CN107790103A - A kind of composite adsorbing material and preparation method thereof - Google Patents
A kind of composite adsorbing material and preparation method thereof Download PDFInfo
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- CN107790103A CN107790103A CN201610747282.0A CN201610747282A CN107790103A CN 107790103 A CN107790103 A CN 107790103A CN 201610747282 A CN201610747282 A CN 201610747282A CN 107790103 A CN107790103 A CN 107790103A
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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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- 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
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/046—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by adsorption, i.e. with the use of solids
Abstract
The invention discloses a kind of composite adsorbing material and preparation method thereof.The composite adsorbing material of the present invention contains metal-organic framework materials, carbon material and silica gel, and wherein the part by weight of metal-organic framework materials, carbon material and the silica gel counted using silica is 1：（0.01~0.07）：（0.5~2.0）.Metal-organic framework materials skeleton structure in composite adsorbing material of the present invention is complete, is not damaged.Furthermore because composite adsorbing material has high mechanical properties, it is not easy efflorescence in pressure-variable adsorption, significantly increases the service life.Composite adsorbing material of the present invention realizes silica gel and metal-organic framework materials Coupling Adsorption, and under Coupling Adsorption effect, composite adsorbing material greatly improves to the adsorption capacity of gas.
Description
Technical field
The present invention relates to a kind of composite adsorbing material and preparation method thereof, particularly answering containing metal-organic framework materials
Close sorbing material and preparation method thereof.
Background technology
Substantial amounts of dry gas can be produced in petroleum refining process, refinery is to reclaim to the universal processing method of dry gas at present
It is sent into fuel pipe network after the hydrogen resource of part to be used to burn, wherein the composition such as ethene with high additive value is not recycled profit
With causing the significant wastage of resource.Produced in addition, also having substantial amounts of methane during oil field production etc., in environmental protection pressure
In the case of increasingly increasing severely, the gas such as economic recovery methane is also extremely urgent.
Metal-organic framework materials（Metal-Organic Frameworks, abbreviation MOFs）It is to contain oxygen element or nitrogen
The netted class zeolitic frameworks material that is self-assembled into by metal-ligand complex effect of organic ligand and transition metal ions, tool
Have that porosity is high, specific surface area is huge, pore structure is regular, surface chemistry group easily modifies the features such as adjustable, in gas separation, inhale
Many-sided great application prospect such as attached, catalysis.
Metal-organic framework materials synthetic method is numerous, as solvent-thermal method, mechanochemical reaction, ultrasonic, microwave method,
Electrochemical process etc., but the normally solid powder of product synthesized.In practical application in industry, then need to carry out at shaping it
Reason, makes it have larger size and certain shape, and have certain mechanical strength, and so adsorption bed can be with after packing
There is less pressure drop, and be not pulverized easily.
At present, the report of existing some MOFs shapings related fields.
（1）In situ synthesis：There will be the matrix material of higher mechanical strength, good heat endurance and chemical stability
Material is immersed in mother liquor, and MOFs crystal is in substrate material surface growth in situ.As Matthias Georg Schwab et al. with
PolyHIPEs be carrier using growth in situ method by HKUST-1 it is immobilized in polymer duct, prepared with compared with
Strong mechanical strength, good thermal stability pearl HKUST-1 materials (Schwab MG, Senkovska I, Rose M,
Koch M, Pahnke J, Jonschker G, et al. MOF@PolyHIPEs[J]. Advanced Engineering
Materials. 2008,10(12):1151-1155).But the easy dry lintings of MOFs of this formed in situ, MOFs material contents are few.
（2）Extrinsion pressing：That is mechanical press pulverulent material, the process need to use adhesive, plasticiser or other add
Agent etc. is added to be molded beneficial to MOFs materials.As K ü sgens et al. mix HKUST-1 powder with plasticiser, kneader is then used
Mediate, obtain HKUST-1 honeycombs integral composite (K ü sgens P, Zgaverdea A, Fritz H-G, Siegle S,
Kaskel S.Metal-OrganicFrameworks in Monolithic Structures[J].Journal of the
American CeramicSociety.2010,93(9):2476-9).CN103586011A discloses a kind of superhigh specific surface area
The non-sintered shaping coating method of MIL-101 materials.The method mixes MIL-101 powder and adhesive, after kneading, extruding
Obtain shaped granule, and with polyvinyl alcohol enwrapped granule, wherein adhesive is inorganic bond or organic bond.Inorganic bond
Agent is silicate, cement, aluminum oxide, and organic bond is polyvinyl alcohol, coal tar asphalt, hydroxymethyl cellulose.
But this extrusion process is acted in journey is molded by external pressure, can cause HKUST-1 skeleton structures
Destroy.Furthermore in order to strengthen the mechanical strength of shaped granule, it is necessary to add the materials such as a large amount of adhesives, such adhesive does not have
There is adsorption capacity, when adhesive addition is bigger, the specific surface area and pore volume of final moulding material decline to a great extent, absorption
Amount declines.
（3）Rotary granulation, i.e., material compacting is made by the particle with certain pattern by centrifugal motion, the process needs
Use adhesive, plasticiser or additive etc..（4）Method of electrostatic spinning, i.e., polymeric fluid electrostatic atomization is made in powder
Special shape, it is not fine droplet that now the material is divided in atomization, but the small jet of polymer, can be run considerably long
Distance, finally it is solidified into fiber.But rotary granulation and electrostatic spinning law technology immature development, and complex process, pair set
Standby to require high, forming process is not easily controlled.
In addition, CN104226256A discloses a kind of spherical shaping Cu Base Metals organic backbone-graphene oxide composite wood
Material and preparation method.Its by ball-milling method by copper acetate, trimesic acid and graphene oxide be mixed with Cu bases organic backbone-
Graphene oxide composite porous material powder；By by water, methylhydroxypropylcellulose, silicic acid resin and Cu bases organic backbone-
Spherical Cu Base Metals organic backbone-graphene oxide composite wood is made in graphene oxide composite porous material powder mixing granulation
Material.This method is to realize growth in situ of the MOFs between the intercalation of graphene oxide by ball grinding technique.But this method due to
Copper acetate disperses independently of each other with trimesic acid in mechanical milling process, more copper acetate and trimesic acid unreacted generation gold
Belong to organic backbone, so as to cause MOFs yields very low, and the MOFs generated is more relatively low than surface.
It is, thus, sought for a kind of simple, quick forming method, directly prepares height using metal-organic framework materials
The shaped granule of mechanical strength, while in forming process, the skeleton structure of metal-organic framework materials is not destroyed, and also it is not clear
Development rings the physical and chemical performance of metal-organic framework materials.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of composite adsorbing material and its preparation side
Method.The composite adsorbing material of the present invention is the shaped granule of high mechanical properties, and the organic bone of metal in composite adsorbing material
Frame material skeleton structure is complete, is not damaged.Furthermore preparation method of the invention is directly made using metal-organic framework materials
The shaped granule of standby high mechanical properties, the skeleton structure of metal-organic framework materials is not destroyed in forming process.
The composite adsorbing material of the present invention, it contains metal-organic framework materials, carbon material and silica gel, and the metal is organic
The part by weight of framework material, carbon material and the silica gel counted using silica is 1：（0.01~0.07）：（0.5~2.0）.
The metal-organic framework materials and carbon material are scattered in silica gel independently of one another.
The compression strength of the composite adsorbing material is 30~85N.
The part by weight of the metal-organic framework materials, carbon material and the silica gel counted using silica is 1：（0.01~
0.07）：（1.3~2.0）, the compression strength of the composite adsorbing material is 50~80N.
The specific surface area of the composite adsorbing material is 450~2500m2·g-1, preferably 600~2300m2·g-1。
Metal-organic framework materials are metal-organic framework materials commonly used in the art, metal-organic framework materials bag
Include the one or more in ZIF-8, HKUST-1, MIL-53, MIL-101.
Carbon material can be preferably the carbon material of not oxidised processing, so that composite adsorbing material has more excellent lead
Hot property.
Carbon material can use the conventional carbon with thermal conductivity, can be in graphene, multi-walled carbon nanotube, graphite
One or more.
The composite adsorbing material is formed body, and its particle diameter is 1~5mm.
Present invention also offers a kind of preparation method of composite adsorbing material described above, comprise the following steps：
（1）All or part of metal-organic framework materials are well mixed with sodium silicate solution, obtain the first suspension；By residue
Part metals organic framework material and carbon material are well mixed with Ludox, obtain the second suspension；
（2）First suspension and the second uniform suspension are mixed and sprayed by shower nozzle, then is contacted instead with inorganic acid solution
Should, then aging, washing, aqueous slkali soaking, washing, drying, obtain described composite adsorbing material.
Step（1）In, metal-organic framework materials can be added all in the first suspension, can also divide two parts, and one
Part is added in the first suspension, another part（I.e. above-mentioned remainder）Add in the second suspension.
The sodium silicate solution is using the content that silica is counted as 10wt%~25wt%, the metal in first suspension
The content of organic framework material is 0.01~0.15g/mL.
The Ludox using the content that silica is counted as 5wt%~20wt%, carbon material in second suspension
Content is 1~50mg/mL, and the content of the metal-organic framework materials in second suspension is 0~0.30g/mL, is preferably
0.05~0.20g/mL.
The part by weight of first suspension, the second suspension and inorganic acid solution is 1:(0.5~2.0):(0.3~
2.0), the concentration of the inorganic acid solution is 15wt%~35wt%.Inorganic acid can use inorganic acid commonly used in the art,
Sulfuric acid, hydrochloric acid etc. can be selected.
All or part of metal-organic framework materials under the first ultrasound condition mix with sodium silicate solution
Even, first ultrasound condition is：After all or part of metal-organic framework materials are added into sodium silicate solution, machinery
10~20min is stirred, first is then carried out and is ultrasonically treated, the described first time being ultrasonically treated was 30~120min, and frequency is
15~50KHz, power are 160~640W.
The remainder metal-organic framework materials and carbon material are mixed with Ludox under the second ultrasound condition
Uniformly, second ultrasound condition is：After remainder metal-organic framework materials and carbon material are added into Ludox, machine
Tool stirs 10~20min, then carries out second and is ultrasonically treated, and the described second time being ultrasonically treated was 30~120min, frequency
For 15~50KHz, power is 160~640W.
Surfactant is added in first suspension and/or the second suspension, the surfactant includes ten
Dialkyl benzene sulfonic acids sodium and/or dodecyl sodium sulfate, and in first suspension or the second suspension, the surface is lived
The addition of property agent is 0.1~5.0mg/mL, preferably 1.0~3.0mg/mL.
The aqueous slkali can be ammoniacal liquor, and the concentration of the aqueous slkali is 0.1wt%~0.2wt%, the aqueous slkali soaking
Time is 10~24h.
The time of the aging is 1~10h, and the temperature of the aging is 20~70 DEG C；The time of the drying be 1~
10h, 80~200 DEG C of the temperature of the drying.
The present invention also provides above-mentioned composite adsorbing material and applied in gas absorption storage, gas absorption separation.
Compared with prior art, the inventive method has following outstanding advantages：
（1）Metal-organic framework materials skeleton structure in the composite adsorbing material of the present invention is complete, is not damaged.Furthermore due to
Composite adsorbing material has high mechanical properties, is not easy efflorescence in pressure-variable adsorption, significantly increases the service life.
The composite adsorbing material of the present invention has the silica gel and MOF materials of high level, not only with high specific surface area, goes back
Aperture with suitable terraced distribution, so as to realize the performance of silica gel and MOF material Coupling Adsorptions.Under Coupling Adsorption effect,
Composite adsorbing material greatly improves to the adsorption capacity of gas.
（2）The composite adsorbing material of the present invention, because carbon material has good heat conductivility, therefore enhances forming material
The heat conductivility of material, be advantageous to the transmission of heat of adsorption.
（3）Because carbon material is insoluble in water and conventional organic solvent, it is difficult to prepare dispersed system in a solvent.This
Invention passes through two kinds of different common plastics of suspension, prepares carbon material dispersion using Ludox, carbon material is uniformly dispersed,
Avoid carbon material deposition problem.Then, acid reaction is met by sodium metasilicate, silica gel is collectively forming with Ludox, so as to by metal
Organic framework material and carbon material wrap up respectively and bonding is integral, and are each evenly dispersed in silica gel, so as to
A kind of forming method of brand-new metal-organic framework materials is developed, i.e., shaping is realized by suspended dispersed, reaction plastic,
Solves carbon material（Graphene, the CNT of especially non-oxidation processes）With other materials（Adhesive）Affinity is very poor,
The problem of extrusion forming is difficult, and extrinsion pressing destroys to the skeleton of metal-organic framework materials.
（4）In the preparation process in accordance with the present invention, aqueous slkali soaking can play silica gel hole in thermal conductivity composite adsorbing material
Structure plays a part of regulation, so as to optimize the pore-size distribution of silica gel.
Embodiment
The composite adsorbing material of the invention containing metal-organic framework materials is further illustrated below by embodiment
Preparation process, but invention should not be deemed limited in following embodiment.In the present invention, wt% is mass fraction.
Embodiment 1
The sodium silicate solution that dioxide-containing silica is 20wt% is prepared, and HKUST-1,1mg/mL amount are added with 0.1g/mL amount
Add dodecyl sodium sulfate, mechanical agitation 15min；Ultrasonic 90min prepares the first suspension, and ultrasonic frequency is 25KHz, work(
Rate is 300W；
The Ludox that dioxide-containing silica is 10wt% is prepared, and HKUST-1,1mg/mL amount addition are added with 0.1g/mL amount
Dodecyl sodium sulfate, 10mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, ultrasonic 60min systems
The second suspension is obtained, ultrasonic frequency is 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 weight is sprayed than uniformly mixed merga pass certain pressure by shower nozzle
Go out, then the first suspension and 25wt% sulfuric acid solution are pressed 1:1 weight generates Silica hydrogel than haptoreaction, in 20 DEG C of agings
10h, it is washed with water, after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h is dried at 100 DEG C, it is compound to obtain thermal conductivity
Sorbing material A, and thermal conductivity composite adsorbing material A particle diameter is highly uniform.The metal organic framework in composite adsorbing material A
The part by weight of material, carbon material and the silica gel counted using silica is 1：0.05：1.6.
Embodiment 2
The sodium silicate solution that dioxide-containing silica is 20wt% is prepared, and is added with 0.1g/mL amount addition ZIF-8,1mg/mL amount
Enter dodecyl sodium sulfate, mechanical agitation 15min, ultrasonic 90min prepare the first suspension, and ultrasonic frequency is 25KHz, power
For 300W；
The Ludox that dioxide-containing silica is 10wt% is prepared, and ZIF-8,1mg/mL amount addition ten are added with 0.1g/mL amount
Dialkyl sulfonates, 10mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, and ultrasonic 60min is made
Second suspension, ultrasonic frequency are 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 weight is sprayed than uniformly mixed merga pass certain pressure by shower nozzle
Go out, then the sulfuric acid solution for being 25wt% by the first suspension and concentration is 1 by weight:1 haptoreaction generates Silica hydrogel, 20
DEG C aging 10h, is washed with water, and after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h is dried at 100 DEG C, obtains heat conduction
Property composite adsorbing material B, and particle diameter is highly uniform.In composite adsorbing material B, metal-organic framework materials, carbon material and
The part by weight for the silica gel counted using silica is 1：0.05：1.6.
Embodiment 3
The sodium silicate solution that dioxide-containing silica is 15wt% is prepared, and is added with 0.1g/mL amount addition ZIF-8,1mg/mL amount
Enter neopelex, mechanical agitation 15min, ultrasonic 60min prepare the first suspension, and ultrasonic frequency is 25KHz, work(
Rate is 300W；
The Ludox that dioxide-containing silica is 10wt% is prepared, and ZIF-8,1mg/mL amount addition ten are added with 0.2g/mL amount
Dialkyl benzene sulfonic acids sodium, 10mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, ultrasonic 90min systems
The second suspension is obtained, ultrasonic frequency is 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 weight is sprayed than uniformly mixed merga pass certain pressure by shower nozzle
Go out, then the sulfuric acid solution for being 15wt% by the first suspension and concentration is 1 by weight:1.2 haptoreactions generate Silica hydrogel,
50 DEG C of aging 5h, are washed with water, and after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h are dried at 100 DEG C, obtains heat conduction
Property composite adsorbing material C, and particle diameter is highly uniform.In composite adsorbing material C, metal-organic framework materials, carbon material and
The part by weight for the silica gel counted using silica is 1：0.03：0.9.
Embodiment 4
The sodium silicate solution that dioxide-containing silica is 15wt% is prepared, and HKUST-1,1mg/mL amount are added with 0.1g/mL amount
Neopelex is added, mechanical agitation 15min, ultrasonic 60min prepare the first suspension, and ultrasonic frequency is 25KHz,
Power is 300W；
The Ludox that dioxide-containing silica is 10wt% is prepared, and HKUST-1,1mg/mL amount addition are added with 0.2g/mL amount
Neopelex, 10mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, ultrasonic 90min
The second suspension is made, ultrasonic frequency is 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 weight is sprayed than uniformly mixed merga pass certain pressure by shower nozzle
Go out, then the first suspension and concentration are pressed 1 for 15wt% sulfuric acid solution:1.2 weight generates Silica hydrogel than haptoreaction,
50 DEG C of aging 5h, are washed with water, and after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h are dried at 100 DEG C, obtains heat conduction
Property composite adsorbing material D, and particle diameter is highly uniform.In composite adsorbing material D, metal-organic framework materials, carbon material and
The part by weight for the silica gel counted using silica is 1：0.03：0.9.
Embodiment 5
The sodium silicate solution that dioxide-containing silica is 20wt% is prepared, and MIL-101,1mg/mL amount are added with 0.1g/mL amount
Add dodecyl sodium sulfate, mechanical agitation 15min, ultrasonic 90min prepares the first suspension, and ultrasonic frequency is 25KHz, work(
Rate is 300W；
The Ludox that dioxide-containing silica is 10wt% is prepared, and MIL-101,1mg/mL amount addition are added with 0.1g/mL amount
Dodecyl sodium sulfate, 10mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, ultrasonic 60min systems
The second suspension is obtained, ultrasonic frequency is 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 amount is uniformly mixed merga pass certain pressure and sprayed by shower nozzle, then
The sulfuric acid solution for being 25wt% by the first suspension and concentration is 1 by weight:1 haptoreaction generates Silica hydrogel, in 20 DEG C of agings
10h, it is washed with water, after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h is dried at 100 DEG C, it is compound to obtain thermal conductivity
Sorbing material E, and particle diameter is highly uniform.In composite adsorbing material E, metal-organic framework materials, carbon material and with dioxy
The part by weight of the silica gel of SiClx meter is 1：0.05：1.6.
Embodiment 6
The sodium silicate solution that dioxide-containing silica is 10wt% is prepared, and HKUST-1,1mg/mL are added with 0.15g/mL amount
Amount adds dodecyl sodium sulfate, and mechanical agitation 15min, ultrasonic 120min prepare the first suspension, and ultrasonic frequency is
25KHz, power 300W；
The Ludox that dioxide-containing silica is 20wt% is prepared, and dodecyl sodium sulfate, 10mg/mL are added with 1mg/mL amount
Amount add the graphene of not oxidised processing, the second suspension, ultrasonic frequency is made in mechanical agitation 15min, ultrasonic 60min
For 25KHz, power 300W.
First suspension and the second suspension are pressed 1:1 amount is uniformly mixed merga pass certain pressure and sprayed by shower nozzle, then
It is 1 by weight by the sulfuric acid solution that the first suspension and concentration are 15wt%:0.9 haptoreaction generates Silica hydrogel, old at 20 DEG C
Change 10h, be washed with water, after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h is dried at 100 DEG C, thermal conductivity is obtained and answers
Sorbing material F is closed, and particle diameter is highly uniform.In composite adsorbing material F, metal-organic framework materials, carbon material and with two
The part by weight of the silica gel of silica meter is 1：0.06：2.
Comparative example 1
The Ludox that dioxide-containing silica is 15wt% is prepared, and HKUST-1,1mg/mL amount addition are added with 0.1g/mL amount
Dodecyl sodium sulfate, 5mg/mL amount add the graphene of not oxidised processing, mechanical agitation 15min, and ultrasonic 60min is made
Suspension, ultrasonic frequency are 25KHz, power 300W.Suspension is sprayed by certain pressure by shower nozzle, in 20 DEG C of agings
10h, it is washed with water, after soaking 10h in the ammoniacal liquor that concentration is 0.1wt%, 10h is dried at 100 DEG C, it is compound to obtain thermal conductivity
Sorbing material G.In composite adsorbing material G, the weight of metal-organic framework materials, carbon material and the silica gel in terms of silica
Ratio is 1：0.05：1.6.
Comparative example 2
The sodium silicate solution that dioxide-containing silica is 20wt% is prepared, and ZIF-8,1mg/mL amount are added with 0.05g/mL amount
Dodecyl sodium sulfate is added, mechanical agitation 15min, ultrasonic 90min prepare suspension；
Compound concentration is 15wt% sulfuric acid, and not oxidised with 0.05g/mL amount addition ZIF-8,3.5mg/mL amount addition
The graphene of processing, mechanical agitation 15min, ultrasonic 60min, ultrasonic frequency is 25KHz, power 300W.
Suspension is sprayed by certain pressure by shower nozzle, then suspension and concentration are pressed into weight for 15wt% sulfuric acid solution
Amount is than being 1:1.8 haptoreactions generate Silica hydrogel, in 20 DEG C of aging 10h, are washed with water, and are soaked in the ammoniacal liquor that concentration is 0.1wt%
After steeping 10h, 10h is dried at 100 DEG C, obtains thermal conductivity composite adsorbing material H.In composite adsorbing material H, the organic bone of metal
The part by weight of frame material, carbon material and the silica gel counted using silica is 1：0.05：1.6.
Metal-organic framework materials and the composite adsorption material after shaping before shaping in Example 1-6 and comparative example 1-2
Material, test b ET specific surface areas, compression strength, particle size range, measurement result such as table 1.Wherein, BET specific surface area is by low temperature liquid nitrogen
Absorption method is measured, and compression strength is measured by KQ-3 type catalyst strength analyzers.
Table 1
| Sample | BET specific surface area/m of metal-organic framework materials before shaping2·g-1 | BET specific surface area/m of composite adsorbing material2·g-1 | The pressure resistance of composite adsorbing material Degree/N | The particle size range of composite adsorbing material/ mm | Remarks |
| Embodiment 1 | 1600 | 820 | 54 | 1~3 | Carbon material is evenly distributed |
| Embodiment 2 | 1200 | 630 | 53 | 1~3 | Carbon material is evenly distributed |
| Embodiment 3 | 1200 | 720 | 43 | 1~3 | Carbon material is evenly distributed |
| Embodiment 4 | 1600 | 920 | 41 | 1~3 | Carbon material is evenly distributed |
| Embodiment 5 | 4100 | 2300 | 53 | 1~3 | Carbon material is evenly distributed |
| Embodiment 6 | 1600 | 730 | 80 | 1~3 | Carbon material is evenly distributed |
| Comparative example 1 | 1600 | 750 | 43 | 1~3 | Carbon material is evenly distributed |
| Comparative example 2 | 1200 | 540 | 45 | 1~3 | Carbon material skewness It is even |
From comparative example 1 and 2, because the suspension of single silicon source easily forms topical gel or local close during plastic
Accumulation, and then steam bubble glue, broken glue in granulation process are produced, in turn result in the problems such as compression strength is inadequate or less than normal than surface；
From comparative example 2, because the carbon material of addition is unable to long-time stable, is evenly dispersed in acid solution, carbon material is caused
The skewness in final composite adsorbing material, heat conductivility are bad.
Claims (19)
1. a kind of composite adsorbing material, it is characterised in that it contains metal-organic framework materials, carbon material and silica gel, the gold
Belong to the part by weight of organic framework material, carbon material and the silica gel counted using silica as 1：（0.01~0.07）：（0.5~
2.0）.
2. composite adsorbing material according to claim 1, it is characterised in that：The metal-organic framework materials and carbon material
It is scattered in independently of one another in silica gel.
3. composite adsorbing material according to claim 1, it is characterised in that：The compression strength of the composite adsorbing material is
30~85N.
4. composite adsorbing material according to claim 1, it is characterised in that：The metal-organic framework materials, carbon material
With the part by weight of silica gel counted using silica as 1：（0.01~0.07）：（1.3~2.0）, the composite adsorbing material
Compression strength is 50~80N.
5. according to the composite adsorbing material described in any one in claim 1-4, it is characterised in that：The composite adsorbing material
Specific surface area be 450~2500m2·g-1, preferably 600~2300m2·g-1。
6. according to the composite adsorbing material described in any one in claim 1-4, it is characterised in that：The metal organic framework
Material includes the one or more in ZIF-8, HKUST-1, MIL-53, MIL-101.
7. composite adsorbing material according to claim 1, it is characterised in that：The carbon material is graphene, more wall carbon are received
One or more in mitron, graphite.
8. the composite adsorbing material according to claim 1 or 7, it is characterised in that：The carbon material is not oxidised processing
Carbon material.
9. according to the composite adsorbing material described in any one in claim 1-4, it is characterised in that：The composite adsorbing material
For formed body, its particle diameter is 1~5mm.
10. the preparation method of a kind of composite adsorbing material as described in claim 1-9 is any, it is characterised in that including as follows
Step：
（1）All or part of metal-organic framework materials are well mixed with sodium silicate solution, obtain the first suspension；By residue
Part metals organic framework material and carbon material are well mixed with Ludox, obtain the second suspension；
（2）First suspension and the second uniform suspension are mixed and sprayed by shower nozzle, then is contacted instead with inorganic acid solution
Should, then aging, washing, aqueous slkali soaking, washing, drying, obtain described composite adsorbing material.
11. according to the method for claim 10, it is characterised in that：Content of the sodium silicate solution in terms of silica be
10wt%~25wt%, the content of the metal-organic framework materials in first suspension is 0.01~0.15g/mL.
12. according to the method for claim 10, it is characterised in that：The Ludox is using the content that silica is counted as 5wt%
~20wt%, the content of the carbon material in second suspension are 1~50mg/mL, and the metal in second suspension is organic
The content of framework material is 0~0.30g/mL, preferably 0.05~0.20g/mL.
13. according to the method for claim 10, it is characterised in that：First suspension, the second suspension and inorganic acid
The part by weight of solution is 1:(0.5~2.0):(0.3~2.0), the concentration of the inorganic acid solution is 15wt%~35wt%.
14. according to the method for claim 10, it is characterised in that：All or part of metal-organic framework materials and silicon
Acid sodium solution is well mixed under the first ultrasound condition, and first ultrasound condition is：Will all or part of gold
Belong to after organic framework material adds sodium silicate solution, 10~20min of mechanical agitation, then carry out first and be ultrasonically treated, described the
One time being ultrasonically treated was 30~120min, and frequency is 15~50KHz, and power is 160~640W.
15. the method according to claim 10 or 14, it is characterised in that：The remainder metal-organic framework materials and
Carbon material is well mixed with Ludox under the second ultrasound condition, and second ultrasound condition is：By remainder parting
After category organic framework material and carbon material are added to Ludox, 10~20min of mechanical agitation, then carry out second and be ultrasonically treated,
Described second time being ultrasonically treated was 30~120min, and frequency is 15~50KHz, and power is 160~640W.
16. according to the method for claim 10, it is characterised in that：In first suspension and/or the second suspension
Surfactant is added, the surfactant includes neopelex and/or dodecyl sodium sulfate, and described
In first suspension or the second suspension, the addition of the surfactant is 0.1~5.0mg/mL, preferably 1.0~
3.0mg/mL。
17. according to the method for claim 10, it is characterised in that：The aqueous slkali is ammoniacal liquor, the concentration of the aqueous slkali
For 0.1wt%~0.2wt%, the aqueous slkali soaking time is 10~24h.
18. according to the method for claim 10, it is characterised in that：The time of the aging is 1~10h, the aging
Temperature is 20~70 DEG C；The time of the drying is 1~10h, 80~200 DEG C of the temperature of the drying.
19. a kind of composite adsorbing material as described in claim 1-9 is any should in gas absorption stores, gas absorption separates
With.
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