CN104525127A - CuCl supported MIL-100(Fe) with high CO adsorption capacity and preparation method thereof - Google Patents

CuCl supported MIL-100(Fe) with high CO adsorption capacity and preparation method thereof Download PDF

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Publication number
CN104525127A
CN104525127A CN201410834381.3A CN201410834381A CN104525127A CN 104525127 A CN104525127 A CN 104525127A CN 201410834381 A CN201410834381 A CN 201410834381A CN 104525127 A CN104525127 A CN 104525127A
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China
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mil
cucl
preparation
supported
adsorption
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CN201410834381.3A
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Inventor
何靓
彭俊洁
廖头根
黄艳
李忠
刘亚
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China Tobacco Yunnan Industrial Co Ltd
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China Tobacco Yunnan Industrial Co Ltd
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Priority to CN201410834381.3A priority Critical patent/CN104525127A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/204—Metal organic frameworks (MOF's)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Abstract

The invention discloses a preparation method of CuCl supported MIL-100(Fe) with high CO adsorption capacity. The preparation method comprises the following three steps: preparing a precursor, evaporating water and activating in vacuum. The CuCl supported MIL-100(Fe) is prepared at normal temperature and pressure, wherein MIL-100(Fe) serves as a supporter, and Cu is supported on the surface of MIL-100(Fe) as a monovalent Cu(I), thus the CO adsorption capacity and selectivity can be improved greatly and by 7 times at most. With the characteristics, the CuCl supported MIL-100(Fe) prepared by adopting the preparation method has good application prospect in abatement of pollution to environment and reclamation of CO as important chemical raw materials from various industrial waste gases.

Description

A kind of preparation method and CuCl@MIL-100 (Fe) material CO to the CuCl@MIL-100 (Fe) of high-adsorption-capacity
Technical field
The invention belongs to material chemistry technical field, specifically, the present invention relates to a kind of under normal temperature and pressure conditions, prepare the method for modified metal organic framework material CuCl@MIL-100 (Fe) CO to high-adsorption-capacity.
Background technology
Carbon monoxide CO is that one has more highly toxic gaseous matter to human body, is also the basic substance of C1 chemical industry simultaneously.In industrial processes; usually a lot of waste gas containing CO can be produced (according to statistics; the CO that China's all types of industries process is discharged every year is up to more than 5,000 ten thousand tons), from these are discarded, carry out recovery or the purification of CO, there is very large economy and environment benefit.In prior art, CO being carried out to one of optimum way of apart evolution is absorption method, namely by consolidating ion-exchange, carrier (as inorganic molecule sieve etc.) and stannous chloride are mixed, be placed in inert gas high-temperature calcination, prepare support type Cu (I) adsorbent, by Cu (I) and CO, σ-π complexing occurs, CO is separated from waste gas.
In recent years, a class is referred to as the MOFs material of metallic organic framework just in fast development, and it has very high specific area and homogeneous pore structure, has very large application prospect in gas absorption separation.But, because its hydrothermal stability of the organic ligand in MOFs carrier is not high, although MOFs has superhigh specific surface area, it has good facilitation to CuCl dispersion, more restriction is received as excellent carrier, application high-temperature calcination very easily destroys the basic structure of MOFs, needs to calcine under the high temperature conditions, can not prepare Cu (I) load type adsorbing agent if ion-exchange is consolidated in application.Therefore, utilize CuCl support type MIL-100 materials adsorption CO not yet to have report, need a kind of new method preparing modified metal organic framework material CO to high-adsorption-capacity badly.
Summary of the invention
The object of the invention is to for deficiency of the prior art, there is provided a kind of under normal temperature and pressure conditions, with MIL-100 (Fe) for carrier, utilize infusion process load copper chloride and copper formate, prepare the method for modified metal organic framework material CuCl@MIL-100 (Fe), the CuCl@MIL-100 (Fe) prepared has high-adsorption-capacity to CO.
Meanwhile, the invention still further relates to a kind of CuCl@MIL-100 (Fe) material.
* except as otherwise noted, the percentage described in the present invention is mass percent.
Object of the present invention is achieved by the following technical programs.
CO is had to a preparation method of the CuCl@MIL-100 (Fe) of high-adsorption-capacity, it is characterized in that: comprise the following steps:
(1) precursor power: the ratio being 1 ~ 14.7:1.14:1 according to mass ratio by carrier MIL-100 (Fe) crystal, copper chloride solution, copper formate solution fully mixes, and obtains precursor liquid, for subsequent use;
(2) moisture evaporation: precursor liquid is placed in the distilling flask of Rotary Evaporators, under the constant temperature of 45 DEG C ~ 90 DEG C, moisture is evaporated, obtain moisture free precursor liquid;
(3) vacuum activating: moisture free precursor liquid being placed in temperature is priming reaction 3 ~ 48h under the vacuum environment of 120 DEG C ~ 270 DEG C, more namely obtains CuCl@MIL-100 (Fe) material after cooling the temperature to room temperature.
Wherein, in described CuCl@MIL-100 (Fe) material, CuCl content presses carrier calculation is 5wt% ~ 150wt%.
A kind of CuCl@MIL-100 (Fe) material, is made by above-mentioned preparation method.
Compared with prior art, the present invention has following beneficial effect:
The present invention can under normal temperature and pressure conditions, with MIL-100 (Fe) for carrier, prepare CuCl@MIL-100 (Fe), Cu is wherein on MIL-100 (Fe) surface with valence state Cu (I) load of monovalence, improve the adsorption capacity of CO and selective significantly, the highest amplification can reach 7 times, no matter the material that these features make the present invention prepare is in the pollution eliminating CO in environment, or reclaiming CO as chemical industry important source material from various industrial waste gas, all have a good application prospect.
Accompanying drawing explanation
Fig. 1 is that CuCl@MIL-100 (Fe) prepared by embodiment 1 ~ 3 characterizes comparison diagram with the XRD of original MIL-100 (Fe).
Fig. 2 is CuCl@MIL-100 (Fe) material CO adsorption isotherm Comparative result figure at normal temperatures prepared by embodiment 1-4.
Detailed description of the invention
Be illustrated the present invention below in conjunction with drawings and the specific embodiments, it should be noted that specific embodiment is limited the present invention never in any form, according to the teachings of the present invention done any change or replacement, all belong to protection scope of the present invention.
Embodiment 1
0.15g MIL-100 (Fe) crystal is added 5mL 0.015mol/L copper formate solution and 5mL0.015mol/L copper chloride solution, now MIL-100 (Fe): copper formate: the mass ratio of copper chloride is at 14.7:1.14:1, mix, 80 DEG C revolve and to anhydrate point on a rotary evaporator, put into vacuum drying chamber 200 DEG C reaction 24h, after being cooled to room temperature, obtain CuCl@MIL-100 (Fe) material that CuCl mass fraction (calculating by carrier) is 10wt%.The material marking obtained is CuCl MIL-100 (Fe) #1.
Embodiment 2
0.3g MIL-100 (Fe) crystal is added 10mL 0.06mol/L copper formate solution and 10mL0.06mol/L copper chloride solution, now MIL-100 (Fe): copper formate: the mass ratio of copper chloride is at 3.7:1.14:1, mix, 45 DEG C revolve and to anhydrate point on a rotary evaporator, put into vacuum drying chamber 120 DEG C reaction 48h, after being cooled to room temperature, obtain CuCl@MIL-100 (Fe) material that CuCl mass fraction (calculating by carrier) is 40wt%.The material marking obtained is CuCl MIL-100 (Fe) #2.
Embodiment 3
0.6g MIL-100 (Fe) crystal is added 20mL 0.12mol/L copper formate solution and 20mL0.12mol/L copper chloride solution, now MIL-100 (Fe): copper formate: the mass ratio of copper chloride is at 1.85:1.14:1, mix, 90 DEG C revolve and to anhydrate point on a rotary evaporator, put into vacuum drying chamber 150 DEG C reaction 12h, after being cooled to room temperature, obtain CuCl@MIL-100 (Fe) material that CuCl mass fraction (calculating by carrier) is 80wt%.The material marking obtained is CuCl MIL-100 (Fe) #3.
Embodiment 4
0.3g MIL-100 (Fe) crystal is added 10mL0.24mol/L copper formate solution and 10mL0.24mol/L copper chloride solution, now MIL-100 (Fe): copper formate: the mass ratio of copper chloride is at 1:1.14:1,60 DEG C revolve and to anhydrate point on a rotary evaporator, 270 DEG C of reaction 3h, obtaining mass fraction (calculating by carrier) after being cooled to room temperature is 150wt%CuCl@MIL-100 (Fe) material.The material marking obtained is CuCl MIL-100 (Fe) #4.
Test example
In order to contrast original MIL-100 (Fe) to the difference of CO absorption property, adopting carrier MIL-100 (Fe) as contrast, being designated as: original MIL-100 (Fe).
MIL-100 (Fe) material obtained by embodiment 1 ~ 4, its CO absorption property and characterization result are described below:
(1) XRD characterizes
Fig. 1 respectively illustrates the XRD figure of original MIL-100 (Fe) and CuCl@MIL100 (Fe) #1-3 obtained by the present invention.As we can see from the figure, the peak type of original MIL-100 (Fe) is very sharp-pointed, shows that the crystal formation of synthetic material is better.And the main peak in MIL-100 (Fe) XRD spectra before and after load still exists, show that the present invention's carrying method used does not destroy the prototype structure of MIL-100 (Fe).
(2) pore structure phenetic analysis
Application ASAP2020 specific area and distribution of pores tester test the pore structure of original material and CuCl@MIL-100 (Fe) #3 material, test result is as shown in table 1, after showing load, specific area decreases, but still has larger porosity.
The parameter of pore structure of material before and after table 1. CuCl
(3) CuCl@MIL-100 (Fe) is to the adsorption capacity of CO
Application ASAP2020 carries out the Static Adsorptive capacity test of the CO when 298K, 1bar to obtained CuCl@MIL-100 (Fe) and original MIL-100 (Fe), the results are shown in Figure 2 and table 2.As shown in Table 2, four kinds of CuCl@MIL-100 (Fe) obtained by the present invention to the adsorbance of CO far above original MIL-100 (Fe), wherein the adsorption capacity of CuCl@MIL-100 (Fe) #3 can reach 2.7mmol/g, is 7 times (0.38mmol/g) of original material.This result shows: the method that the present invention takes successfully goes up the absorption property of load CuCl, CuCl@MIL-100 (Fe) far above original MIL-100 (Fe) material at MIL-100 (Fe).
To the absorption property (25 DEG C) of CO before and after table 2. CuCl
Conclusion:
Application the inventive method can obtain serial CuCl@MIL-100 (Fe) material, this composite can keep the crystalline structure of good similar MIL-100 (Fe), shows that the present invention's carrying method used does not destroy the crystal structure of MIL-100 (Fe).The more important thing is, compared with original MIL-100 (Fe), prepared serial CuCl@MIL-100 (Fe) composite, although its specific area reduces, it significantly improves the absorption property of CO, and the highest amplification can reach 7 times.Cu (I)@MIL-100 (Fe) material that these features make the present invention prepare no matter in the pollution eliminating CO in environment, or reclaiming CO as chemical industry important source material from various industrial waste gas, all has a good application prospect.

Claims (3)

1. CO is had to a preparation method of the CuCl MIL-100 (Fe) of high-adsorption-capacity, it is characterized in that: comprise the following steps:
(1) precursor power: the ratio being 1 ~ 14.7:1.14:1 according to mass ratio by carrier MIL-100 (Fe) crystal, copper chloride solution, copper formate solution fully mixes, and obtains precursor liquid, for subsequent use;
(2) moisture evaporation: precursor liquid is placed in the distilling flask of Rotary Evaporators, under the constant temperature of 45 DEG C ~ 90 DEG C, moisture is evaporated, obtain moisture free precursor liquid;
(3) vacuum activating: moisture free precursor liquid being placed in temperature is priming reaction 3 ~ 48h under the vacuum environment of 120 DEG C ~ 270 DEG C, more namely obtains CuCl@MIL-100 (Fe) material after cooling the temperature to room temperature.
2. preparation method CO to the CuCl@MIL-100 (Fe) of high-adsorption-capacity according to claim 1, is characterized in that: in CuCl@MIL-100 (Fe) material described in step (3), CuCl content is calculated as 5wt% ~ 150wt% by carrier.
3. CuCl MIL-100 (Fe) material, is characterized in that: made by the preparation method of the CuCl MIL-100 (Fe) CO described in claim 1 or 2 to high-adsorption-capacity.
CN201410834381.3A 2014-12-29 2014-12-29 CuCl supported MIL-100(Fe) with high CO adsorption capacity and preparation method thereof Pending CN104525127A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105854944A (en) * 2016-03-31 2016-08-17 华南理工大学 Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same
CN110652960A (en) * 2018-06-28 2020-01-07 中国科学院大连化学物理研究所 Carbon monoxide adsorbent and preparation method and application thereof
CN111345497A (en) * 2020-04-16 2020-06-30 江苏大亚滤嘴材料有限公司 Cuprous ion-based MOFs-gel composite material with CO specific adsorption capacity and application thereof to cigarette filter stick

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CN104190364A (en) * 2014-08-25 2014-12-10 云南中烟工业有限责任公司 Low-toxicity preparation method of MIL-100(Fe) crystal with high capacity of adsorbing CO

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US20140212944A1 (en) * 2013-11-29 2014-07-31 Beijing Star New Material Co., Ltd. MOF-based hierarchical porous materials, methods for preparation, methods for pore regulation and uses thereof
CN104190364A (en) * 2014-08-25 2014-12-10 云南中烟工业有限责任公司 Low-toxicity preparation method of MIL-100(Fe) crystal with high capacity of adsorbing CO

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105854944A (en) * 2016-03-31 2016-08-17 华南理工大学 Copper doped ferrous metal organic framework material as well as preparation method and method for activating persulfate to treat organic wastewater by using same
CN105854944B (en) * 2016-03-31 2018-06-22 华南理工大学 A kind of Copper-cladding Aluminum Bar ferrous metal organic framework material and preparation method and application is in the method for organic wastewater treatment through persulfate activation
CN110652960A (en) * 2018-06-28 2020-01-07 中国科学院大连化学物理研究所 Carbon monoxide adsorbent and preparation method and application thereof
CN111345497A (en) * 2020-04-16 2020-06-30 江苏大亚滤嘴材料有限公司 Cuprous ion-based MOFs-gel composite material with CO specific adsorption capacity and application thereof to cigarette filter stick

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