CN108620023A - A kind of enhanced thermal conduction type metal organic framework formed body and preparation method thereof - Google Patents
A kind of enhanced thermal conduction type metal organic framework formed body and preparation method thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The present invention relates to a kind of enhanced thermal conduction type metal organic framework formed bodys and preparation method thereof, including（1）One layer of conductive metal is plated on graphite powder, and graphite metal composite material is made；（2）After mixing by graphite metal composite material obtained and MOFs materials, binder, moulding dose and liquid, kneading, extruded moulding；（3）By step（2）The drying of extruded moulding product, roasting, you can enhanced thermal conduction type metal organic framework formed body is made.Metal organic framework formed body prepared by the present invention has many advantages, such as that good heat conductivity, specific surface area are high, mechanical strength is good.
Description
Technical field
The invention belongs to metal-organic framework materials field shaping techniques, and in particular to a kind of enhanced thermal conduction type metal is organic
Skeleton forming body and preparation method thereof.
Background technology
Metal-organic framework materials（Metal-Organic Frameworks, MOFs）It is that family emerging in recent years is micro-
Hole/mesoporous material, with large specific surface area, pore structure is flourishing, stability is good, duct is adjustable and can be made according to target call
The advantages that chemical modification, thus know in gas storage, gas absorption separation, selectivity and chiral catalyst, microreactor, molecule
Not, the various fields such as drug delivery, photoelectric properties application have broad application prospects.
However, the MOFs materials of conventional method synthesis, are usually all powdered crystalline materials, be easy to be blown away by gas and
It is not easily recycled, and will increase transmittance process resistance and pressure drop.Therefore, MOFs materials forming technique is the porous material industrialization
One of committed step of application.In addition, MOFs thermal conductivity of material is poor, and would generally be put when gas absorption or catalysis reaction
Go out a large amount of heat, causes MOFs materials to absorb the energy of release in absorption or catalytic process and heated, seriously affect gas
Body adsorption capacity or catalytic efficiency, this significantly limits its commercial Application.
CN105056896A discloses a kind of MOFs adsorbents and application, adsorbent are made by following steps：With MOFs materials
On the basis of expecting original powder, it is 2~50% binders, 3~60% extrusion aids and 1~30% water, stirring that addition, which accounts for MOFs material original powder quality,
After mediating uniformly, molding；Molding MOFs adsorbents are made in drying, roasting.CN104968425A discloses a kind of prepare and contains
The method of MOFs material molded compacts, includes the following steps：(a) composition containing MOF and at least one additive is mixed；With
(b) this composition is extruded as formed body, wherein MOF is dried before step (a).Wherein, at least one additive contains
It is to be selected from the organic adhesive of oxide adhesive and part to have at least one adhesive, described adhesive.But above method system
The problems such as standby MOFs formed bodys are poor there are heat conductivility, is unable to give full play the function of MOFs materials.
Ramos-Fernandez et al. is green coated in cellular violet by MIL-101 (Cr) using secondary seed crystal growth method
In stone duct, MIL-101/ cordierite composite materials are obtained（Ramos Fernandez EV, Garcia Domingos M, etc.
MOFs meet monoliths: Hierarchical structuring metal organic framework
catalysts[J]. Applied Catalysis A: General.2011, 391(1-2): 261-7）.But it is this with former
MOFs contents are low in MOFs formed bodys prepared by position growth method, and specific surface area is less than normal, and adsorption capacity ratio MOFs powders decline more.
In addition, there is also the problems of heat conductivility difference for the formed body.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of enhanced thermal conduction type metal organic framework formed body and its systems
Preparation Method.It is excellent that metal organic framework formed body prepared by the present invention has that good heat conductivity, specific surface area are high, mechanical strength is good etc.
Point.
The preparation method of enhanced thermal conduction type metal organic framework formed body provided by the invention, includes the following steps：
（1）One layer of conductive metal is plated on graphite powder, and graphite-metal composite material is made；
（2）After mixing by graphite-metal composite material obtained and MOFs materials, binder, moulding dose and liquid, it mixes
It pinches, extruded moulding；
（3）By step（2）The drying of extruded moulding product, roasting, you can enhanced thermal conduction type metal organic framework formed body is made.
Step（1）The graphite powder is graphite powder commonly used in the art, and mesh number is generally no greater than 300 mesh, preferably
200-300 mesh.Graphite powder preferably uses crystalline graphite powder, heat conductivility more preferable.Using the distinctive layer structure of crystalline graphite powder,
So that graphite-metal composite material can not only increase the bonding force between material, but also the outer of metal between material and extrusion can be reduced
Frictional force is easy demoulding.
Step（1）The conductive metal be conductive metal, such as iron, aluminium, copper, zinc, silver, gold, manganese, chromium, cadmium,
One or both of one or more of nickel, titanium etc., preferably copper, silver.
Step（1）The method of the graphite powder plating metal is the chemical plating metal method or galvanoplastic of this field routine, such as work
The methods of cyanide electroplating, acid copper-plating and the pyrophosphate copper plating that industry copper facing uses, the cyaniding plant of silver of silver-plated use, niacin plating
Silver, the methods of thiosulfate is silver-plated, imidazoles-sulfosalicylic acid is silver-plated, sulphite is silver-plated.
Step（1）The mass content of metal is 20%~80%, preferably 40%~80% in the graphite-metal composite material.
Step（2）The MOFs materials are the metal-organic framework materials routinely used, and specific surface area is more than 1000m2·g-1.Such as can be one kind in IRMOF, ZIF, MIL, HK or CPL series, preferred one kind in ZIF, MIL, HK etc..
Step（2）The binder is to be selected from oxide adhesive and part organic bond, such as can be aluminium oxide, oxygen
One or more of SiClx, boehmite, kaolin, clay and organo-silicon compound etc., preferably aluminium oxide intend thin water aluminium
Stone etc..
Step（2）Described moulding dose is hydrophilic polymer, such as can be methylcellulose, starch, polyacrylate, gather
Methacrylate, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene and PolyTHF, preferably methylcellulose form sediment
Powder, polyvinyl alcohol etc..These substances have mainly promoted by connecting primary particle the shape during kneading, molding and drying steps
At plastic material, it is ensured that the mechanical stability of the moulded work during molding with optionally drying technique.
Step（2）The liquid is water or water-miscible alcohol, such as methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutyl
Alcohol, tert-butyl alcohol etc..If desired molding MOFs is stable in water, and preferably water is exclusive solvents；If desired molding MOFs
Water stability is poor, preferably the mixture of water and alcohol, and the mass ratio of water and alcohol is 1：0.1~10, preferably 1：1~5.
Step（2）The MOFs materials, binder, graphite-metal composite material, the moulding dose of mass ratio between liquid
It is 100：2~30：5~60：2~20：20~170.
Step（3）It is dried at 80~100 DEG C, 1~12h is roasted at 180~300 DEG C.
Enhanced thermal conduction type metal organic framework formed body of the present invention is prepared using aforementioned present invention method.With weight
Gauge, in metal organic framework formed body, the content of MOFs materials is 40%~90%, preferably 60%~90%；Content of graphite is 1%
~20%, conductive metal content is 1%~25%, and binder content is 2%~20%, and moulding agent content is 2%~15%.
Enhanced thermal conduction type metal organic framework formed body prepared by the present invention can be applied to gas absorption, gas absorption is deposited
In storage, gas absorption separation, especially in carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane, propane absorbing and storing,
And carbon dioxide/methane, carbon dioxide/carbon monoxide, titanium dioxide carbon/nitrogen gas, carbon dioxide/oxygen, hydrogen/titanium dioxide
In being selectively adsorbing and separating of the gaseous mixtures such as carbon, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene, propane/propylene, have good
Application effect.
Compared with prior art, the invention has the advantages that：
（1）Metal organic framework formed body prepared by the present invention not only remains the larger specific surface of original MOFs dusty materials
Product and open pore structure have actual industrialization and apply necessary certain pattern, mechanical strength and toughness, especially have
There is good heat conductivility so that MOFs materials have good thermal conductivity in absorption or catalytic process, do not interfere with gas
Adsorption capacity or catalytic efficiency.
（2）Enhanced thermal conduction type metal organic framework formed body prepared by the present invention, is noteworthy characterized by being molded pug
The graphite-metal composite material with Thermal conductivity is added, three-dimensional network passage of heat is effectively formed, to improve
The heat conductivility of metal organic framework formed body.In addition, the rigid structure of graphite-metal composite material can also increase molding
The mechanical strength of body.
（3）Enhanced thermal conduction type metal organic framework formed body prepared by the present invention can be used for gas absorption, gas absorption
In storage, gas absorption separation, have many advantages, such as that good heat conductivity, specific surface area are high, mechanical strength is good.
Description of the drawings
Fig. 1 is the X-ray collection of illustrative plates of 1 formed body A of HKUST-1 powder and embodiment（XRD）；
Fig. 2 is the X-ray collection of illustrative plates of ZIF-8 powder and the formed body C of embodiment 3（XRD）；
Fig. 3 is the X-ray collection of illustrative plates of MIL-53 (Al) powder and the formed body D of embodiment 4（XRD）.
Specific implementation mode
The preparation process and effect of metal organic framework formed body are further illustrated the present invention below by embodiment, but
It invention should not be deemed limited in embodiment below.
Embodiment 1
（1）Graphite/silver composite material is prepared with galvanoplastic.24g silver nitrates and 56g succimides are dissolved in 200ml respectively to steam
In distilled water, then succimide solution is slowly added in silver nitrate solution under stiring, is allowed to production clarification complex liquid.It adjusts
Section solution ph is alkalescent, and electroplate liquid is obtained after adding 1300ml distilled water.The graphite of 300 mesh of 12g is added in electroplate liquid
Powder opens DC power supply and starts to be electroplated after stirring evenly, control current density is 0.3Adm-2, distilled water is used after 30min is electroplated
Graphite/silver composite material is rinsed to neutrality, puts it into drying box, is dried under 100 DEG C of temperature condition later.It is obtained
Graphite/silver composite material, wherein the weight ratio of silver is the 70% of composite material quality.
（2）After mixing by 100g HKUST-1 powder, 10g aluminium oxide, 50g graphite/silver composite material, 12g starch,
It is slowly added to 20g water and 120g alcohol mixed solutions, after mediating uniformly, extruded moulding after being dried at 100 DEG C, is roasted at 200 DEG C
HKUST-1 formed bodys are made in 10h.The a diameter of 2mm of molded samples is labeled as sample A.
By x-ray photoelectron spectroscopy and differential thermal-thermogravimetric analysis it is found that by weight, MOFs materials contains in formed body A
Amount is 61.2%, content of graphite 8.8%, silver content 20.1%, alumina content 5.9%, content of starch 4.0%.
Embodiment 2
（1）The production method of graphite/silver composite material is the same as embodiment 1.
（2）By 100g HKUST-1 powder, 5g boehmites, 30g graphite/silver composite material, 10g polyvinyl alcohols
After uniformly, it is slowly added to 40g water and 40g alcohol mixed solutions, after mediating uniformly, extruded moulding, after being dried at 100 DEG C, 200
DEG C roasting 10h, is made HKUST-1 formed bodys.The a diameter of 2mm of molded samples is labeled as sample B.
By x-ray photoelectron spectroscopy and differential thermal-thermogravimetric analysis it is found that by weight, MOFs materials contains in formed body B
Amount is 71.4%, content of graphite 6.4%, silver content 14.7%, boehmite content 2.4%, polyvinyl alcohol content 5.1%.
Embodiment 3
（1）Graphite/carbon/carbon-copper composite material is prepared with galvanoplastic.16g cupric sulfate pentahydrates and the 40ml concentrated sulfuric acids are added to 1500ml to steam
It is configured to electroplate liquid in distilled water, the graphite powder of 300 mesh of 10g is then added, DC power supply is opened after stirring evenly and starts to be electroplated,
Control current density is 6Adm-2, distilled water flushing graphite/carbon/carbon-copper composite material to neutrality is used after 70min is electroplated, is put later
Enter in drying box, is dried under 100 DEG C of temperature condition.Graphite/carbon/carbon-copper composite material obtained, the wherein weight ratio of copper are compound
The 43% of quality of materials.
（2）100g ZIF-8 powder, 25g silica, 15g graphite/silver composite material, 3g methylcellulose are mixed equal
After even, be slowly added to 80g water, after mediating uniformly, after being dried at 80 DEG C, 4h is roasted at 200 DEG C for extruded moulding, be made ZIF-8 at
Type body.The a diameter of 2mm of molded samples is labeled as sample C.
By x-ray photoelectron spectroscopy and differential thermal-thermogravimetric analysis it is found that by weight, MOFs materials contains in formed body C
Amount is 71.9%, content of graphite 5.3%, copper content 5.2%, dioxide-containing silica 15.5%, and Methyl cellulose cellulose content is 2.1%.
Embodiment 4
（1）The production method of graphite/carbon/carbon-copper composite material is the same as embodiment 3.
（2）By 100g MIL-53（Al）Powder, 5g boehmites, 40g graphite/carbon/carbon-copper composite material, the mixing of 15g starch
After uniformly, it is slowly added to 60g water, after mediating uniformly, after being dried at 100 DEG C, 6h is roasted at 270 DEG C, MIL- is made for extruded moulding
53（Al）Formed body.The a diameter of 2mm of molded samples is labeled as sample D.
By x-ray photoelectron spectroscopy and differential thermal-thermogravimetric analysis it is found that by weight, MOFs materials contains in formed body D
Amount is 62.5%, content of graphite 12.5%, copper content 12.5%, boehmite content 3.1%, content of starch 9.4%.
Embodiment 5
Preparation method is same as Example 1, and difference is that graphite uses crystalline graphite powder, sample to be labeled as E.By X-ray light
Electron spectrum and differential thermal-thermogravimetric analysis are it is found that by weight, the content of MOFs materials is 63.5% in formed body A, content of graphite
It is 8.9%, silver content 18.1%, alumina content 5.7%, content of starch 3.8%.
Comparative example 1
Preparation method is same as Example 1, and difference is to be added without graphite/carbon/carbon-copper composite material in forming process, is made
HKUST-1 formed bodys F.
Comparative example 2
Preparation method is same as Example 1, and difference is to save graphite plating metal step（1）, in forming process step（2）Directly
50g graphite is added, HKUST-1 formed bodys G is made.
Comparative example 3
Preparation method is same as Example 1, and difference is to save graphite plating metal step（1）, in forming process step（2）In it is straight
It connects and 15g graphite and 35g copper powders is added, HKUST-1 formed bodys H is made.
Test case 1
Crystal phase structure test is carried out to MOFs powder used in embodiment 1,3 and 4 and the formed body made from the MOFs powder, it is used
Instrument is 6000 type X-ray diffractometers of Shimadzu, Japan XRD, and determination condition is：Cu K alpha rays, 2 θ of scanning range=
5~50 °, 4 °/min of sweep speed, specific XRD spectra is as shown in Figs. 1-3.
From Fig. 1-3 as can be seen that compared with the XRD spectra of MOFs powder, the formed body made from the MOFs powder
XRD spectra characteristic peak positions are identical, and feature peak intensity slightly reduces, and illustrates binder in formed body, graphite/metal composite wood
The addition of material, moulding dose and liquid slightly influences the crystal form of MOFs powder, but destroys the crystal structure of material itself, at
Type body still keeps more complete crystalline structure, crystalline framework to stablize.
Test case 2
The physico-chemical property of the formed body of embodiment 1-5 and the formed body A-H of comparative example 1-3 is measured, concrete outcome is shown in Table 1.Its
In, BET specific surface area is measured by low temperature liquid nitrogen absorption method, and compression strength is measured by detector for strength of particles, and thermal coefficient is by steady
State method measures, test temperature 300K.
The physicochemical property of table 1 embodiment 1-5 and comparative example 1-3 formed bodys
As can be seen from Table 1, compared with sample A prepared by embodiment 1, the thermal coefficient of sample E prepared by embodiment 5 increases,
This illustrates that the heat conductivility of crystalline graphite powder is more preferable.Compared with sample F prepared by comparative example 1, the sample A of embodiment 1-2 preparations,
B specific surface areas reduce, and compression strength is significantly increased, thermal coefficient from 0.094 W/ (m K) be respectively increased 0.472 W/ (m K) and
0.368 W/(m∙K)；Compared with sample G and H prepared by comparative example 2, comparative example 3, the sample A's of the preparation of the embodiment of the present invention 1
Side pressure strength and thermal coefficient are relatively high, this is because graphite/metal composite material disperses in formed body prepared by the present invention
Uniformly, bulky grain agglomeration when being directly added into graphite or graphite/metal is can effectively prevent, continuous three-dimensional network is formed and passes
Heat structure, to improve the side pressure strength and thermal coefficient of formed body.
Claims (14)
1. a kind of preparation method of enhanced thermal conduction type metal organic framework formed body, it is characterised in that include the following steps：
（1）One layer of conductive metal is plated on graphite powder, and graphite-metal composite material is made；
（2）After mixing by graphite-metal composite material obtained and MOFs materials, binder, moulding dose and liquid, it mixes
It pinches, extruded moulding；
（3）By step（2）The drying of extruded moulding product, roasting, you can enhanced thermal conduction type metal organic framework formed body is made.
2. according to the method for claim 1, it is characterised in that：Step（1）The mesh number of the graphite powder is not more than 300 mesh,
Preferably 200-300 mesh.
3. according to the method for claim 1, it is characterised in that：Step（1）The graphite powder uses crystalline graphite powder.
4. according to the method for claim 1, it is characterised in that：Step（1）The conductive metal be iron, aluminium, copper, zinc, silver,
One or more of gold, manganese, chromium, cadmium, nickel, titanium.
5. according to the method for claim 1, it is characterised in that：Step（1）The method of the graphite powder plating metal is chemistry
Metallization or galvanoplastic.
6. according to the method for claim 1, it is characterised in that：Step（1）Metal in the graphite-metal composite material
Mass content is 20%~80%, preferably 40%~80%.
7. according to the method for claim 1, it is characterised in that：Step（2）The MOFs materials be IRMOF, ZIF, MIL,
One kind in HK or CPL series.
8. according to the method for claim 1, it is characterised in that：Step（2）The binder be selected from aluminium oxide, silica,
One or more of boehmite, kaolin, clay and organo-silicon compound etc..
9. according to the method for claim 1, it is characterised in that：Step（2）Described moulding dose be methylcellulose, starch,
Polyacrylate, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene or PolyTHF.
10. according to the method for claim 1, it is characterised in that：Step（2）The liquid is water or water-miscible
Alcohol, the alcohol are methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutanol or the tert-butyl alcohol.
11. according to the method for claim 1, it is characterised in that：Step（2）The MOFs materials, binder, graphite-gold
Belong to composite material, the moulding dose of mass ratio between liquid is 100：2~30：5~60：2~20：20~170.
12. according to the method for claim 1, it is characterised in that：Step（3）It is dried at 80~100 DEG C, at 180~300 DEG C
Roast 1~12h.
13. the enhanced thermal conduction type metal organic framework formed body prepared using any the methods of claim 1-12, feature
It is：By weight, in metal organic framework formed body, the content of MOFs materials is 40%~90%, preferably 60%~90%；Graphite
Content is 1%~20%, and conductive metal content is 1%~25%, and binder content is 2%~20%, and moulding agent content is 2%~15%.
14. the application of enhanced thermal conduction type metal organic framework formed body described in claim 13, it is characterised in that：Enhanced thermal conduction type
Metal organic framework formed body is applied in gas absorption, gas absorption storage, gas absorption separation, and the gas is titanium dioxide
Carbon, hydrogen, methane, carbon monoxide, nitrogen, ethane, propane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717888A (en) * | 2021-01-18 | 2021-04-30 | 太原理工大学 | Application of ultra-microporous MOF adsorbent material in hydrocarbon gas separation |
| CN113117647A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Foam metal supporting adsorption material and preparation method thereof |
| CN115501859A (en) * | 2021-06-23 | 2022-12-23 | 中国石油化工股份有限公司 | Metal organic framework forming body, preparation method thereof, method for removing small molecule gas by using metal organic framework forming body and application of metal organic framework forming body |
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