CN106268554A - A kind of core-shell type MOFs composite particles and its preparation method and application - Google Patents
A kind of core-shell type MOFs composite particles and its preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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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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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
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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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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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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
- B01J20/28—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
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
Abstract
The present invention relates to a kind of core-shell type MOFs composite particles and its preparation method and application.The preparation method of this core-shell type MOFs composite particles comprises the following steps: porous material and shaping assistant is mixed, wet granulation, roasting, obtains spherical core；Described core is soaked in binder solution, in the former powder of MOFs, then rolls pelletize, drying, obtain core-shell type MOFs composite particles.This core-shell type MOFs composite particles achieves the compound of core-shell material by the way of mechanical bond, and technique is simple, overcomes the limitation of core-shell material limitednumber in the mode that tradition in-situ chemical is compound, applied widely, interface binding power is strong, and yield is high, it is easy to commercial production.
Description
Technical field
The invention belongs to the technical field of Organic-inorganic composite porous material and preparation method thereof.
Background technology
Metal-organic framework materials (metal-organic frameworks, MOFs) is before a class has wide application
The novel porous materials of scape, is assembled generation by metal ion with organic ligand, by building different secondary structure units, can make
It has abundant pore passage structure, the specific surface area and porosity of super large and relatively low skeletal density.At present, MOFs becomes
One of the study hotspot of Material Field and forward position, exchange at gas storages, adsorbing separation, photoelectrocatalysis, ion, biological activity and
The fields such as molecular recognition show potential application prospect.
MOFs composite becomes fusion MOFs advantage and makes up its defect because having the combination property of independent component
A kind of new material, wherein MOFs Core-shell structure material is the study hotspot of chemical material field in recent ten years, and MOFs can make
Core, also can make shell, and complex method is mainly chemical synthesis process, such as epitaxial growth method, rear synthetic modification method etc..
Such as, Kondo et al. [Kondo A, Takanashi S, Maeda K.New insight into
mesoporous silica for nano metal–organic framework[J].Journal of colloid and
Interface science, 2012,384 (1): 110-115.] by being chemically synthesized mesoporous silicon oxide and metal has
Machine skeleton (MOFs) micropore-mesopore composite, preparation method is as follows: MOF presoma adds the mesoporous dioxy prepared
In SiClx, then by water heat transfer MOF, the adsorption rate of ethanol is higher than individually under 303K by the composite obtained
CuBTC micron-sized crystals.Zhang et al. [Zhang Y, Bo X, Nsabimana A, Han C, Li M, Guo
L.Electrocatalytically active cobalt-based metal–organic framework with
incorporated macroporous carbon composite for electrochemical applications
[J] .Journal of Materials Chemistry A, 2015,3,732-738.] it is prepared for Co-MOF and mesoporous carbon
(MPC) composite, method is as follows: first with mesoporous TiO2For templated synthesis mesoporous carbon, then Co-MOF presoma is added mesoporous
Mix homogeneously in carbon, synthesizes Co-MOF-MPC by one step hydro thermal method.The existence of MPC greatly improves electro-chemical activity, compound
Product oxidation hydrazine, reduction aminobenzene are outstanding than independent material.Kitagawa etc. [Fukushima T, Horike S,
Kobayashi H,Tsujimoto M,Isoda S,Foo M L,Kubota Y,Takata M,Kitagawa S.Modular
design of domain assembly in porous coordination polymer crystals via
reactivity-directed crystallization process[J].Journal of the American
Chemical Society, 2012,134 (32): 13341-13347.] synthesize porous by the method for molecular modules self assembly
Coordination polymer [{ Cu2(ndc)2(dabco)}n]@[{Zn2(ndc)2(dabco)}n] composite single crystal.This composite uses
Relatively simple hydrothermal method synthesis, in the reactant solution that shell crystal will be joined as the monocrystalline of core, anti-under uniform temperature
The composite crystal of nucleocapsid structure should be obtained a period of time.This method is that the different MOF of identical topological structure are compound provides thinking.
In above-mentioned traditional chemically composited method, the selection limitednumber of core-shell material, preparation process generally include by
The nuclear material prepared is put in the precursor solution of shell, growth in situ shell material outside nuclear material, it is desirable in shell material
Under the reaction condition of material, nuclear material to remain intact.Gained core-shell material is usually powder sample, is not easy to commercial Application.
Summary of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of core-shell type MOFs composite particles and preparation side thereof
Method and application.This core-shell type MOFs composite particles can overcome the defect that in traditional chemically composited method, step is numerous and diverse, uses
Molding composite integrated technology, technique is simple, it is simple to commercial Application.
In order to achieve the above object, the invention provides the preparation method of a kind of core-shell type MOFs composite particles, it includes
Following steps:
Porous material and shaping assistant are mixed, wet granulation, roasting, obtain spherical core；
Described core is soaked in binder solution, then in the cylinder having been placed in the former powder of MOFs roll pelletize with
Core surface forms shell, drying, obtains core-shell type MOFs composite particles, wherein it is possible to by controlling core in binder solution
The number of times soaked and roll in cylinder, the thickness of the shell of regulation core-shell type MOFs composite particles.
In above-mentioned preparation method, soak and roll the step of pelletize and can repeat as required.
In above-mentioned preparation method, it is preferable that the step of described wet granulation is: by molten to porous material, shaping assistant
Liquid stirs and makes wet feed group, wet feed group is put in the mould of banded extruder, uses extrusion process to be squeezed into bar, then
Pelletize.The wet granulation step of other routines is also applied for the present invention.
In above-mentioned preparation method, it is preferable that described porous nuclear material is 15:1-with the mass ratio of the former powder of described MOFs
3:1；The quality of described shaping assistant accounts for the 3%-40% of described core-shell type MOFs composite particles gross mass.
In above-mentioned preparation method, it is preferable that the particle diameter of described porous material is 1 μm-10 μm, after wet granulation
The particle diameter of grain is 1mm-5mm, and the thickness of described shell is 0.3mm-0.6mm.
In above-mentioned preparation method, it is preferable that described porous material is in molecular sieve, porous carbon and Woelm Alumina
A kind of.
In above-mentioned preparation method, it is preferable that the former powder of described MOFs is HKUST-1.The former powder of MOFs of other routines is all
It is applicable to the present invention.
In above-mentioned preparation method, it is preferable that described roasting is with the ramp of 2-6 DEG C/min, is warming up to 120
After DEG C-600 DEG C, roasting 5h-8h.
In above-mentioned preparation method, it is preferable that described shaping assistant include camphene, Alumina gel, Ludox, dust technology,
One or more in starch, dextrin and water；Preferably, during described binding agent includes dextrin, starch and Ludox, Alumina gel
One or more, the mass concentration of described binder solution is 5wt%-40wt%.The shaping assistant of other routines and bonding
Agent is readily adaptable for use in the present invention.
In above-mentioned preparation method, it is preferable that described be dried as vacuum drying, described dry temperature is 150 DEG C-
180 DEG C, the time is 5h-12h.
In above-mentioned preparation method, it is preferable that the rolling time of described rolling granulation step is 5min-30min, rotating speed
For 60-120r/min.
The present invention also provides for a kind of by above-mentioned preparation method preparation-obtained core-shell type MOFs composite particles.This core-shell type
The radial direction crush strength of MOFs composite particles is 20N/cm-100N/cm, and wear rate is 1%-5%, and specific surface area is 100m2/
g-1200m2/g。
The present invention also provides for the application in industrial circle of the above-mentioned core-shell type MOFs composite particles, it is preferable that described industry
Field includes gas absorption separation, gas storage, medicament slow release, catalysis or liquid phase separation field.
The preparation method of the core-shell type MOFs composite particles of the present invention achieves core-shell material by the way of mechanical bond
Compound, technique is simple, overcomes the limitation of core-shell material limitednumber in the mode that tradition in-situ chemical is compound, is suitable for model
Enclosing extensively, interface binding power is strong, and yield is high, it is easy to commercial production.Additionally, use molding composite integrated technology, eliminate powder
Powder composite material uses the moulding process in step.The core-shell type MOFs composite particles that the present invention prepares radially resistance to crusing is strong
Degree height, wear rate is low, and specific surface area is big, it is possible to be well applied to gas absorption separation, gas storage, medicament slow release, catalysis
Or the industrial circle such as liquid phase separation.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the core-shell type MOFs composite particles of embodiment 4 synthesis.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.In all embodiments
The former powder of MOFs all be HKUST-1 powder.
Embodiment 1
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
Being put into by 100g alumina powder in ceramic crucible and mix, instilling 200ml mass percent concentration wherein is
The dilute nitric acid solution of 15wt%, stirs with Glass rod, obtains wet feed group, and wet feed group is put into extrusion in band extrusion molding machine,
Then strip products formed is put into granulating and forming in Chinese medicinal pills preparing machine, it is thus achieved that the spherical particle of a diameter of 2mm；Spherical particle is whole
Put into after type in Muffle furnace, with the ramp of 2-6 DEG C/min to 120 DEG C, then, high-temperature roasting 5 hours at 120 DEG C,
To spherical core.
Above-mentioned core is soaked in the dextrin solution that mass percent concentration is 10% uniformly, put into and have been added to HKUST-
In the cylinder of the Chinese medicinal pills preparing machine of 1, after the scroll 30min of 90r/min, repeat the step soaked and roll, at core
It is the shell of 0.6mm that surface forms thickness, then puts in vacuum drying oven by the granule obtained, and at 180 DEG C, evacuation is dried
12h, prepares core-shell type MOFs composite particles, and its radial direction crush strength, abrasion resistance properties and BET specific surface area result are such as
Shown in table 1.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Table 1
Embodiment 2
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
Preparation method as described in example 1 above prepares core.
Above-mentioned core is soaked in the starch solution that mass percent concentration is 10% uniformly, put into and have been added to HKUST-
In the cylinder of the Chinese medicinal pills preparing machine of 1, after the scroll 30min of 90r/min, repeat the step soaked and roll, at core
It is the shell of 0.6mm that surface forms thickness, then puts in vacuum drying oven by the granule obtained, and at 180 DEG C, evacuation is dried
12h, prepares core-shell type MOFs composite particles, and its radial direction crush strength, abrasion resistance properties and BET specific surface area result are such as
Shown in table 1.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Embodiment 3
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
Preparation method as described in example 1 above prepares core.
Above-mentioned core is soaked in the mixed solution of the starch that mass percent concentration is 20% and dextrin uniformly, put into
Through add HKUST-1 Chinese medicinal pills preparing machine cylinder in, after the scroll 30min of 90r/min, repeat soak and roll
Step, forming thickness on the surface of core is the shell of 0.6mm, then puts in vacuum drying oven by the granule obtained, at 180 DEG C
Evacuation is dried 12h, prepares core-shell type MOFs composite particles, and radially crush strength, abrasion resistance properties and BET compare table for they
Area result is as shown in table 1.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Embodiment 4
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
1g porous carbon powder, 0.03g starch are put in ceramic crucible and mixed, instills 2ml mass percent wherein dense
Degree is the dilute nitric acid solution of 15%, stirs with Glass rod, obtains wet feed group, wet feed group is put in band extrusion molding machine and squeezes
Bar, then puts into granulating and forming in Chinese medicinal pills preparing machine by strip products formed, it is thus achieved that the spherical particle of a diameter of 2mm；By spherical
Put in Muffle furnace after grain integer, with the ramp of 2-6 DEG C/min to 120 DEG C, then, within 5 hours, obtain in 120 DEG C of high-temperature roastings
Obtain spheroidal particle, obtain spherical core.
Preparation method in above-mentioned core such as embodiment 2 is prepared core-shell type MOFs composite particles, its radially resistance to crusing
Intensity, abrasion resistance properties and BET specific surface area result are as shown in table 1, and powder X-ray RD after pulverizing is as shown in Figure 1.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Embodiment 5
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
Preparation method as described in example 4 above prepares core.
Core is soaked in the starch solution that mass percent concentration is 20% uniformly, put into and have been added to HKUST-1's
In the cylinder of Chinese medicinal pills preparing machine, after the scroll 15min of 90r/min, forming thickness on the surface of core is the shell of 0.3mm,
Then putting in vacuum drying oven by the granule obtained, at 180 DEG C, evacuation is dried 12h, prepares core-shell type MOFs multiple
Closing granule, radially crush strength, abrasion resistance properties and BET specific surface area result are as shown in table 1 for they.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Embodiment 6
Present embodiments providing the preparation method of a kind of core-shell type MOFs composite particles, it comprises the following steps:
10g Y type molecular sieve is put in ceramic crucible, instills the silicon that 6ml mass percent concentration is 20% wherein molten
Glue, stirs with Glass rod, obtains wet feed group, wet feed group puts into extrusion in band extrusion molding machine, then by strip products formed
Put into granulating and forming in Chinese medicinal pills preparing machine, it is thus achieved that the spherical particle of a diameter of 2mm；Muffle furnace is put into after spherical particle integer
In, with the ramp of 2～6 DEG C/min to 550 DEG C, then, in 550 DEG C of high-temperature roastings 6 hours, obtain spherical core.
Above-mentioned core is soaked in the starch solution that mass percent concentration is 10% uniformly, put into and have been added to HKUST-
In the cylinder of the Chinese medicinal pills preparing machine of 1, after the scroll 15min of 90r/min, forming thickness on the surface of core is 0.3mm's
Shell, then, puts in vacuum drying oven by the granule obtained, and at 180 DEG C, evacuation is dried 12h, prepares core-shell type
MOFs composite particles, radially crush strength, abrasion resistance properties and BET specific surface area result are as shown in table 1 for they.
This core-shell type MOFs composite particles may be directly applied to gas absorption separation, gas storage, medicament slow release, catalysis and
The industrial circles such as liquid phase separation.
Claims (10)
1. a preparation method for core-shell type MOFs composite particles, it comprises the following steps:
Porous material and shaping assistant being mixed, wet granulation obtains spherical particle, roasting, obtains spherical core；
Being soaked in binder solution by described core, then in the former powder of MOFs, rolling pelletize to form shell on core surface, through dry
Dry, obtain core-shell type MOFs composite particles.
2. preparation method as claimed in claim 1, wherein, the mass ratio of described porous nuclear material powder former with described MOFs is
(15:1)-(3:1)；The quality of described shaping assistant accounts for the 3%-40% of described core-shell type MOFs composite particles gross mass.
3. preparation method as claimed in claim 1 or 2, wherein, the particle diameter of described porous material is 1 μm-10 μm, described wet method
The particle diameter of the spherical particle after pelletize is 1mm-5mm, and the thickness of described shell is 0.3mm-0.6mm.
4. the preparation method as according to any one of claim 1-3, wherein, described porous material be molecular sieve, porous carbon and
One in Woelm Alumina.
5. the preparation method as according to any one of claim 1-4, wherein, described roasting is the speed liter with 2-6 DEG C/min
Temperature, after being warming up to 120 DEG C-600 DEG C, roasting 5h-8h.
6. the preparation method as according to any one of claim 1-5, wherein, described shaping assistant includes camphene, Alumina gel, silicon
One or more in colloidal sol, dust technology, starch, dextrin and water；Described binding agent includes dextrin, starch, Ludox and aluminum
One or more in colloidal sol, the mass percent concentration of described binder solution is 5wt%-40wt%.
7. the preparation method as according to any one of claim 1-6, wherein, described be dried into vacuum drying, described dry
Temperature is 150 DEG C-180 DEG C, and the time is 5h-12h；The rolling time of described rolling granulation step is 5min-30min, and rotating speed is
60-120r/min。
8. utilize the core-shell type MOFs composite particles that the preparation method according to any one of claim 1-7 prepares.
9. core-shell type MOFs composite particles as claimed in claim 8, wherein, the radial direction of described core-shell type MOFs composite particles resists
Crushing strength is 20N/cm-100N/cm, and wear rate is 1%-5%, and specific surface area is 100m2/g-1200m2/g。
10. the application in industrial circle of the core-shell type MOFs composite particles described in claim 8 or 9, it is preferable that described industry
Field includes gas absorption separation, gas storage, medicament slow release, catalysis or liquid phase separation field.
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