CN106492754A - A kind of preparation method of adsorbent, method of modifying and application - Google Patents
A kind of preparation method of adsorbent, method of modifying and application Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- -1 salt hydrates Chemical class 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 230000001413 cellular effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000008246 gaseous mixture Substances 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000006011 modification reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002171 ethylene diamines Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229950000845 politef Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of adsorbent, method of modifying and application, adsorbent is obtained by ultrasonic wave added solvent-thermal process method or microwave process for synthesizing using metal salt hydrates and dihydric para-phthalic acid, modified to which with organic amine again, modified adsorbent is obtained, is applied to adsorb the CO in gaseous mixture by bi-material2, higher selectivity and adsorption capacity is shown, there is good application prospect in gas separation field.
Description
Technical field
The present invention relates to a kind of preparation method of adsorbent, method of modifying and application, belong to metal-organic framework adsorbent
The preparation of material and its application.
Background technology
Metal-organic framework compound（MOFs）It is the tool by multiple tooth organic ligand and metal ion by being self-assembly of
There is a class supermolecule porous crystalline material of periodic network structure, it has the secondary structure unit of clear and definite geometry and solely
Special physics and chemical property advantage.In fields such as adsorbing separation, catalysis, drug targetings, material metal center is not both which
Property and the major influence factors of performance, next to that the degree of saturation of metal-complexing.
Compared with the metallo organic material that saturation is coordinated with metal center, it is with excellent that metal center is coordinated undersaturated material
Gesture：Undersaturated metal-complexing can improve the interaction position of MOFs materials and adsorbate, make sorbent material show compared with
Good selectivity and adsorption capacity.Additionally, undersaturated metal-complexing is also MOFs to be changed on atom and molecular level
Enter design and surface-functionalized modification provides more accurate, more effective approach, it is sufficient to tackle current CO2Absorption, epoxidation are urged
The challenge of the technology such as change.
The traditional preparation method of MOFs materials is longer the time required to mostly being hydrothermal synthesis method, the method, it usually needs 2 ~ 3 days
Or longer, and crystalline product size is uneven, the moisture in simultaneous reactions reagent can take the unsaturated site in material, affect
Its absorption property.Although the hydrone of metal center end can be removed after synthesis in the way of heat treatment or acid treatment, by
Many in the hydrone for taking unsaturated site, easily make the mechanical strength of the material basic framework be affected.
The present invention prepares MOFs adsorbents using ultrasonic wave added solvent-thermal process method and microwave process for synthesizing, and reaction reagent is avoided
Solvent is used water as, and greatly shortens the response time, obtained adsorbent absorption property is better than prior art；The adsorbent is carried out
Modified, its absorption property is further lifted.
Content of the invention
It is an object of the invention to provide a kind of energy consumption preparation method low, simple to operate is solving conventional hydrothermal synthetic method
The problems such as crystalline product size of preparation is uneven, crystallization time length, hydrone take unsatuated metal position, while pass through surface
Functional modification improves cellular solid in gaseous mixture to CO2Absorption property.
Realize that technical scheme is as follows：
A kind of preparation method of adsorbent and method of modifying, are carried out as follows：
（1）Take dimethylformamide（DMF）Mixed solvent is made with anhydrous alcoholic solvent；
（2）Take step（1）Obtained mixed solvent, metal salt hydrates are dissolved, metal salt hydrates, DMF, anhydrous alcoholic solvent
Mol ratio be (1.2 ~ 1.8):(39~58):58；
（3）Step is separately taken（1）Obtained mixed solvent, by dihydric para-phthalic acid（H2DOBDC）Dissolving, H2DOBDC、DMF、
The mol ratio of anhydrous alcoholic solvent is 1: (39~58):58；
（4）By step（2）And step（3）Obtained two kinds of solution mix homogeneously obtain mixed solution, metal salt hydrates and dihydroxy
The mol ratio of base p-phthalic acid is 1.2 ~ 1.8:1；
（5）By step（4）Obtained mixed solution 30～60min of supersound process at 40～50 DEG C, then moves into reaction under high pressure
In kettle, at 85～110 DEG C, 10～15h is reacted, take out reactor and be cooled to room temperature, filter, and use and step（1）Middle identical
Absolute alcohol solvent clean repeatedly, in 120～165 DEG C of vacuum environment dries 10～15h, obtains final product adsorbent；
（6）By step（5）Obtained adsorbent, is added in the anhydrous toluene solution containing organic amine, adsorbent and organic amine matter
Amount is than being 4 ~ 6:1, surface modification reaction is carried out at 100～115 DEG C, the response time is 9～12h, obtains intermediate product；
（7）By step（6）Gained intermediate product is cooled to room temperature, filters, is washed with dichloromethane, in 40～70 DEG C of vacuum ring
1～4h is dried in border, modified adsorbent is obtained.
Step（5）Can be replaced：By step（4）Obtained mixed solution is directly moved in autoclave, and by high pressure
Reactor is put in microwave reaction device, at 90～110 DEG C reacts 0.5～1.5h, is taken out reactor and is cooled to room temperature, mistake
Filter, and use and step（1）Middle identical absolute alcohol solvent clean is multiple, dry 10 in 120～165 DEG C of vacuum environment～
15h, obtains final product adsorbent.
Step（1）Described in metal salt hydrates be copper, scandium, chromium, in aluminum the nitrate hydrate of any one element or
Chlorination salt hydrate.
The anhydrous alcoholic solvent is absolute methanol, dehydrated alcohol, the one kind in anhydrous propyl alcohol.
Step（6）Described in organic amine be ethylenediamine, diethylenetriamine, the one kind in triethylene tetramine.
Adsorbent and modified adsorbent obtained in above-mentioned preparation method can be applicable to industrial mixed gas and separate, such as selectivity
CO in absorption flue gas2Gas.
Compared with existing prior synthesizing method, the present invention has advantages below：
（1）Preparation time is short.Prior art generally needs 2 ~ 3 days or longer, and the present invention can shorten for about 50% time；
（2）Without water as solvent.Conventional hydrothermal synthetic method makees solvent using water, and in the product of synthesis, large quantity of moisture can take
Unsatuated metal site so that when the hydrone of metal center end is subsequently removed in the way of heat treatment or acid treatment, pole
The mechanical strength of the basic framework of product is easily made to be affected；In product obtained in of the invention, though still there is metal salt hydrates institute
The water of crystallization for containing takes unsaturated site, but relative to product obtained in conventional hydrothermal synthetic method, hydrone content is substantially reduced.
Therefore, the hydrone of high-temperature process removal metal center end is had little to no effect to its structure；
（3）The present invention adopts ultrasound for microwave condition, makes obtained Product size uniform, and specific surface area is about 1350m2/ g is more than
The 1270m of hydrothermal synthesis method product2/g.
（4）The present invention is modified to adsorbent using organic amine, provides amino to adsorbent, as amino has necessarily
Alkalescence, adsorbent can be improved to CO2Adsorptive selectivity, and amido functional group take metal position while can be by metal center
Position is made and CO to point2Interaction position increases, and adsorbance of the adsorbance than conventional hydrothermal synthetic method product 105mg/g averagely increases
Plus 43.9%.
Description of the drawings
Fig. 1 is adsorbent electron microscope obtained in embodiment 1.
Specific embodiment
The present invention is described in further details with reference to example, but the protection of the present invention is not limited to the content.
Embodiment 1
（1）The preparation of adsorbent
Weigh 7.32g Gerhardites first and 5g dihydric para-phthalic acids be dissolved in by 76mL dimethylformamides respectively and
In the mixed solvent that 110mL anhydrous propyl alcohols are made, 15min is stirred in constant temperature blender with magnetic force and obtain clear liquor；Secondly by two
Clear liquor mixing is planted, and 10min is stirred in constant temperature blender with magnetic force, is stirred, obtain mixed solution；Then by mixed solution
Move in wide mouthed bottle, after Ultrasonic Heating process 60min at 40 DEG C, reactant is moved into politef rustless steel reaction under high pressure
In kettle, 14h is reacted in 85 DEG C of baking ovens；Room temperature is finally cooled to, is filtered, anhydrous propyl alcohol is washed 3 times, and at 160 DEG C
10h is dried in vacuum, adsorbent is obtained；As shown in Figure 1, obtained adsorbent size is uniform；
（2）The preparation of modified adsorbent
Take step（1）Obtained coordination unsaturation cellular solid 2g is added to the anhydrous toluene solution containing 0.4g ethylenediamines
In, surface modification reaction is carried out at 110 DEG C, the time is 9h；Room temperature is cooled to, is filtered, is washed with dichloromethane, at 60 DEG C
2h is dried in vacuum environment, modified adsorbent is obtained.
It is used for adsorbing N by two kinds of products of the present embodiment2/CO2CO in gaseous mixture2, adsorbance is shown in Table with selective data
1.
Embodiment 2
（1）The preparation of adsorbent
Weigh 11.36g ANN aluminium nitrate nonahydrates first and 5g dihydric para-phthalic acids are dissolved in respectively by 76mL dimethylformamides
In the mixed solvent that makes with 85mL dehydrated alcohol, stir to being completely dissolved；Secondly it is mixed and stirred for uniform to mix by two solution
Close solution；Then by mixed solution, at 45 DEG C, Ultrasonic Heating is processed after 45min, and reactant is moved in autoclave, in
13h is reacted in 90 DEG C of baking ovens；Room temperature is finally cooled to, is filtered, absolute ethanol washing 4 times, and done in 150 DEG C of vacuum
Dry 12h, obtains adsorbent；
（2）The preparation of modified adsorbent
Take step（1）It is molten that obtained coordination unsaturation cellular solid 3.6g is added to the dry toluene containing 0.6g ethylenediamines
In liquid, surface modification reaction is carried out at 100 DEG C, the time is 12h；Room temperature is cooled to, is filtered, is washed with dichloromethane, 40
DEG C vacuum environment in dry 4h, obtain modified adsorbent.
It is used for adsorbing N by two kinds of products of the present embodiment2/CO2CO in gaseous mixture2, adsorbance is shown in Table with selective data
1.
Embodiment 3
（1）The preparation of adsorbent
Weigh six nitric hydrate scandiums of 11.98g first and 5g dihydric para-phthalic acids are dissolved in respectively by 85mL dimethylformamides
In the mixed solvent that makes with 59mL absolute methanols, stir to being completely dissolved；Secondly it is mixed and stirred for uniform to mix by two solution
Close solution；Then by mixed solution, at 50 DEG C, Ultrasonic Heating is processed after 30min, and reactant is moved in autoclave, in
11h is reacted in 100 DEG C of baking ovens；Room temperature is finally cooled to, is filtered, absolute methanol is washed 4 times, and in 130 DEG C of vacuum
14h is dried, adsorbent is obtained；
（2）The preparation of modified adsorbent
Take step（1）Obtained coordination unsaturation cellular solid 6g is added to the dry toluene containing 1.5g diethylenetriamines
In solution, surface modification reaction is carried out at 105 DEG C, the time is 11h；Room temperature is cooled to, products therefrom is filtered, is used dichloromethane
Washing, in 50 DEG C of vacuum environment dries 3h, obtains modified adsorbent
It is used for adsorbing N by two kinds of products of the present embodiment2/CO2CO in gaseous mixture2, adsorbance and selective data are shown in Table 1.
Embodiment 4
（1）The preparation of adsorbent
Weigh 14.14g Chromium nitrate (Cr(NO3)3),nonahydrates first and 5g dihydric para-phthalic acids are dissolved in respectively by 88mL dimethylformamides
In the mixed solvent that makes with 110mL anhydrous propyl alcohols, stir to being completely dissolved；Secondly it is mixed and stirred for uniform to mix by two solution
Close solution；Then mixed solution is placed in politef autoclave, 105 DEG C of reactions in microwave reaction device
0.5h；Room temperature is finally cooled to, and product is through filtering, anhydrous propyl alcohol is washed 3 times, and dries 11h in 155 DEG C of vacuum,
Obtain adsorbent；
（2）The preparation of modified adsorbent
Take step（1）Obtained coordination unsaturation cellular solid 2g is added to the dry toluene containing 0.4g triethylene tetramines
In solution, surface modification reaction is carried out at 115 DEG C, the time is 10h；Room temperature is cooled to, products therefrom is filtered, is used dichloromethane
Washing, in 70 DEG C of vacuum environment dries 1h, obtains modified adsorbent.
It is used for adsorbing N by two kinds of products of the present embodiment2/CO2CO in gaseous mixture2, adsorbance is shown in Table with selective data
1.
Embodiment 5
（1）The preparation of adsorbent
Weigh 10.09g Hexaaquachromium chlorides first and 5g dihydric para-phthalic acids are dissolved in respectively by 110mL dimethylformamides
In the mixed solvent that 110mL anhydrous propyl alcohols are made, stir to being completely dissolved；Secondly it is mixed and stirred for uniform to mix by two solution
Solution；Then mixed solution is moved into autoclave, 95 DEG C of reaction 1.5h in microwave reaction device；Finally it is cooled to
Room temperature, product is through filtering, anhydrous propyl alcohol is washed 3 times, and dries 15h in 120 DEG C of vacuum, obtains adsorbent；
（2）The preparation of the unsaturated cellular solid of modified adsorbent coordination
Take step（1）Obtained coordination unsaturation cellular solid 2g is added to the dry toluene containing 0.4g diethylenetriamines
In solution, surface modification reaction is carried out at 110 DEG C, the time is 9h；Room temperature is cooled to, products therefrom is filtered, is used dichloromethane
Washing, in 60 DEG C of vacuum environment dries 2h, obtains modified adsorbent.
It is used for adsorbing N by two kinds of products of the present embodiment2/CO2CO in gaseous mixture2, adsorbance is shown in Table with selective data
1.
The adsorptive selectivity and CO of 1 embodiment 1-5 product of table2Adsorbance
As shown in Table 1, the adsorbent and modified adsorbent of present invention preparation is in N2/CO2To CO in mixed system2There is higher suction
Attached selectivity and adsorbance.The adsorbent and modified adsorbent can be additionally used in other containing CO2Mixed gas system, realize efficiently
Selective absorption CO2.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by examples detailed above
System.Other any spirit without departing from the present invention and the change, modification, replacement that is made under principle, simplification is combined, all should
For equivalent transformation mode, it is included within protection scope of the present invention.
Claims (12)
1. a kind of preparation method of adsorbent, comprises the following steps：
（1）Take dimethylformamide and anhydrous alcoholic solvent makes mixed solvent；
（2）Take step（1）Obtained mixed solvent, metal salt hydrates are dissolved；
（3）Step is separately taken（1）Obtained mixed solvent, dihydric para-phthalic acid is dissolved；
（4）By step（2）And step（3）Obtained two kinds of solution mix homogeneously obtain mixed solution；
（5）By step（4）Obtained mixed solution 30～60min of supersound process at 40～50 DEG C, then moves into reaction under high pressure
In kettle, at 85～110 DEG C, 10～15h is reacted, take out reactor and be cooled to room temperature, filter, and use and step（1）Middle identical
Absolute alcohol solvent clean, after drying 10～15h, obtains adsorbent in 120～165 DEG C of vacuum.
2. preparation method according to claim 1, it is characterised in that step（1）The anhydrous alcoholic solvent be absolute methanol,
One kind in dehydrated alcohol, anhydrous propyl alcohol.
3. preparation method according to claim 1, it is characterised in that step（2）Described in metal salt hydrates be copper,
The nitrate hydrate of any one element or chlorination salt hydrate in scandium, chromium, aluminum.
4. preparation method according to claim 1, it is characterised in that step（2）Middle metal salt hydrates, dimethyl formyl
Amine, the mol ratio of anhydrous alcoholic solvent are (1.2 ~ 1.8): (39~58):58.
5. preparation method according to claim 1, it is characterised in that step（3）Middle dihydric para-phthalic acid, dimethyl
Methanamide, the mol ratio of anhydrous alcoholic solvent are 1:(39~58):58.
6. preparation method according to claim 1, it is characterised in that metal salt hydrates are with dihydric para-phthalic acid's
Mol ratio is 1.2 ~ 1.8:1.
7. preparation method according to claim 1, it is characterised in that step（5）Replace with：By step（4）Obtained mixed
Closing solution to move in autoclave, and autoclave being put in microwave reaction device, 0.5 is reacted at 90～110 DEG C
～1.5h, takes out reactor and is cooled to room temperature, filter, and use and step（1）Middle identical absolute alcohol solvent clean, then 120
After 10～15h is dried in～165 DEG C of vacuum, adsorbent is obtained.
8. the method for modifying of adsorbent obtained in preparation method described in claim 1 to 7 any one, comprises the following steps：
（1）Obtained adsorbent is added in the anhydrous toluene solution containing organic amine, carry out surface and change at 100～115 DEG C
Property reaction, the response time be 9～12h, obtain intermediate product；
（2）By step（1）Obtained intermediate product is cooled to room temperature, filters, is washed with dichloromethane, in 40～70 DEG C of vacuum
1～4h is dried in environment, modified adsorbent is obtained.
9. method of modifying according to claim 8, it is characterised in that step（1）Described in organic amine be ethylenediamine, diethyl
One kind in alkene triamine, triethylene tetramine.
10. method of modifying according to claim 8, it is characterised in that step（1）Middle coordination unsaturation cellular solid
It is 4 ~ 6 with organic amine mass ratio:1.
The application of adsorbent obtained in preparation method described in 11. claim 1 to 7 any one, for CO absorption2.
The application of modified adsorbent obtained in method of modifying described in 12. claim 8 to 10 any one, for CO absorption2.
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| CN111068786A (en) * | 2019-12-24 | 2020-04-28 | 新疆大学 | Alkaline functionalized F-Mn-MOF-74 nano catalytic material for efficiently catalyzing carbon dioxide cycloaddition reaction |
| CN111495431A (en) * | 2020-05-08 | 2020-08-07 | 中国地质大学（北京） | Photocatalyst and preparation method thereof |
| CN112029106A (en) * | 2020-08-05 | 2020-12-04 | 盐城工学院 | Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane |
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| CN107899559A (en) * | 2017-11-29 | 2018-04-13 | 中南大学 | A kind of defect MIL 53 (Al) metal organic framework and its preparation method and application |
| CN107899559B (en) * | 2017-11-29 | 2020-07-31 | 中南大学 | Defect MI L-53 (Al) metal organic framework and preparation method and application thereof |
| CN111068786A (en) * | 2019-12-24 | 2020-04-28 | 新疆大学 | Alkaline functionalized F-Mn-MOF-74 nano catalytic material for efficiently catalyzing carbon dioxide cycloaddition reaction |
| CN111495431A (en) * | 2020-05-08 | 2020-08-07 | 中国地质大学（北京） | Photocatalyst and preparation method thereof |
| CN112029106A (en) * | 2020-08-05 | 2020-12-04 | 盐城工学院 | Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane |
| CN112029106B (en) * | 2020-08-05 | 2021-12-10 | 盐城工学院 | Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane |
| CN112619399A (en) * | 2020-12-18 | 2021-04-09 | 浙江解氏新材料股份有限公司 | Tail gas treatment method in nitrosyl sulfuric acid preparation process |
| CN112619399B (en) * | 2020-12-18 | 2022-07-12 | 浙江解氏新材料股份有限公司 | Tail gas treatment method in nitrosyl sulfuric acid preparation process |
| CN113683784A (en) * | 2021-08-30 | 2021-11-23 | 西安理工大学 | Preparation method and application of carbon dioxide adsorbing material with metal organic framework |
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