CN106673992A - Bimetal organic framework material as well as preparation and application thereof - Google Patents
Bimetal organic framework material as well as preparation and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/105—Removal of contaminants of nitrogen
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- 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
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- B01D2253/204—Metal organic frameworks (MOF's)
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Abstract
The invention relates to a bimetal organic framework material adsorbent applied to methane/nitrogen separation and a preparation method thereof. The bimetal organic framework material adsorbent is a compound with super-molecular porous network structure, wherein the compound is formed by coordinating two metal ions with an organic ligand HCOOH under the action of an adjusting agent; at least one of the two metal ions is Ni(II); the coordination conditions of different metals are controlled by adjusting complexation of Ni(II) to obtain several bimetal organic framework materials with different metal ratios. The prepared adsorbent has rich micro-porous structures; the purpose of adjusting pore properties microscopically is achieved; the NH4/N2 separation effect is excellent; the material is simple to prepare and low in cost, and is extremely applicable to development and recycling of low-quality methane separated under low pressure.
Description
Technical field
The invention belongs to technical field of chemical engineering adsorbent, and in particular to one kind is detached for methane-nitrogen adsorption
Bimetallic sorbent and preparation method thereof.
Background technology
Energy shortage and environmental pollution are the two large focal spot problems that China currently faces.Methane (CH4) it is current
Internationally recognized low-carbon (LC) clear energy sources, its exploitation and clean utilization become solution China energy availability and demand contradiction,
Realize energy variation, keep one of Major Strategic of economic environment sustainable development.According to China's energy rule
Draw, intend bringing up to 12% to ratio of the year two thousand twenty natural gas in primary energy consumption, equivalent to annual consumption
For 4000 billion cubic meters, natural gas resource breach is up to 1500 billion cubic meters, and imbalance between supply and demand is becoming increasingly acute.
Except the Persisting exploitation of conventional gas, the exploitation of the huge Unconventional gas of total resources will be using will have
Power is supplemented.But in such low-concentration methane gas purification process, because of N2Molecule and CH4Physicochemical properties
Closely become a key common technology difficult problem for unconventional methane gas purification/recovery process, be current China
One of maximum technology barrier that natural gas development is faced with energy-saving and emission-reduction strategy.
At present the separation method of report mainly has Deep Cooling Method, membrance separation, hydrate, liquid phase scrubbing and absorption
Partition method, wherein pressure-variable adsorption (Pressure Swing Adsorption, PSA) technology because process is simple, small investment,
Product gas concentration is high and cause separating-purifying CH4Become more economical and effective.Separated using PSA technology
CH4/N2The performance that it is critical only that adsorbent, there is presently no can really meet CH4/N2Efficient absorption point
From can industrial applications adsorbent, thus the research and development of new adsorbent receive much concern always.
Say from microcosmic angle mechanism, design prepares CH4-N2The key of high-efficiency adsorbent is exactly to increase as far as possible
CH4With N2Both active force differences and adsorbing material between.Activated carbon, CMS, modified clinoptilolite,
Sr-ETS-4 is in CH4-N2Separation process in present the performance of respective uniqueness, but CH is not implemented4
With N2High efficiency separation, main reason is that：(1) pore distribution and surface functional group of active carbon-supported catalyst
It is complicated and changeable and uncontrollable；(2) surface enhanced of Si-Al molecular sieve class material high degree of polarization CH4It is preferential
Adsorptivity, with its kinetics prioritizing selection N2Characteristic it is inconsistent；(3) conflicting CH4、N2Four dipoles
Square and polarizability difference, cause metal ion (Li+、Na+、K+、Mg2+Or Ca2+) exchange and Si/Al ratio
The orientation adjustment of modulation screening type adsorbent surface potential field difficult to realize；(4) speed type CMS and screening type
Sr-ETS-4 adsorbents duct it is too little (Left and right), cause adsorbent easy in inactivation or efficiency to decline to a great extent.It is aobvious
So, it is reinforcing CH to control duct electric field intensity inside high and separator window size4-N2The key of separation efficiency.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) have pore structure in order, ratio
Surface area is big, hole shape and the features such as adjustable size.With conventional porous materials compared with zeolite, activated carbon, most
Significant advantage can construct the suction of endless different pore properties by the different part of selection and metal ion
Attached dose.MOFs materials are expected to become further improve CH4-N2One of optimal material of adsorption separation efficiency,
And the regulating microstructure research for adsorbing material provides an exercisable platform.Various MOFs materials
Such as ZIF-68, ZIF-69, MOF-74, HKUST-1, MIL-47 (V), Al-BDC,3∞ [Cu (Me-4py-trz-ia)], MOF-5 and MOF-177 are used for CH4/N2Adsorbing separation (J.Mater.
Chem.2012,22:10274；J.Phys.Chem.C.2010,114:8515；J.Am.Chem.Soc.2014,
136:698；Langmuir.2009,25:5918).Due to the exposure of micro-porous adsorption gesture, ligand functional groups or metal
The effect of position, these materials show good CH4/N2Separating property.Appoint recently and wait (Micropor.
Mesopor.Mater.2014,186:137) CH is prepared for using HCOOH and Ni4/N2Separation factor is high
Up to 6.5 adsorbent, good prospects for commercial application is presented.But these adsorbents are mainly organic by adjusting
Part seldom investigates the tune of different metal ions and many kinds of metal ions to duct changing the property of structure
Section is acted on.It is simultaneously expensive, be not suitable for commercial Application.
The content of the invention
The purpose of the present invention is to purify the problem existed with purification for current methane, there is provided a class methane/nitrogen
Separating adsorbent, to realize efficiently separating for methane and nitrogen.
It is of the present invention for the detached nano-pore metal-organic framework materials of methane/nitrogen adsorption, be a kind of
Acted on by ligand complex in a solvent by bimetallic ion and organic ligand and be self-assembly of with oversubscription
The compound of sub- porous network structure.This framework material contains two metal ion species, and one of which is Ni (II)；
Wherein, described metal ion is derived from Mg (NO3)2·6H2O、Cr(NO3)2·9H2O、
Mn(NO3)2·4H2O、FeSO4·7H2O、Fe(NO3)3·9H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、
Cu(NO3)2·3H2O、Zn(NO3)2·6H2O、Cd(NO3)2·4H2O、Mg(Ac)2·4H2O、Mn(Ac)2·4H2O、
Ni(Ac)2·4H2O、Co(Ac)2·4H2O、Zn(Ac)2·2H2O、Cu(Ac)2·H2O、Cd(Ac)2·2H2O、
Fe(ClO4)3·9H2O。
Described organic ligand from formic acid, methyl formate, Ethyl formate, sodium formate, the one of potassium formate
Plant or its mixture, the present invention is preferred to recommend organic ligand formic acid, formic acid of the special recommendation more than 88%.
Nano-pore metal-organic framework materials of the present invention, its duct is that one-dimensional Z-shaped is received on b directions
Metre hole road, hole size between 0.43-0.72nm, Langmuir methods N2Specific surface area is between 50-500m2/g。
The invention provides the preparation method of the nano-pore metal-organic framework materials, it is characterised in that include
Following steps：A () is by the slaine of nickel, regulator and organic ligand HCOOH according to certain ratio point
In not being dissolved in two parts of mixed solvents, after stirring a period of time, mix and obtain homogeneous mixture.
Regulator Main Function is to carry out complexation with nickel ion in the step (a), so regulator can
To be carbonyl class, amine, pyridines, ammonia and cyanide compound, wherein it is preferred that aminated compoundss, special
Tui Jian not tripolycyanamide and ethylenediamine.
Different mixings time can affect its complexation degree, so control mixing time is a key factor,
Preferred mixing time is greater than 30min,.
In the step (a) mixed solvent for methanol, ethanol, ethylene glycol one or more with DMF's
The volume ratio of mixed liquor, alcohols and DMF is 1：0 to 0：In the range of 1 (0 represents do not have).Preferred ratio
Example is 1:5～1:20, particularly preferably 1:5～1:10.
Regulator and the mol ratio of nickel metal precursor are 2 in the step (a):1～1:10, regulator trimerization
The mol ratio of cyanamide, triethylene diamine, ethylenediamine and nickel metal precursor is 1:1～1:3, ammonia, Cyanogran.
It is 1 with the mol ratio of nickel metal precursor:4～1:6.
B () adds another slaine after mixed liquor in step (a) is stirred into one section, mixed solution is placed in
A few hours are reacted in high-pressure reactor under preset temperature.
Metal ion in the step (b) in another slaine is selected from Mg2+、Mn2+、Fe3+、Co2+、
Cu2+、Zn2+ or Cd2+。
Mol ratio in the step (b) between nickel metal precursor and another kind of slaine is 20:1 to 1:20
In the range of.Preferred scope is 8:1 to 1:2.Preferred scope is 5:1 to 1:1.
Described nickel ion is 6 with the mol ratio of manganese ion or iron ion:1-4:1, particularly preferably than being 5:1；Nickel
Ion is 5 with the mol ratio of copper ion:1-2:1；Nickel ion is 4 with the mol ratio of magnesium ion or zinc ion:1-2:1,
Particularly preferably than being 3:1；Nickel ion is 1.5 with the mol ratio of cobalt ion, cadmium ion:1-1:1.5, particularly preferably
Than for 1:1.
Preset temperature range is 10 DEG C～200 DEG C in the step (b).Preferred scope is 80 DEG C～150 DEG C.
It is more than or equal to 1h that mixed solution needs at least reaction a few hours in the step (b).It is preferred anti-
6h is greater than or equal between seasonable.The preferred response time is greater than or equal to 24h.
Adsorbent is obtained Jing after centrifugation, washing, dry, activation and molding, in 0.4MPa, 298K conditions
Under, 20sccm mol ratios are 1:1 CH4/N2Gaseous mixture carries out dynamic adsorption test.
Nano-pore bimetallic organic framework sorbent prepared by the present invention, using different metal ions as coordination
Center, under modulator effect, can simply adjust the content and proportioning of metal in organic backbone, make suction
Attached agent material changes pore size and inner surface electric potential field on microcosmic, realizes the controllable adjustment of pore properties,
So as to improve adsorbent to CH4/N2Adsorption separation performance.
There is nano-pore bimetallic organic framework material prepared by the present invention micropore for enriching and suitable aperture to exist
Application in mixed gas separation, can efficiently separate CH4/N2, be conducive to China to increase opening for natural gas
Send out and utilize, especially scale, the industrialization of Unconventional gas is to meet China's clean energy resource demand,
Solve environmental problem and provide technical guarantee.
Specific embodiment
The principle and feature of the present invention are described below in conjunction with specific embodiment, example below is served only for
The present invention is further described, but it is not thereby limiting the invention.
Embodiment 1：Solvent-thermal process Ni0.65Mg0.35(HCOO)2
(1) 4.362g Ni (NO are weighed3)2·6H2O and 1.261g tripolycyanamide is dissolved in 30ml DMF and 6ml
In the mixed solvent of methanol, stirring 50min forms solution A；3.1ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 20min and obtains mixed solution C；
(2) by 1.282g Mg (NO3)2·6H2O is dividedly in some parts in mixed solution C, stirs 1h, then will
Mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in 100 DEG C of bakings
Case reacts 36h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 3.273g shallow green powders.
The N measured by the Autosorb IQ-2 of Kang Ta instrument companies of the U.S.2Specific surface area is 298.04m2/g
(determination of Langmuir methods), CH4/N2Separation factor be 5.1.
Embodiment 2：Solvent-thermal process Ni0.8Mn0.2(HCOO)2
(1) 5.816g Ni (NO are weighed3)2·6H2O and 1.513g tripolycyanamide is dissolved in 30ml DMF and 6ml
In the mixed solvent of methanol, stirring 40min forms solution A；5.6ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 20min and obtains mixed solution C；
(2) by 1.000g Mn (NO3)2·4H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
120 DEG C of baking ovens react 36h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 4.132g shallow green powders.
The N that Autosorb IQ-2 are measured2Specific surface area is 313.53m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.0.
Embodiment 3：Solvent-thermal process Ni0.7Fe0.2(HCOO)2
(1) 5.816g Ni (NO are weighed3)2·6H2O and 0.784g Cyanogran .s are dissolved in 40ml DMF and 12ml
In the mixed solvent of methanol, stirring 50min forms solution A；3.8ml HCOOH are dissolved in 20ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 20min and obtains mixed solution C；
(2) by 1.616g Fe (NO3)3·9H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
100 DEG C of baking ovens react 48h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain the brick-red powder of 4.016g.
The N that Autosorb IQ-2 are measured2Specific surface area is 265.14m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.0.
Embodiment 4：Solvent-thermal process Ni0.5Co0.5(HCOO)2
(1) 2.908g Ni (NO are weighed3)2·6H2O and 1.513g tripolycyanamide is dissolved in 30ml DMF and 3ml
In the mixed solvent of methanol, stirring 50min forms solution A；4.7ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 30min and obtains mixed solution C；
(2) by 2.911g Co (NO3)2·6H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
120 DEG C of baking ovens react 48h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 3.612g aubergine powder.
The N that Autosorb IQ-2 are measured2Specific surface area is 230.22m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.8.
Embodiment 5：Solvent-thermal process Ni0.63Cu0.37(HCOO)2
(1) 4.071g Ni (NO are weighed3)2·6H2O and 0.84ml ethylenediamines are dissolved in 40ml DMF and 12ml
In the mixed solvent of methanol, stirring 30min forms solution A；4.8ml HCOOH are dissolved in 20ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 30min and obtains mixed solution C；
(2) by 1.691g Cu (NO3)2·3H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
100 DEG C of baking ovens react 48h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain the light green powder of 3.061g.
The N that Autosorb IQ-2 are measured2Specific surface area is 231.21m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 6.4.
Embodiment 6：Solvent-thermal process Ni0.8Cu0.2(HCOO)2
(1) 4.362g Ni (NO are weighed3)2·6H2O and 0.45ml ethylenediamines are dissolved in 40ml DMF and 15ml
In the mixed solvent of methanol, stirring 1h forms solution A；2.8ml HCOOH are dissolved in 20ml DMF, are stirred
Mix to form solution B, solution B is added in solution A, continue stirring 30min and obtain mixed solution C；
(2) by 0.725g Cu (NO3)2·3H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
100 DEG C of baking ovens react 48h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain the light green powder of 3.175g.
The N that Autosorb IQ-2 are measured2Specific surface area is 289.03m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 6.1.
Embodiment 7：Solvent-thermal process Ni0.53Zn0.47(HCOO)2
(1) 5.234g Ni (NO are weighed3)2·6H2O and 0.757g tripolycyanamide is dissolved in 30ml DMF and 6ml
In the mixed solvent of methanol, stirring 30min forms solution A；2.8ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 30min and obtains mixed solution C；
(2) by 1.785g Zn (NO3)2·6H2O is slowly added in mixed solution C, continues to stir 40min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
120 DEG C of baking ovens react 24h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 4.252g shallow green powders.
The N that Autosorb IQ-2 are measured2Specific surface area is 255.64m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.5.
Embodiment 8：Solvent-thermal process Ni0.65Zn0.35(HCOO)2
(1) 4.362g Ni (NO are weighed3)2·6H2O and 1.261g tripolycyanamide is dissolved in 30ml DMF and 6ml
In the mixed solvent of methanol, stirring 50min forms solution A；3.1ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 30min and obtains mixed solution C；
(2) by 1.487g Zn (NO3)2·6H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
120 DEG C of baking ovens react 36h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 3.851g shallow green powders.
The N that Autosorb IQ-2 are measured2Specific surface area is 223.54m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.0.
Embodiment 9：Solvent-thermal process Ni0.45Cd0.55(HCOO)2
(1) 3.199g Ni (NO are weighed3)2·6H2O and 1.261g tripolycyanamide is dissolved in 50ml DMF and 5ml
In the mixed solvent of methanol, stirring 40min forms solution A；4.3ml HCOOH are dissolved in 30ml DMF,
Stirring forms solution B, and solution B is added in solution A, continues stirring 30min and obtains mixed solution C；
(2) by 3.393g Cd (NO3)2·4H2O is slowly added in mixed solution C, continues to stir 30min,
Then mixed solution is transferred to sealing tight in teflon-lined 120ml autoclaves, is placed in
100 DEG C of baking ovens react 24h, Temperature fall.
(3) it is centrifuged, after washing solid with methanol (2 × 25ml), pressed powder is dried into 10h at 100 DEG C,
Obtain 3.351g shallow green powders.
The N that Autosorb IQ-2 are measured2Specific surface area is 215.82m2/ g (determination of Langmuir methods),
CH4/N2Separation factor be 5.3.
Claims (10)
1. bimetallic organic framework material, it is characterised in that：Described metal-organic framework materials are by double gold
Category ion and organic ligand acted on by ligand complex and be self-assembly of with supermolecule porous network structure
Compound；This framework material contains two metal ion species, and one of which is Ni (II)；Another metal ion species
Selected from Mg2+、Mn2+、Fe3+、Co2+、Cu2+、Zn2+Or Cd2+；Ni rubs with another metal ion species
That ratio is between 8:1 to 1:Between 2.
2. bimetallic organic framework material according to claim 1, it is characterised in that：Organic ligand is
HCOOH。
3. bimetallic organic framework material according to claim 1, it is characterised in that：Described metal
The duct of organic framework materials is one-dimensional Z-shaped nano pore on b directions, and hole size is between 0.43-0.72nm
Between, Langmuir methods N2Specific surface area is between 50-500m2/g。
4. the preparation method of the bimetallic organic framework material described in a kind of claim 1,2 or 3, it is special
Levy and be, it comprises the steps：
(1) nickel metal precursor and regulator are added in solvent, solution A, organic ligand is formed after stirring
HCOOH is added in another part solvent and forms solution B, solution B is added drop-wise in solution A and is formed
Mixed liquor；
(2) during the salt of another metal ion to be added the mixed solution of step (1), by solvent thermal reaction
Precipitum is obtained, Jing after filtering, wash, is dried；
Described nickel metal precursor is nickel nitrate, nickel sulfate, Nickel dichloride., nickelous bromide, nickelous carbonate and acetic acid
One or two or more kinds in nickel；
Described regulator is the one kind in tripolycyanamide, triethylene diamine, ethylenediamine, ammonia, Cyanogran.
Or more than two kinds；
Described reaction dissolvent is one or two or more kinds mixing with DMF in methanol, ethanol, ethylene glycol
Thing；The volume ratio of described solvent methanol, ethanol or ethylene glycol and DMF is 1:5～1:10；
The salt of another described metal ion is the one kind or two in nitrate, perchlorate or acetate
More than kind, its metal ion is selected from Mg2+、Mn2+、Fe3+、Co2+、Cu2+、Zn2+ or Cd2+。
5. the preparation method of bimetallic organic framework material according to claim 4, it is characterised in that：
The mol ratio of described regulator tripolycyanamide, triethylene diamine or ethylenediamine and nickel metal precursor is
1:1～1:3, ammonia or Cyanogran. and the mol ratio of nickel metal precursor are 1:4～1:6.
6. the preparation method of bimetallic organic framework material according to claim 4, it is characterised in that：
Time for adding solution B being added drop-wise in solution A is more than or equal to 30min.
7. the preparation method of bimetallic organic framework material according to claim 4, it is characterised in that：
Described nickel ion is 6 with the mol ratio of manganese ion or iron ion:1-4:1, the mol ratio of nickel ion and copper ion
For 5:1-2:1, nickel ion is 4 with the mol ratio of magnesium ion or zinc ion:1-2:1, nickel ion and cobalt ion, cadmium
The mol ratio of ion is 1.5:1-1:1.5.
8. the preparation method of bimetallic organic framework material according to claim 4, it is characterised in that：
Described solvent heat condition is reaction 12-48 hours at 80～140 DEG C.
9. the application of the bimetallic organic framework material described in a kind of claim 1,2 or 3, its feature exists
In：Described bimetallic organic framework material is used to be selectively adsorbing and separating the separation of methane in methane mixed gas.
10. application according to claim 9, it is characterised in that：Gaseous mixture is that methane and nitrogen mix
Gas, equilibrium adsorption separation factor is more than or equal to 5, has excellent selectivity to methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510771689.2A CN106673992A (en) | 2015-11-11 | 2015-11-11 | Bimetal organic framework material as well as preparation and application thereof |
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|---|---|---|---|
| CN201510771689.2A CN106673992A (en) | 2015-11-11 | 2015-11-11 | Bimetal organic framework material as well as preparation and application thereof |
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| CN108285538A (en) * | 2018-04-17 | 2018-07-17 | 武汉大学 | It is a kind of have fixed coordination configuration and can accuracy controlling coordination bond lengths molecule tong-like metal-organic framework material preparation method |
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| CN108285538B (en) * | 2018-04-17 | 2020-04-24 | 武汉大学 | Preparation method of molecular pincer-like metal organic framework material with fixed coordination configuration and capable of accurately regulating and controlling length of coordination bond |
| WO2020037310A1 (en) * | 2018-08-17 | 2020-02-20 | Trustees Of Dartmouth College | Conductive bimetallic metal-organic frameworks for the detection of analytes |
| CN109225339B (en) * | 2018-09-28 | 2021-05-25 | 合肥工业大学 | Hierarchical assembly method and application of high-activity synergistic MOF catalyst |
| CN109225339A (en) * | 2018-09-28 | 2019-01-18 | 合肥工业大学 | A kind of high activity cooperates with classification assemble method and the application of MOF catalyst |
| CN111187417A (en) * | 2018-11-15 | 2020-05-22 | 中国科学院大连化学物理研究所 | Modification method and application of metal organic framework material |
| CN109400906A (en) * | 2018-12-12 | 2019-03-01 | 太原理工大学 | The method of more metal MOFs materials is directly prepared using bimetal complex |
| CN109400906B (en) * | 2018-12-12 | 2021-04-30 | 太原理工大学 | Method for directly preparing multi-metal MOFs material by utilizing bimetallic complex |
| CN110787840A (en) * | 2019-11-06 | 2020-02-14 | 中国科学院过程工程研究所 | Bimetallic MOFs catalyst and preparation method and application thereof |
| WO2021088196A1 (en) * | 2019-11-06 | 2021-05-14 | 中国科学院过程工程研究所 | Dual metal mofs catalyst, and preparation method therefor and use thereof |
| CN110787840B (en) * | 2019-11-06 | 2022-10-14 | 中国科学院过程工程研究所 | Bimetallic MOFs catalyst and preparation method and application thereof |
| CN111378148A (en) * | 2020-03-24 | 2020-07-07 | 安徽中烟工业有限责任公司 | Preparation method of binary metal MOFs material and application of binary metal MOFs material in reducing harm of cigarette smoke |
| CN116063688A (en) * | 2021-11-01 | 2023-05-05 | 广东美的白色家电技术创新中心有限公司 | Flexible metal-organic framework material and preparation method thereof |
| CN114479106A (en) * | 2022-01-25 | 2022-05-13 | 桂林理工大学 | Metal organic framework material with ammonia response and antibacterial functions and preparation method thereof |
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