CN106622140A - Composite zeolitic imidazolate framework material as well as preparation method and application thereof - Google Patents
Composite zeolitic imidazolate framework material as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite zeolitic imidazolate framework material as well as a preparation method and application thereof. The composite zeolitic imidazolate framework material provided by the invention is prepared from a zeolitic imidazolate framework material and a microcapsule, wherein the surface of the microcapsule is clad with the zeolitic imidazolate framework material; a shell layer of the microcapsule is SiO2; an inner core of the microcapsule is an organic phase-change material. The composite zeolitic imidazolate framework material provided by the invention not only has quite high crystallinity, specific surface area and total pore volume, but also has a quite low heat effect.
Description
Technical field
It is composite zeolite imidazate framework material for being applied to during gas absorption, gas absorption storage, gas absorption are separated and preparation method thereof more specifically the present invention relates to a kind of zeolitic imidazolate framework material and preparation method thereof.
Background technology
Zeolitic imidazolate framework material (Zeolitic
Imidazolate frameworks, ZIFs it is) that a class is acted on the rigid backbone material for being formed by metal ion and organic ligand by self assembly, its topological structure is similar to Si-Al zeolite molecular sieve, therefore, there is huge potential application foreground, the particularly prospect in terms of energy gas such as methane and hydrogen adsorption in fields such as gas-selectively absorption, catalysis, storage, medical science, optics and electromagnetism materials more to attract people's attention.
The absorption of gas would generally release substantial amounts of heat; and the heat conductivility of the adsorbent such as activated carbon, zeolite, composite zeolite imidazate framework material is poor; adsorbent is caused the energy of release to be absorbed in adsorption process and is heated; there is larger temperature rise in whole adsorption bed, serious to reduce gas absorption capacity.Similar situation is applied to desorption, and the reduction of temperature can have a negative impact to desorption process, cause a part of gas to be particularly heavy constituent and remain in adsorbent, affect release capacity and the life-span of adsorbent.
CN 103230777A disclose a kind of a large amount of preparations of sorbing material ZIF-8 and forming method.DMF is injected in polytetrafluoroethyllining lining, zinc nitrate and 2-methylimidazole is added fully to dissolve, it is then placed in reactor carrying out crystallization by self-generated pressure, crystallization temperature is 100～140 DEG C, time is 12～36h, finally cooling, suction filtration, wash and grind after compressing tablet, obtain sheet ZIF-8 material.The method crystallization time is long, and the yield of product is relatively low, and the ZIF-8 crystal grain for preparing is larger, and grinding is needed before the forming；Additionally, material fuel factor in gas absorption-desorption is obvious, the more theoretical adsorption capacity gap of its memory capacity is larger.
CN 102220626A disclose a kind of method that dynamic crystallization prepares nano-zeolite metal-organic framework compound crystal.Metal precursor and organic ligand are dissolved in into respectively solvent preparing metal precursor solution A and organic ligand solution B, to be placed in the reactor with agitating device after solution A and solution B mixing, 30～180 DEG C of reaction 10min～96h, reaction is cooled down after terminating, termination crystal growth, and centrifugation, washing obtain target product.The method can effectively reduce crystalline size, it is adaptable to the preparation of various ZIFs crystal.But crystal exterior appearance prepared by the method is irregular and is difficult to control to crystal size；Additionally, the material there is also obvious fuel factor in gas absorption-desorption.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of zeolitic imidazolate framework material and preparation method thereof, and application of the composite zeolite imidazate framework material in gas absorption, gas absorption storage, gas absorption are separated.The zeolitic imidazolate framework material of the present invention not only has very high degree of crystallinity, specific surface area, total pore volume, but also with very low fuel factor.
A kind of composite zeolite imidazate framework material that the present invention is provided, it includes zeolitic imidazolate framework material and microcapsules, and the zeolitic imidazolate framework material is coated on the surface of the microcapsules, and the shell of the microcapsules is SiO2, the kernel of the microcapsules is organic phase change material.
The property of composite zeolite imidazate framework material of the present invention is as follows：Specific surface area is 900m2/ g～2000m2/ g, preferably 1300m2/ g～2000m2/ g, total pore volume is 0.4cm3/ g～0.8cm3/ g, preferably 0.5cm3/ g～0.7cm3/g。
On the basis of the weight of the composite zeolite imidazate framework material, the content of the zeolitic imidazolate framework material is 80wt%～99wt%, and the content of microcapsules is 1wt%～20wt%.
In the composite zeolite imidazate framework material, the SiO2It is with the part by weight of the organic phase change material（0.2～1.2）：1.
The relative crystallinity of the composite zeolite imidazate framework material is 100%～200%.
The average grain diameter of the composite zeolite imidazate framework material is 100nm～600nm, preferably 150nm～500nm.
In the composite zeolite imidazate framework material, the thickness of the zeolitic imidazolate framework material is 50nm～400nm, and the particle diameter of the microcapsules is 50nm～200nm.
The zeolitic imidazolate framework material is zeolitic imidazolate framework material ZIF-8.
In microcapsules, organic phase change material can be paraffin, C14～C24N-alkane, C9～C18Higher fatty acids and its esters in one or more, C14～C24N-alkane be, for example, one or more in n-tetradecane hydrocarbon, hexadecane hydrocarbon, n-heptadecane hydrocarbon, n-octadecane hydrocarbon, NSC 77136 hydrocarbon, n-eicosane hydrocarbon, n-docosane hydrocarbon, n-tricosane hydrocarbon, n-tetracosane hydrocarbon, C9～C18Higher fatty acids be, for example, one or more in capric acid, laurate, palmitic acid, the acid of pearly-lustre ester, stearic acid, oleic acid, linoleic acid, C9～C18High-grade aliphatic ester be, for example, one or more in BS, isopropyl stearate, isobutyl stearate, glyceride.Paraffin is preferably 18#Paraffin, 20#Paraffin, 25#Paraffin, 30#Paraffin, 35#One or more in paraffin.Organic phase change material is preferably 18#One or more in paraffin, 20# paraffin, 25# paraffin, 30# paraffin, 35# paraffin and BS.
A kind of preparation method of composite zeolite imidazate framework material that the present invention is also provided, it comprises the steps：
（1）Organic phase change material and surfactant are added in ethanol water, then heating makes phase-change material melt and stir, the emulsion containing organic phase change material is obtained, then tetraethyl orthosilicate and acid catalyst is added to be hydrolyzed reaction in emulsion, after stirring, ageing, filtration, drying, the microcapsules of coated with silica phase-change material are obtained final product；
（2）The microcapsules are added in organic solvent, the suspension of microcapsules is obtained.
（3）Zinc source and 2-methylimidazole are added to into step（2）Suspension in, and fully shaking dissolves, and obtains mixed liquor, and then mixed liquor is transferred in autoclave carries out synthetic reaction, and product is filtered, and is then washed and is dried, you can prepared composite zeolite imidazate framework material.
The organic phase change material, surfactant and ethanol water part by weight are 10：（0.1～3）：（20～100）, ethanol is with the weight ratio of water in the ethanol water（1～5）:1.
The surfactant can be one or more in polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate etc., one or two preferably in lauryl sodium sulfate and sodium tetradecyl sulfate.
The part by weight of the organic phase change material, tetraethyl orthosilicate and acid catalyst is 10：（5～40）：（0.1～5）.
The acid catalyst is inorganic acid solution or organic acid soln, and the inorganic acid is one or more in hydrochloric acid, nitric acid, sulfuric acid, and the organic acid is 0.5wt%～10.0wt% for the concentration of acetic acid, inorganic acid solution or organic acid soln.
In step（2）In, the microcapsules are with organic solvent part by weight（1～5）：1000.
In step（2）In, the organic solvent be DMF, DMA, N, one or more in N- DEFs.
In step（3）In, the Zn in the zinc source2+It is 1 with the mol ratio of 2-methylimidazole：（1～6）, preferably 1：（2～4）.
In step（3）In, the zinc source is one or more in zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, preferably zinc nitrate.
In step（3）In, the temperature of the synthetic reaction is 90 DEG C～180 DEG C, and preferably 100 DEG C～150 DEG C, the time is 3h～20h, preferably 6h～16h.
The method also includes post-processing step：After drying, with soaked in absolute ethyl alcohol 12h～36h, 4～36h is then vacuum dried at 80 DEG C～120 DEG C.
Present invention also offers application of the above-mentioned composite zeolite imidazate framework material in middle gas absorption, gas absorption storage, gas absorption are separated.
Described composite zeolite imidazate framework material is stored in hydrogen, methane adsorption, and methane/carbon dioxide, methane/nitrogen mixture are selectively adsorbing and separating the application in methane.
The composite zeolite imidazate framework material of the present invention, the application that can be used in gas absorption, gas absorption storage, gas absorption separation, especially in carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane or propane absorbing and storing, and carbonoxide/methane, carbon dioxide/carbon monoxide, titanium dioxide carbon/nitrogen gas, carbon dioxide/oxygen, hydrogen/carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene or propane/propylene gaseous mixture are selectively adsorbing and separating.
Compared with prior art, the invention has the advantages that：
（1）The composite zeolite imidazate framework material of the present invention, fuel factor when can reduce gas absorption-desorption affects, and is embodied in：During adsorbed gas, PCM@SiO2Phase-change material in crystal seed undergoes phase transition, and absorbs gas absorption liberated heat and reduces temperature rise, improves gas absorption amount；During desorption gas, phase-change material can discharge the heat of absorption and reduce temperature drop, improve desorbing gas amount.
Furthermore, the composite zeolite imidazate framework material of the present invention has very high degree of crystallinity, specific surface area, total pore volume, so as in the gas absorption selectivity such as hydrogen, methane, ethane, propane, carbon dioxide, hence it is evident that better than the zeolitic imidazolate framework material of Conventional solvents thermal synthesis method.
（2）The present invention is in the preparation process of composite zeolite imidazate framework material, in the organic phase change material emulsion containing surfactant, when tetraethyl orthosilicate is hydrolyzed under acidic catalyst effect, in the superficial growth of emulsion droplet, the microcapsules for obtaining have the SiO that neat appearance, surface flatness are higher and surface silanol group is very more to silica2Shell, then in SiO2Zeolitic imidazolate framework material is grown on shell, such that it is able to avoid zeolitic imidazolate framework material in SiO2Out-phase grows highly difficult problem on substrate surface.
Furthermore, because zeolitic imidazolate framework material has sodalite molecular sieve type structure, with PCM@SiO2The shell SiO of microcapsules2Structure it is similar, therefore PCM@SiO2Microcapsules can induce the growth of crystal grain as crystal seed, so not only can not only be used for the introduction of nucleus formation, seed particles are made to produce epitaxial nucleation and epitaxial growth, effectively reduce surface energy barrier potential during zeolitic imidazolate framework material nucleation, reduce the activation energy of nucleation, accelerate crystal transition, greatly shorten crystallization time；But also can make that the crystal grain of zeolitic imidazolate framework material is less and size is homogeneous, specific surface area and pore volume are greatly improved, and yield increases.
Description of the drawings
Fig. 1 is PCM@SiO prepared by embodiment 12Microcapsules electron scanning micrograph（SEM）；
The sample A that Fig. 2 is prepared for embodiment 1-5 and comparative example 2,3, the X-ray collection of illustrative plates of B, C, D, E, G, H（XRD）；
Fig. 3 is sample A sweep electron micrograph prepared by embodiment 1（SEM）；
Fig. 4 is sample G electron scanning micrographs prepared by comparative example 2（SEM）.
Specific embodiment
The preparation process of composite zeolite imidazate framework material of the present invention is further illustrated below by embodiment, but be invention should not be deemed limited in below example, wherein wt% is mass fraction.
Embodiment
1
（1）Take that 10 weight portion phase transition temperatures are 25 DEG C 25#Paraffin and 2 weight portion lauryl sodium sulfate are added in the 70 parts by weight of ethanol aqueous solution, and wherein absolute ethyl alcohol and the mass ratio of water are 4：1.Heat in 50 DEG C of water-baths, mechanical agitation 30 minutes after material molten to be phased obtain finely dispersed emulsion；Be added dropwise the 1wt% hydrochloric acid of 8 weight portion tetraethyl orthosilicates and 0.25 weight portion in above-mentioned emulsion, continue constant temperature and stir 3 hours, ageing under room temperature, filter, washing, be dried after obtain final product PCM@SiO2Microcapsules.As shown in Figure 1, PCM@SiO2Microcapsules Size is 80nm～120nm, even particle size distribution, and the shape matching of microcapsules is regular, and surface is smooth, containing very many surface silanol groups.
（2）By 0.5 weight portion PCM@SiO2Microcapsules are added in 100 weight portion DMFs, and PCM@SiO are obtained obtaining after stirring2The suspension of microcapsules.
（3）Add 1.1 weight portion 2-methylimidazoles and 1 weight portion zinc nitrate hexahydrate in above-mentioned suspension, after fully shaking dissolving, above-mentioned mixed liquor is transferred to being reacted in teflon-lined autoclave；Autoclave is placed in temperature programmed control baking oven, with the heating rate of 5 DEG C/min 100 DEG C are risen to, be incubated 12h；After autoclave is cooled to room temperature, product is filtered, cleaned with DMF three times, after being dried soaked in absolute ethyl alcohol 24h is used；Product is vacuum dried into 12h at 80 DEG C, you can composite zeolite imidazate framework material A is obtained, XRD signs is carried out to sample, as shown in Figure 2, it can be seen that the sample of synthesis is ZIF-8, and degree of crystallinity is very high.From figure 3, it can be seen that sample A surfaces are smooth, grain size range is 190nm～300nm, and size distribution is more homogeneous.
Embodiment
2
Preparation method is substantially the same manner as Example 1, and difference is by PCM@SiO2The weight of microcapsules reduces to 0.2 weight portion, and composite zeolite imidazate framework material B is obtained.
Embodiment
3
（1）Take that 10 weight portion phase transition temperatures are 35 DEG C 35#Paraffin and 2 weight portion sodium tetradecyl sulfates are added in the 50 parts by weight of ethanol aqueous solution, and wherein absolute ethyl alcohol and the mass ratio of water are 4：1.Heat in 50 DEG C of water-baths, mechanical agitation 30 minutes after material molten to be phased obtain finely dispersed emulsion；Be added dropwise 16 weight portion tetraethyl orthosilicates and 5 weight portion 4wt% acetic acid in above-mentioned emulsion, continue constant temperature and stir 4 hours, ageing under room temperature, filter, washing, be dried after obtain final product PCM@SiO2Microcapsules.PCM@SiO2Microcapsules Size is 100nm～150nm, is distributed more uniform.
（2）By 0.3 weight portion PCM@SiO2Microcapsules are added in 100 weight portion DMFs, and PCM@SiO are obtained obtaining after stirring2The suspension of microcapsules.
（3）Add 1.01 weight portion 2-methylimidazoles and 1.2 weight portion zinc nitrate hexahydrates in above-mentioned suspension, after fully shaking dissolving, above-mentioned mixed liquor is transferred to being reacted in teflon-lined autoclave；Autoclave is placed in temperature programmed control baking oven, with the heating rate of 3 DEG C/min 140 DEG C are risen to, be incubated 6h；After autoclave is cooled to room temperature, product is filtered, cleaned with DMF three times, after being dried soaked in absolute ethyl alcohol 24h is used；Product is vacuum dried into 12h at 100 DEG C, you can composite zeolite imidazate framework material C is obtained, XRD signs is carried out to sample, as shown in Figure 2, it can be seen that the sample C of synthesis is ZIF-8, and degree of crystallinity is high, and sample is pure.
Embodiment
4
Preparation method is substantially the same manner as Example 3, and difference is that autoclave is placed in temperature programmed control baking oven, and with the heating rate of 3 DEG C/min 100 DEG C are risen to, and is incubated 6h, and composite zeolite imidazate framework material D is obtained.
Embodiment
5
（1）Take BS that 10 weight portion phase transition temperatures are 18 DEG C～22 DEG C and 3 weight portion lauryl sodium sulfate are added in the 90 parts by weight of ethanol aqueous solution, wherein absolute ethyl alcohol and the mass ratio of water are 3：1.Heat in 40 DEG C of water-baths, mechanical agitation 30 minutes after material molten to be phased obtain finely dispersed emulsion；Be added dropwise 24 weight portion tetraethyl orthosilicates and 3 weight portion 2wt% sulfuric acid in above-mentioned emulsion, continue constant temperature and stir 4 hours, ageing under room temperature, filter, washing, be dried after obtain final product PCM@SiO2Microcapsules.PCM@SiO2Microcapsules Size is 110nm～166nm, is distributed more uniform.
（2）By 0.1 weight portion PCM@SiO2Microcapsules are added in 100 weight portion DMFs, and PCM@SiO are obtained obtaining after stirring2The suspension of microcapsules.
（3）Add 0.79 weight portion 2-methylimidazole and 1.4 weight portion zinc nitrate hexahydrates in above-mentioned suspension, after fully shaking dissolving, above-mentioned mixed liquor is transferred to being reacted in teflon-lined autoclave；Autoclave is placed in temperature programmed control baking oven, with the heating rate of 4 DEG C/min 120 DEG C are risen to, be incubated 16h；After autoclave is cooled to room temperature, product is filtered, cleaned with DMF three times, after being dried soaked in absolute ethyl alcohol 24h is used；Product is vacuum dried into 12h at 120 DEG C, you can composite zeolite imidazate framework material E is obtained, XRD signs is carried out to sample, as shown in Figure 2, it can be seen that the sample E of synthesis is ZIF-8, and degree of crystallinity is very high.
Comparative example 1 （According toThe preparation method of CN103230777A）
1.1 weight portion 2-methylimidazoles and 1 weight portion zinc nitrate hexahydrate are added in 100 weight portion DMFs, after fully shaking dissolving, above-mentioned mixed liquor are transferred to being reacted in teflon-lined autoclave；Autoclave is placed in temperature programmed control baking oven, with the heating rate of 5 DEG C/min 100 DEG C are risen to, be incubated 12h；After autoclave is cooled to room temperature, it is found that autoclave base generates very small amount of zeolitic imidazolate framework material F.
Comparative example
2
With comparative example 1, difference is that the temperature retention time by autoclave at 100 DEG C is changed into 24h from 12h to preparation method, and obtained sample is G.Characterize from the XRD of Fig. 2 and understand, the composite zeolite imidazate framework material of synthesis is G, but degree of crystallinity to be not so good as sample A high.From shown in Fig. 4, it can be seen that sample G surfaces are smooth not as sample A, and crystal size distribution is uneven, its size range is 130nm～550nm.
Comparative example
3
（1）Take that 10 weight portion phase transition temperatures are 25 DEG C 25#Paraffin and 2 weight portion lauryl sodium sulfate are added in the 70 parts by weight of ethanol aqueous solution, and wherein absolute ethyl alcohol and the mass ratio of water are 4：1.Heat in 50 DEG C of water-baths, mechanical agitation 30 minutes after material molten to be phased obtain finely dispersed emulsion；
Under 40 DEG C of stirring conditions, sodium silicate solution and cetyl trimethylammonium bromide (CTAB) ethanol solution of the mass concentration for 5wt%～20wt% is added dropwise in above-mentioned emulsion, the amount of dropwise addition is 1 with the mass ratio of sodium metasilicate, cetyl trimethylammonium bromide for phase-change material：0.4：0.005, after being sufficiently stirred for, then be added dropwise ammonia spirit to pH be 10, continue constant temperature stir 3 hours, under room temperature ageing, filter, washing, be dried after obtain final product SiO2Particle.SiO2The profile of particle is irregular, and surface is very coarse, and particle size is uneven.
（2）Take 0.5 weight portion SiO2Particle is added in 100 weight portion DMFs, and SiO is obtained obtaining after stirring2Suspension.
（3）Add 1.1 weight portion 2-methylimidazoles and 1 weight portion zinc nitrate hexahydrate in above-mentioned suspension, after fully shaking dissolving, above-mentioned mixed liquor is transferred to being reacted in teflon-lined autoclave；Autoclave is placed in temperature programmed control baking oven, with the heating rate of 5 DEG C/min 100 DEG C are risen to, be incubated 12h；After autoclave is cooled to room temperature, product is filtered, cleaned with DMF three times, after being dried soaked in absolute ethyl alcohol 24h is used；Product is vacuum dried into 12h at 80 DEG C, you can composite zeolite imidazate framework material H is obtained.XRD signs are carried out to sample H, as shown in Figure 2, it can be seen that the characteristic peak of the ZIF-8 of sample H is very weak, and degree of crystallinity is very low.After testing, sample H is not crystal state, only in SiO2Particle surface has the metal-organic framework materials of thin layer, and poor with silica associativity, easily drops.
Test case
1
The physico-chemical property of the zeolitic imidazolate framework material of the composite zeolite imidazate framework material and comparative example 2 of embodiment 1-5 is determined, concrete outcome is shown in Tables 1 and 2.Wherein, yield is by based on zinc source.BET specific surface area, pore volume are measured by low temperature liquid nitrogen absorption method.Relative crystallinity, to buy the Basolite of BASF Corp. of Germany's production®On the basis of Z1200, set its degree of crystallinity and be calculated as 100%, degree of crystallinity is determined by XRD methods.
The physicochemical property of each material of table 1
| Sample | Crystallization time/h | Yield/wt% | Specific surface area/m2·g-1 | Total pore volume/cm3·g-1 | Relative crystallinity/% | Grain size/nm | Crystal shape |
| A | 12 | 84 | 1723 | 0.68 | 181 | 190～300 | Surface is smooth, uniform in size |
| B | 12 | 69 | 1445 | 0.61 | 145 | 250～430 | Surface is smooth, uniform in size |
| C | 6 | 77 | 1532 | 0.64 | 163 | 260～380 | Surface is smooth, uniform in size |
| D | 6 | 72 | 1626 | 0.57 | 136 | 230～370 | Surface is smooth, uniform in size |
| E | 16 | 73 | 1341 | 0.62 | 121 | 320～500 | Surface is smooth, uniform in size |
| G | 24 | 56 | 1210 | 0.50 | 84 | 130～550 | Surface is smooth, size is uneven |
| H | 12 | 32 | 983 | 0.52 | 21 | 120～760 | Rough surface, size are uneven |
As can be seen from Table 1, the sample G that the sample A-E that prepared by embodiment of the present invention 1-5 are prepared with comparative example 2,3, H are compared, and shorten crystallization time, improve yield and degree of crystallinity, increase specific surface area and pore volume, crystal grain have been uniformed, with more obvious advantage.Sample F prepared by comparative example 1 is considerably less due to measuring, it is impossible to carry out characterization test.
Test case
2
The adsorption capacity and temperature rise value of the methane of the zeolitic imidazolate framework material of the composite zeolite imidazate framework material and comparative example 2 of embodiment 1-5 are determined, test result is shown in Table 2.Concrete method of testing is as follows：
The 500g samples of preparation are loaded into respectively in the 1.2L heat-insulation storage tanks with thermocouple, the heat-insulation storage tank is then closed.Methane gas is filled with to the container at 25 DEG C, initial pressure is normal pressure, sets the blowing pressure as 50bar, determine bed central temperature change in 5 minutes, and the heat-insulation storage tank before and after inflation is weighed.
The each material adsorbing separation effect of table 2
| Sample | Temperature rising value, DEG C | Methane adsorption amount, mg/g |
| A | 23 | 84 |
| B | 26 | 80 |
| C | 25 | 82 |
| D | 24 | 82 |
| E | 27 | 78 |
| G | 42 | 64 |
The adsorbing separation effect data that table 2 is given is further illustrated, and is found through test, and the temperature rise of sample A is 23 DEG C, and adsorption capacity is 84mg/g, and the temperature rise of the sample G of comparative example 2 is up to 42 DEG C, and adsorption capacity is 64mg/g.Sample A adsorbs 31% methane gas more than sample G.Composite zeolite imidazate framework material prepared by the present invention has higher CH4Adsorption capacity.
Claims (22)
1. a kind of composite zeolite imidazate framework material, it is characterised in that it includes zeolitic imidazolate framework material and microcapsules, the zeolitic imidazolate framework material is coated on the surface of the microcapsules, and the shell of the microcapsules is SiO2, the kernel of the microcapsules is organic phase change material.
2. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：The property of described composite zeolite imidazate framework material is as follows：Specific surface area is 900m2/ g～2000m2/ g, preferably 1300m2/ g～2000m2/ g, total pore volume is 0.4cm3/ g～0.8cm3/ g, preferably 0.5cm3/ g～0.7cm3/g。
3. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：On the basis of the weight of the composite zeolite imidazate framework material, the content of the zeolitic imidazolate framework material is 80wt%～99wt%, and the content of microcapsules is 1wt%～20wt%.
4. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：In the composite zeolite imidazate framework material, the SiO2It is with the part by weight of the organic phase change material（0.2～1.2）：1.
5. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：The relative crystallinity of the composite zeolite imidazate framework material is 100%～200%.
6. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：The average grain diameter of the composite zeolite imidazate framework material is 100nm～600nm, preferably 150nm～500nm.
7. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：In the composite zeolite imidazate framework material, the thickness of the zeolitic imidazolate framework material is 50nm～400nm, and the particle diameter of the microcapsules is 50nm～200nm.
8. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：The zeolitic imidazolate framework material is zeolitic imidazolate framework material ZIF-8.
9. according to the composite zeolite imidazate framework material described in claim 1, it is characterised in that：The organic phase change material is paraffin, C14～C24N-alkane, C9～C18Higher fatty acids and its esters in one or more.
10. a kind of preparation method of the composite zeolite imidazate framework material as described in claim 1-9, it is characterised in that comprise the steps：
（1）Organic phase change material and surfactant are added in ethanol water, then heating makes phase-change material melt and stir, the emulsion containing organic phase change material is obtained, then tetraethyl orthosilicate and acid catalyst is added to be hydrolyzed reaction in emulsion, after stirring, ageing, filtration, drying, the microcapsules of coated with silica phase-change material are obtained final product；
（2）The microcapsules are added in organic solvent, the suspension of microcapsules is obtained；
（3）Zinc source and 2-methylimidazole are added to into step（2）Suspension in, and fully shaking dissolves, and obtains mixed liquor, and then mixed liquor is transferred in autoclave carries out synthetic reaction, and product is filtered, and is then washed and is dried, you can prepared composite zeolite imidazate framework material.
11. in accordance with the method for claim 10, it is characterised in that：The organic phase change material, surfactant and ethanol water part by weight are 10：（0.1～3）：（20～100）, ethanol is with the weight ratio of water in the ethanol water（1～5）:1.
12. according to the method described in claim 10 or 11, it is characterised in that：The surfactant is one or more in polyethylene glycol, sucrose ester, polysorbate, octadecyl benzenesulfonic acid, lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate, preferably lauryl sodium sulfate and/or sodium tetradecyl sulfate.
13. in accordance with the method for claim 10, it is characterised in that：The part by weight of the organic phase change material, tetraethyl orthosilicate and acid catalyst is 10：（5～40）：（0.1～5）.
14. in accordance with the method for claim 10, it is characterised in that：The acid catalyst is inorganic acid solution or organic acid soln, and the inorganic acid is one or more in hydrochloric acid, nitric acid, sulfuric acid, and the organic acid is 0.5wt%～10.0wt% for the concentration of acetic acid, inorganic acid solution or organic acid soln.
15. in accordance with the method for claim 10, it is characterised in that：In step（2）In, the microcapsules are with organic solvent part by weight（1～5）：1000.
16. in accordance with the method for claim 10, it is characterised in that：In step（2）In, the organic solvent be DMF, DMA, N, one or more in N- DEFs.
17. in accordance with the method for claim 10, it is characterised in that：In step（3）In, the Zn in the zinc source2+It is 1 with the mol ratio of 2-methylimidazole：（1～6）, preferably 1：（2～4）.
18. in accordance with the method for claim 10, it is characterised in that：In step（3）In, the zinc source is one or more in zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, preferably zinc nitrate.
19. in accordance with the method for claim 10, it is characterised in that：In step（3）In, the temperature of the synthetic reaction is 90 DEG C～180 DEG C, and preferably 100 DEG C～150 DEG C, the time is 3h～20h, preferably 6h～16h.
20. in accordance with the method for claim 10, it is characterised in that：The method also includes post-processing step：After drying, with soaked in absolute ethyl alcohol 12h～36h, 4～36h is then vacuum dried at 80 DEG C～120 DEG C.
Application of the composite zeolite imidazate framework material in 21. claims 1-9 described in any one in middle gas absorption, gas absorption storage or gas absorption are separated.
22. according to the application described in claim 21, described gas absorption is stored as carbon dioxide, hydrogen, methane, carbon monoxide, nitrogen, ethane or propane absorbing and storing, and gas absorption is separated into carbon dioxide/methane, carbon dioxide/carbon monoxide, titanium dioxide carbon/nitrogen gas, carbon dioxide/oxygen, hydrogen/carbon dioxide, hydrogen/nitrogen, methane/nitrogen, ethane/ethylene or propane/propylene gaseous mixture and is selectively adsorbing and separating.
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