and selectivity is higher new
Type adsorbent 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 for the first time
Using Zn (BDC) (Dabco)0.5(MOF 1) is used for C6Alkane Isomers adsorbing separation, discovery 1 material of MOF are preferentially inhaled
Attached straight chain C6Alkane.Na Chang research group research discovery ZIF-8 material is to straight chain C6Alkane and branch C6Alkane has separation
Performance, and Preferential adsorption straight chain C6Alkane；The discovery such as Patrick S.Ba ' rcia UiO-66 can also be used for C6Alkane is different with dividing
Structure body adsorbing separation and Preferential adsorption branch C6Alkane, it is longer that reason is that the tetrahedroid duct of UiO-66 cannot accommodate carbochain
N-hexane；0.6Kpa, at 430 DEG C, 2,2- dimethylbutanes/n-hexane and 2, the choosing of 2- dimethylbutane/3- methylpentane
Selecting 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 sequence are as follows: n-hexane > 2- methylpentane > 3- methylpentane > 2,3- dimethylbutane
≈ 2,2- dimethylbutane, but there are adsorbing separation C6The selectively lower problem of isomer.
Summary of the invention
In order to overcome the above problems, the present invention provides a kind of couple of C6Isomer has the iron-based of high adsorptive selectivity
Metal-organic framework materials and the preparation method and application thereof.
Ferrous metals organic framework material (Fe-hifpbb) of the invention is by iron cluster Fe3(CH3COO)6And organic ligand
2,2- bis- (4- carboxyl phenyl) hexafluoropropane pass through three-dimensional porous framework material made of self assembly.Fe-hifpbb is to C6Alkane
Isomer has excellent adsorption separation performance, and the mainly kinetic diameter of its aperture and n-hexane is closer, causes
Its Preferential adsorption n-hexane.What is particularly worth mentioning is that making the materials chemistry stability due to the strong coordination of ferric iron and ligand
It is good, it can acid and alkali-resistance immersion.In addition, containing a large amount of fluorine atom on organic ligand, stronger hydrophobic performance is made it have.Material is dredged
Aqueous when can guarantee to carry out adsorbing separation in wet condition, the duct of material and adsorption site are not occupied by hydrone, are kept away
Exempt from the problem of material reduces its adsorption capacity due to adsorbing steam and forming competitive Adsorption occur.The material is in C6Isomer point
There is good potential application foreground from aspect.
The purpose of the present invention is achieved through the following technical solutions.
A kind of couple of C6Isomer has the preparation method of the ferrous metals organic framework material of high adsorptive selectivity, packet
Include following steps:
(1) bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- and iron cluster are dissolved separately in DMF, obtain bis- (the 4- carboxyls of 2,2-
Phenyl) DMF solution of hexafluoropropane and the DMF solution of iron cluster；
(2) DMF solution of bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- is added dropwise in the DMF solution of iron cluster, then by
Drop addition glacial acetic acid, and stir, obtain mixed liquor；
(3) mixed liquor is packed into stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；
(4) it is successively washed after reaction with DMF and methylene chloride, centrifugal filtration is extracted, and is placed in oven and dried, is obtained iron
Base Metal organic framework material is labeled as Fe-hifpbb.
Preferably, the preparation of step (1) the iron cluster is the following steps are included: 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 instilled to ferric nitrate dropwise molten
In liquid, stirring forms mixed solution；Mixed solution is filtered again, and successively uses deionized water and ethanol washing, is put into baking
It is dried in case, obtains 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 be 8~for 24 hours.
Preferably, bis- (4- carboxyl phenyl) hexafluoropropane of 2, the 2-/iron cluster/glacial acetic acid/DMF mass ratio is 1:(1
~2): (11.6~20): (126.4~150).
Preferably, the temperature programmed control process of step (3) described hydrothermal synthesis reaction are as follows:
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 140~150 DEG C keep 12~for 24 hours;
Program temperature-fall period: setting rate of temperature fall as 0.4~1 DEG C/min, reaction solution is down to from 140~150 DEG C to 25~
50℃。
It is further preferred that the temperature programmed control process of step (3) described hydrothermal synthesis reaction are as follows:
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 150 DEG C keep 12~for 24 hours;
Program temperature-fall period: rate of temperature fall is set as 0.4~1 DEG C/min, reaction solution is down to 35 DEG C from 150 DEG C.
Preferably, the revolving speed of step (4) described centrifugation is 6000~9000r/min.
Preferably, the temperature of step (4) described drying is 80~150 DEG C.
A kind of couple of C as made from above-described preparation method6Isomer has the iron-based gold of high adsorptive selectivity
Belong to 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 technical effect:
1. chemical stability is good, soaking-resistant, acid and alkali-resistance, it is basic that skeleton structure is impregnated in pH=2 and the solution of pH=10
It remains unchanged.
2. having good hydrophobicity, it is 110 ° that hydrophobicity, which tests contact angle,.
3.Fe-hifpbb is to C6Alkane Isomers have good adsorptive selectivity, can efficiently separate straight chain and branch
Chain C6Alkane.
Detailed description of the invention
Fig. 1 is Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and Fe- prepared by the embodiment of the present invention 1~4
The XRD diagram of hifpbb-4.
Fig. 2 is Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and 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, 2,2- dimethylbutanes Fe- prepared by the embodiment of the present invention 1
Adsorbance on hifpbb-1 changes over time curve.
Fig. 4 is the XRD diagram after Fe-hifpbb-1 prepared by the embodiment of the present invention 1 impregnates in different pH solution.
Fig. 5 is the contact angle test figure of 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 penetrates
Curve graph.
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 range of embodiment statement.
Embodiment 1
(1) 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 instilled in iron nitrate aqueous solution dropwise, and 8h is stirred, obtains mixed liquor；3. will mixing
Liquid carries out filtering to obtain brown solid, and successively uses deionized water and ethanol washing product, and product is put under 70 DEG C of vacuum ovens
Freeze-day with constant temperature 7 hours, iron cluster [Fe is made3(CH3COO)6]。
(2) synthesis of Fe-hifpbb: 1. by 450mg ligand 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2- and 450mg iron cluster
It is dissolved separately in 30ml (28.44g) n,N-Dimethylformamide (DMF)；2. by 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2-
DMF solution be added dropwise in the DMF solution of iron cluster, then 5.0ml (5.25g) glacial acetic acid is added dropwise, and stir 30 min extremely
Mixed liquor is uniform；3. mixed liquor is packed into 100ml stainless steel autoclave, temperature programmed control hydrothermal synthesis reaction is carried out；Setting
Temperature program are as follows: 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
Reaction solution is down to 25 DEG C with the rate of temperature fall of 0.4 DEG C/min；4. product successively carries out DMF and methylene chloride washing each two
Secondary, centrifuge speed is 6000r/min centrifugation, and the product after washing is put into 80 DEG C of baking ovens and is dried for standby, and marks this sample to be
Fe-hifpbb-1。
Embodiment 2
(1) 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 instilled in iron nitrate aqueous solution dropwise, and stir for 24 hours, obtains mixed liquor；3. by mixed liquor into
Row filters to obtain brown solid, and successively uses deionized water and ethanol washing product, and product is put into constant temperature under 70 DEG C of vacuum ovens
It is 7 hours dry, iron cluster [Fe is made3(CH3COO)6]。
(2) synthesis of Fe-hifpbb: 1. by 450mg ligand 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2- and 900mg iron cluster
It is dissolved separately in 35.6ml (33.75g) n,N-Dimethylformamide (DMF)；2. by 2, bis- (4- carboxyl phenyl) hexafluoros third of 2-
The DMF solution of alkane is added dropwise in the DMF solution of iron cluster, then 8.57ml (9.0g) glacial acetic acid is added dropwise, and stir 30min
It is uniform to mixed liquor；3. mixed liquor is packed into 100ml stainless steel autoclave, temperature programmed control hydrothermal synthesis reaction is carried out；If
Determine temperature program are as follows: reaction solution is heated to 150 DEG C with the heating rate of 10 DEG C/min, is heated for 24 hours at a temperature of 150 DEG C,
Then reaction solution is down to 50 DEG C with the rate of temperature fall of 1 DEG C/min；4. product successively carries out DMF and methylene chloride washing each two
Secondary, centrifuge speed is 9000r/min centrifugation, and the product after washing is put into 80 DEG C of baking ovens and is dried for standby, and marks this sample to be
Fe-hifpbb-2。
Embodiment 3
(1) 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 instilled in iron nitrate aqueous solution dropwise, and 16h is stirred, obtains mixed liquor；3. by mixed liquor into
Row filters to obtain brown solid, and successively uses deionized water and ethanol washing product, and product is put into constant temperature under 70 DEG C of vacuum ovens
It is 7 hours dry, iron cluster [Fe is made3(CH3COO)6]。
(2) synthesis of Fe-hifpbb: 1. by 450mg ligand 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2- and 675mg iron cluster
It is dissolved separately in 32.8ml (31.1g) n,N-Dimethylformamide (DMF)；2. by 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2-
DMF solution be added dropwise in the DMF solution of iron cluster, then 6.785ml (7.125g) glacial acetic acid is added dropwise, and stir 30min
It is uniform to mixed liquor；3. mixed liquor is packed into 100ml stainless steel autoclave, temperature programmed control hydrothermal synthesis reaction is carried out；If
Determine temperature program are as follows: reaction solution is heated to 145 DEG C with the heating rate of 7.5 DEG C/min, is heated for 24 hours at a temperature of 145 DEG C,
Then reaction solution is down to 37.5 DEG C with the rate of temperature fall of 0.7 DEG C/min；4. product successively carries out DMF and methylene chloride washing
Respectively twice, centrifuge speed is 7500r/min centrifugation, and the product after washing is put into 115 DEG C of baking ovens and is dried for standby, and marks this
Sample is Fe-hifpbb-3.
Embodiment 4
(1) 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 instilled in iron nitrate aqueous solution dropwise, and 8h is stirred, obtains mixed liquor；3. will mixing
Liquid carries out filtering to obtain brown solid, and successively uses deionized water and ethanol washing product, and product is put under 70 DEG C of vacuum ovens
Freeze-day with constant temperature 7 hours, iron cluster [Fe is made3(CH3COO)6]。
(2) synthesis of Fe-hifpbb: 1. by 450mg ligand 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2- and 675mg iron cluster
It is dissolved separately in 32.8ml (31.1g) n,N-Dimethylformamide (DMF)；2. by 2, bis- (4- carboxyl phenyl) hexafluoropropane of 2-
DMF solution be added dropwise in the DMF solution of iron cluster, then 6.785ml (7.125g) glacial acetic acid is added dropwise, and stir 30min
It is uniform to mixed liquor；3. mixed liquor is packed into 100ml stainless steel autoclave, temperature programmed control hydrothermal synthesis reaction is carried out；If
Determine temperature program are as follows: reaction solution is heated to 145 DEG C with the heating rate of 7.5 DEG C/min, is heated for 24 hours at a temperature of 145 DEG C,
Then reaction solution is down to 37.5 DEG C with the rate of temperature fall of 0.7 DEG C/min；4. product successively carries out DMF and methylene chloride washing
Respectively twice, centrifuge speed is 7500r/min centrifugation, and the product after washing is put into 115 DEG C of baking ovens and is dried for 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.'s Micro company ASAP-2020 specific surface pore-size distribution instrument to prepared by 1-4 of the embodiment of the present invention
The pore structure of Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 are characterized, as a result such 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 up to 0.088cm3/ g, wherein mesopore pore size is about in 8-13nm or so；This illustrates this
Four kinds of embodiments of invention all have relatively-stationary micropore and mesopore pore size skeleton structure；Fe-hifpbb ferrous metals are organic
Framework material has middle micro-diplopore skeleton structure, is conducive to low-pressure state and forms strong suction-operated to small-molecule substance, and
The aperture of its micropore and the kinetic diameter of n-hexane are more nearly, it is caused 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 prepared by 1-4 of the embodiment of the present invention
The crystal structure of Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 are characterized respectively, wherein grasping
Make condition are as follows: Cu target KαLight source radiates intraductal electric current 40mA, and voltage 40kv, continuous scanning mode, scanning angle range is 5-
45 °, scanning speed is 0.1 second/step, and scanning step is 0.02 °.
Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 prepared by 1-4 of the embodiment of the present invention are 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 all have identical XRD spectra,
Main feature peak position is identical, synthesized substance crystal structure having the same under the conditions of this four kinds of explanation.
(3) Fe-hifpbb ferrous metals organic framework material thermal stability
Using the thermogravimetric analyzer of HTG-1/2 to Fe-hifpbb-1, Fe- prepared by 1-4 of the embodiment of the present invention
Hifpbb-2, Fe-hifpbb-3 and Fe-hifpbb-4 carry out thermal stability characterization, operating condition are as follows: and 30 DEG C of initial temperature,
500 DEG C of final temperature, heating rate 5 DEG C/min, nitrogen flow 30mL/min.
Shown in Fig. 2 Fe-hifpbb-1, Fe-hifpbb-2, Fe-hifpbb-3 prepared by 1-4 of the embodiment of the present invention and
The thermogravimetric curve of Fe-hifpbb-4, from figure 2 it can be seen that four kinds of Fe-hifpbb samples occur it is weightless three times: first
Before step weight loss temperature range is 100 DEG C, this stage is mainly the guest molecules such as remaining water, acetic acid in material pore structure
It loses, weight loss is the 5% of total weight, belongs to physical change process；Second stage weightless temperature range is 200 DEG C~300 DEG C,
The stage is mainly that bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- lose, and weight loss is the 15% of total weight, is illustrated in the rank
Its skeleton structure of section starts to collapse；Phase III weightless temperature range is 390 DEG C~495 DEG C, and mainly iron cluster loses, weightless
Amount is the 60% of total weight, which collapses completely.
(4) curve of adsorption kinetics of the Fe-hifpbb ferrous metals organic framework material to C6
Curve of adsorption kinetics uses Britain Hiden IGA-003 weight adsorption analysis-e/or determining.Fig. 3 is under 373K, 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 are as follows: by sample vacuum drying 10h at 150 DEG C, vacuum degree is up to 4-8Pa.
As seen from Figure 3, the n-hexane at 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.Furthermore as shown in Figure 3 the material to C6Alkane Isomers tool
There is good separating property, for n-hexane/2,2- dimethylbutane system, adsorption capacity ratio is 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 Fe- prepared by the embodiment of the present invention 1
Hifpbb-1 chemical stability is characterized, wherein operating condition are as follows: Cu target KαLight source radiates intraductal electric current 40mA, voltage
40kv, continuous scanning mode, scanning angle range is 5-40 °, and scanning speed is 0.1 second/step, and scanning step is 0.02 °.
As seen from Figure 4, Fe-hifpbb-1 prepared by embodiment 1 water impregnate two weeks or pH=2-10 solution
It is middle impregnate 24 hours after, obtained XRD diagram and the XRD before not impregnating is almost the same, and material is in 2 θ=3.5 °, 11 °, 14 °,
15.2 ° etc. of characteristic diffraction peak still exist, illustrate impregnate front and back material crystal framework structure substantially there is no variation,
Keep original pore structure.Illustrate that Fe-hifpbb-1 soaking-resistant, acid and alkali-resistance, chemical stability prepared by embodiment 1 are good
It is good.
(6) Fe-hifpbb ferrous metals organic framework material hydrophilicity and hydrophobicity is tested
Using German dataphysics company OCA40Micro type Surface Tension Surface contact angle tester to of the invention real
The hydrophobic performance for applying Fe-hifpbb-1 prepared by example 1 is characterized, wherein operating condition are as follows: brightness-adjustable monochrome cold light
LED backlight light source, test method are sessile drop method, and sample diameter 13mm, with a thickness of 0.5mm, measuring resolution is 0.01 °, test
Precision is 0.1 °, and sample stage size is 120*120*30mm.
As seen from Figure 5, the contact angle of Fe-hifpbb-1 and water prepared by embodiment 1 are 110 °, illustrate the material
For strong hydrophobic material.The strong-hydrophobicity of material can guarantee to carry out C in wet condition6When isomer adsorbing separation, material
The duct of material and adsorption site are not occupied by hydrone, and avoiding the occurrence of material reduces due to adsorbing steam and forming competitive Adsorption to C6
The case where adsorption capacity of isomer.
(7) Fe-hifpbb tests the absorption H103 resin of C6 isomer
Using GC9560 type gas chromatograph, flame ionization ditector (FID) detection outlet C6Alkane concentration.Chromatography
Column is GDX5023DX502 type stainless stee l packed column, filler 149mg, a length of 2cm of filled column.Nitrogen buffer gas, using six
Port valve sample introduction, sample introduction gas are the n-hexane/3- methylpentane gaseous mixture or n-hexane/2,2- that each component concentration is all 1500ppm
Dimethylbutane gaseous mixture, carrier gas flux 18.5ml/min, chromatogram column temperature 363K, detector temperature 473K.
As seen from Figure 6, for concentration than n-hexane/2,2- dimethylbutane gaseous mixture for 1:1, 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
Fe-hifpbb-1 prepared by example 1 has Preferential adsorption n-hexane for n-hexane/2,2- dimethylbutane mixed system
Performance.
As seen from Figure 7, made in embodiment 1 for concentration than the n-hexane for 1:1/3- methylpentane gaseous mixture
The time that H103 resin on standby Fe-hifpbb-1 occurs through point is respectively about 15min and 1min, illustrates embodiment 1
Prepared Fe-hifpbb-1 is selected for n-hexane/3- methylpentane mixed system, to n-hexane with higher absorption
Property.
It is possible thereby to illustrate 1 material of embodiment to n-hexane, 3- methylpentane and 2, the adsorbing separation of 2- dimethylbutane
Performance has biggish difference, therefore can use the effective adsorbing separation n-hexane of Fe-hifpbb1,3- methylpentane and 2,2- diformazan
The Fe-hifpbb and Fe-hifpbb1 of base butane, other embodiments preparation has the same effect.
Claims (8)
1. a kind of couple of C6Isomer has the preparation method of the ferrous metals organic framework material of high adsorptive selectivity, special
Sign is, comprising the following steps:
(1) bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- and iron cluster are dissolved separately in DMF, obtain 2,2- bis- (4- carboxyl phenyls)
The DMF solution of hexafluoropropane and the DMF solution of iron cluster；
(2) DMF solution of bis- (4- carboxyl phenyl) hexafluoropropane of 2,2- is added dropwise in the DMF solution of iron cluster, then added dropwise
Acetic acid on the rocks, and stir, obtain mixed liquor；
(3) mixed liquor is packed into stainless steel autoclave, carries out temperature programmed control hydrothermal synthesis reaction；
(4) it is successively washed after reaction with DMF and methylene chloride, centrifugal filtration is extracted, and is placed in oven and dried, is obtained iron-based gold
Belong to organic framework material, is labeled as Fe-hifpbb；
The preparation of step (1) the iron cluster is the following steps are included: first by anhydrous sodium acetate and Fe (NO3)3·9H2O is dissolved separately in
In water, sodium acetate solution and iron nitrate solution are obtained；Then sodium acetate solution is instilled in iron nitrate solution dropwise, is stirred, formed
Mixed solution；Mixed solution is filtered again, and successively uses deionized water and ethanol washing, is put into baking oven and dries, obtain iron
Cluster；
The temperature programmed control process of step (3) described hydrothermal synthesis reaction are as follows:
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 140 ~ 150 DEG C keep 12 ~ for 24 hours;
Program temperature-fall period: rate of temperature fall is set as 0.4 ~ 1 DEG C/min, reaction solution is down to 25 ~ 50 DEG C from 140 ~ 150 DEG C.
2. preparation method according to claim 1, which is characterized in that the anhydrous sodium acetate and Fe (NO3)3·9H2O's
Mass ratio is (3.147 ~ 4): 1.
3. preparation method according to claim 1, which is characterized in that the time stirred in the preparation process of the iron cluster is
8~24 h。
4. preparation method according to claim 1, which is characterized in that bis- (4- carboxyl phenyl) hexafluoropropane of 2,2-/
Iron cluster/glacial acetic acid/DMF mass ratio is 1:(1 ~ 2): (11.6 ~ 20): (126.4 ~ 150).
5. preparation method according to claim 1, which is characterized in that the revolving speed of step (4) described centrifugation is 6000 ~ 9000
r/min。
6. preparation method according to claim 1, which is characterized in that the temperature of step (4) described drying is 80 ~ 150 DEG C.
7. a kind of couple of C as made from preparation method described in any one of claims 1-66Isomer has high absorption selection
The ferrous metals organic framework material of property.
8. a kind of couple of C described in claims 76Isomer has the ferrous metals organic backbone material of high adsorptive selectivity
Material is applied to C6In the separation of isomer.
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