CN109772379A - A kind of nano level metal fluoride catalysts of confinement formula structure and its preparation method and application - Google Patents
A kind of nano level metal fluoride catalysts of confinement formula structure and its preparation method and application Download PDFInfo
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Abstract
The invention discloses nano level metal fluoride catalysts of a kind of confinement formula structure and its preparation method and application.The preparation process of the catalyst are as follows: exist under effect in mineralizer, metal salt and organic ligand carry out crystallization in a solvent and MOF material are made, MOF material be placed under inert atmosphere carry out calcining carbonization treatment obtain carbon doping metals composite material, carbon doping metals composite material is placed in progress Calcination for removing carbon under oxidizing atmosphere and handles to obtain the nano-scale carbon doping metals composite material of confinement formula structure, the composite material, which is placed under fluorination atmosphere, carries out gas phase fluorination processing to get the nano level metal fluoride catalysts for arriving the confinement formula structure.Metal active constituent therefore has the characteristics that strong anti-sintering, strong anti-carbon with the dispersion of atomic level in carbon based material in catalyst of the invention, shows good catalytic activity in fluorine chemical field with its unique design feature.
Description
Technical field
The invention belongs to a kind of preparation method of carbon-based material doping metals, in particular to a kind of nanometer of confinement formula structure
Grade metal fluoride catalysts and its preparation method and application.
Background technique
Metal-organic framework materials (abbreviation MOFs) be it is a kind of by metal ion and organic ligand by complexing from group
The novel class zeolite porous material with periodic network structure formed is filled, because it has incomparable huge specific surface area, multiplicity
Skeleton structure, aperture is adjustable and the uniform dispersion of metal ion height in the frame, become and a kind of prepare carbon, metal oxygen
The presoma of the various multi-functional hybrid materials such as compound, metal sulfide, metal phosphide, metal carbides, thus by people
Extensive concern.
Chromium, magnesium, aluminium fluoride be a kind of common solid-acid material, in fluorine chemical field since its is good corrosion-resistant
Property, it can be used as catalyst or carrier be applied to the exchange of fluorine chlorine, dehydrochlorination, de- a variety of reactions such as (adding) hydrogen and isomerization reaction
System.Currently, but lead to catalyst inactivation due to being easy to produce carbon distribution and sintering in catalysis reaction, influence catalyst life.
The nano particle of small size can inhibit carbon distribution but easy-sintering, therefore be badly in need of developing a kind of nano level metal of confinement formula structure
Fluoride catalysts can not only inhibit carbon distribution but also can prevent sintering cause grain size grow up and caused by deactivation prob.
Currently, carbon dope metallic composite is not common, and the nano level metal fluoride for preparing confinement formula structure is even more
It has not been reported.Wang Hong et al. [CN201711370331.4] is by the way that poly ion liquid to be immersed in inorganic salts, using high temperature
The composite material of metal carbon dope is obtained after carbonization, and it is characterized.Wang Jingyu et al. [CN201810060676.8] is logical
It crosses after the graphite phase carbon nitride of carbon auto-dope is dispersed in water, then after the alcoholic solution of titanium salt is added dropwise, then high temperature cabonization obtains
To the graphite phase carbon nitride titanic oxide nano compound material of carbon auto-dope.
It can be seen that usually metal fluoride carbon dope material is all that metal precursor is supported on carbon substrate by infusion process
After on material, further carbonization treatment is obtained.
Summary of the invention
For above-mentioned technical problem of the existing technology, the purpose of the present invention is to provide a kind of receiving for confinement formula structure
Meter level metal fluoride catalysts and its preparation method and application.
A kind of preparation method of the nano level metal fluoride catalysts of the confinement formula structure, it is characterised in that including
Following steps:
1) in the case where mineralizer has effect, metal salt and organic ligand carry out crystallization in a solvent, and MOF material is made
Material, the metal salt are at least one of Cr salt, Mg salt, Al salt；
2) MOF material obtained by step 1) being placed under inert atmosphere, calcining at constant temperature handles 3-5h at 300~450 DEG C,
Organic matter in MOF material gradually decomposes carbonization, is then naturally cooling to room temperature, obtains carbon doping metals composite material；
3) carbon doping metals composite material obtained by step 2) is placed under oxidizing atmosphere, constant temperature is forged at 300~500 DEG C
It burns 1~10h and carries out carbon removal treatment, extra part carbon is removed in carbon doping metals composite material, keeps part metals component sudden and violent
Expose, be then naturally cooling to room temperature, obtains the nano-scale carbon doping metals composite material of confinement formula structure；
4) nano-scale carbon doping metals composite material obtained by step 3) is placed under fluorination atmosphere, it is permanent at 200~300 DEG C
2~5h of temperature calcining carries out gas phase fluorination processing, is naturally cooling to room temperature then to get the nanometer grade gold of the confinement formula structure is arrived
Belong to fluoride catalysts.
A kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that step
1) in, MOF material obtained is at least one of MIL-101, MIL-32, MIL-34, MIL-53, MIL-74；The crystallization
The temperature of reaction is 180~220 DEG C, and the time of crystallization is 3~240h.
A kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that step
1) in, the metal salt is nine water chromic nitrates, nine water aluminum nitrates, magnesium nitrate hexahydrate, aluminium isopropoxide, aluminium carbide or aluminium hydroxide；
The organic ligand be terephthalic acid (TPA), benzene tricarbonic acid's triethyl, 2,5- dihydric para-phthalic acid, three (2- aminoethyl) amine or
Ring butylamine；The solvent is one or more mixtures of deionized water, DMF, ethyl alcohol；The mineralizer is hydrogen fluorine
Acid, nitric acid, sodium hydroxide or phosphoric acid.
A kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that step
2) in, the gas of inert atmosphere is nitrogen, argon gas or helium.
A kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that step
3) in, the gas of oxidizing atmosphere is oxygen, air, carbon dioxide or nitrogen oxygen atmosphere, preferably nitrogen oxygen atmosphere；The nitrogen
In oxygen gas mixture, the volume ratio of nitrogen and oxygen is 1:99.
A kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that step
4) in, the gas for being fluorinated atmosphere is fluoroform, monochlorodifluoromethane or HF and N2Gaseous mixture；The HF and N2In gaseous mixture, HF
And N2Volume ratio be 1:4.
The nano level metal fluoride catalysts of the confinement formula structure prepared according to the method described above.
The nano level metal fluoride catalysts of the confinement formula structure take off HF in fluorine-containing alkane cracking and prepare fluorine-containing alkene
The application of hydrocarbon reaction.
The nano level metal fluoride catalysts of the confinement formula structure take off HF in fluorine-containing alkane cracking and prepare fluorine-containing alkene
The application of hydrocarbon reaction, it is characterised in that it is 200~500 DEG C that fluorine-containing alkane cracking, which takes off HF to prepare the temperature of Fluorine containing olefine reaction, instead
Answering pressure is normal pressure.
The nano level metal fluoride catalysts of the confinement formula structure take off HF in fluorine-containing alkane cracking and prepare fluorine-containing alkene
The application of hydrocarbon reaction, it is characterised in that the fluorine-containing alkane is 1,1- Difluoroethane, 1,1,1- trifluoroethane, 1,1,1,2- tetrafluoro
At least one of ethane, 1,1,1,3,3- pentafluoropropane；The Fluorine containing olefine be vinyl fluoride, vinylidene, trifluoro-ethylene, 1,
At least one of 1,1,3- tetrafluoropropene.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
1) present invention by hydro-thermal method being combined together metal salt and organic ligand high-sequential, be allowed to form one kind
The metal-organic framework material of high-sequential.The dispersion of metal component high-sequential in entire skeleton；Thus the present invention most
Metal component in the nano level metal fluoride catalysts of the confinement formula structure obtained eventually disperses in carbon-based material high-sequential,
Therefore have the characteristics that strong anti-sintering, strong anti-carbon；
2) the metal-organic framework material that the present invention obtains is divided into three step heat treatment processes: the first step, by metal carbon dope
Material, which is placed in, to be risen to 300~450 DEG C/min under inert atmosphere (nitrogen, argon gas, helium) with 3 DEG C/min of heating rate and is carbonized
Processing, the organic matter in metal-organic framework material is gradually decomposed into carbon in the process, and it is multiple to obtain a kind of carbon doping metals
Condensation material, in the process carburizing temperature cannot excessively high otherwise skeleton structure can complete collapse, so that the specific surface of material is significantly
Decline.Second step, by carbon doping metals composite material obtained above, in oxidizing atmosphere, (oxygen, carbon dioxide, is mixed air
Close gas (N2/O2=1/99, volume ratio)) under 300~500 DEG C/min risen to 3 DEG C/min of heating rate carry out at Calcination for removing carbon
Reason, part carbon extra in carbon doping metals composite material is removed in the process, so metal component be exposed to get
To a kind of nano-scale carbon doping metals composite material of confinement formula structure, in the process except the carbon time cannot too long otherwise big portion
The carbon divided can be all removed, thus metal component agglomeration；Third step answers the nano-scale carbon doping metals of confinement formula structure
Condensation material (HF/N in fluorination atmosphere2(1/4, volume ratio), fluoroform, monochlorodifluoromethane) with 3 DEG C/min of heating rate
It rises to 200~300 DEG C/min and carries out gas phase fluorination processing, the nano-scale carbon doping metals of confinement formula structure are compound in the process
Metal component in material is fluorinated to arrive a kind of nano level metal fluoride of confinement formula structure, in the process gas phase
The fluorinated time cannot be too short, and otherwise fluorination is not thorough and then generates the oxyfluoride of metal；
3) present invention is exposed the metal component in metal-organic framework materials on the surface of the material in the form of fluoride,
And fixed metal component with carbon-based material, to obtain a kind of nano level metal fluoride of confinement formula structure.It is prepared
Obtained material therefore has high-specific surface area because of the skeleton structure of inherently high-sequential, and thermostabilization is good, and mechanical property is good
The advantages that good with continuity, can be used for multiple catalytic fields such as photocatalysis, electro-catalysis, heterogeneous catalysis.
Detailed description of the invention
Fig. 1 is the XRD diagram that the MIL-101 carbonization that embodiment 1 obtains removes the composite material after carbon.
Fig. 2 is the SEM figure that the MIL-101 carbonization that embodiment 2 obtains removes the composite material after carbon.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1
By 3.33g terephthalic acid (TPA) (C8H6O4) and nine water chromic nitrate (Cr (NO of 8g3)3·9H2O) be dissolved in 160mL go from
In sub- water, 0.92mL hydrofluoric acid (concentration 40%) is added, magnetic agitation 10min obtains solution, and above-mentioned solution is placed in 250mL
In the stainless steel autoclave of polytetrafluoroethyllining lining, and the crystallization 8h at 220 DEG C in air dry oven, after reaction,
Stainless steel autoclave is taken out, after its cooled to room temperature, the reaction product mixed liquor in stainless steel autoclave is removed.It will
Reaction product mixed liquor is centrifugally separating to obtain crude MIL-101.Then crude MIL-101 is gone at 70 DEG C with 500mL
Ion water washing 6h, then be centrifugated and gained sample is washed into 12h with 500mLDMF at 70 DEG C, then be centrifugated gained sample
Product wash 6h and washing 2 times with 300mL dehydrated alcohol at 70 DEG C, then are centrifugated gained sample using 500mL at 70 DEG C
NH4F aqueous solution (NH4The amount of the substance of F is 30mmol) washing 12h, finally with deionized water centrifuge washing 3 times to remove NH4F。
Gained sample is placed at 80 DEG C and is dried overnight up to presoma MIL-101.
Resulting presoma MIL-101 is placed in N2The lower 400 DEG C of roastings 3h, N of atmosphere2Flow is 30mL/min, wait roast knot
Shu Hou, by N2It is switched to gaseous mixture (N2/O2=1/99, volume ratio), roasting removes carbon 2h at 330 DEG C, after roasting except carbon
Atmosphere is switched to N2Until being naturally cooling to the room temperature composite material chromium-doped to get the nano-scale carbon to confinement formula structure
(XRD characterization is carried out to the composite material, characterization result is as shown in Figure 1, the composite material remains as can be seen from Figure 1
The characteristic peak of partial MIL-101, i.e., the described composite material still keep the part skeleton structure of MIL-101.And not
The diffraction maximum of chrome green shows that the partial size of chrome green is very small, the detection limit lower than XRD), by the composite material
It is placed in gaseous mixture (HF/N2=1/4, volume ratio) the lower 300 DEG C of roasting 2h progress gas phase fluorination of atmosphere, HF/N2Gaseous mixture total flow is
20mL/min, to gas phase fluorination after atmosphere is switched to N2Until being naturally cooling to room temperature to get confinement formula structure is arrived
Nanoscale is fluorinated chrome catalysts.
The nanoscale fluorination chrome catalysts of the above-mentioned confinement formula structure being prepared are used to be catalyzed five fluorine of 1,1,1,3,3-
Propane (HFC-245fa) cracking prepares tetrafluoropropene, and reaction equation is as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 245fa, N2Flow 20mL/min, HFC-245fa flow 5mL/min, N2It is always empty with HFC-245fa mixed gas
Speed is 750/h, and reaction temperature is 350 DEG C.5h sampling analysis is reacted, as a result are as follows: the conversion of 1,1,1,3,3- pentafluoropropane of reactant
Rate is 82.0%, selectivity 88% of the product along anti-1,3,3,3- tetrafluoropropene (HFO-1234ze).
Embodiment 2
By 3.33g terephthalic acid (TPA) (C8H6O4) and nine water chromic nitrate (Cr (NO of 8g3)3·9H2O) be dissolved in 160mL go from
In sub- water, 0.92mL hydrofluoric acid (concentration 40%) is added, magnetic agitation 10min obtains solution, and above-mentioned solution is placed in 250mL
In the stainless steel autoclave of polytetrafluoroethyllining lining, and the crystallization 8h at 220 DEG C in air dry oven, after reaction,
Stainless steel autoclave is taken out, after its cooled to room temperature, the reaction product mixed liquor in stainless steel autoclave is removed.It will
Reaction product mixed liquor is centrifugally separating to obtain crude MIL-101.Then crude MIL-101 is gone at 70 DEG C with 500mL
Ion water washing 6h, then be centrifugated and gained sample is washed into 12h with 500mL DMF at 70 DEG C, then be centrifugated gained
Sample washs 6h and washing 2 times with 300mL dehydrated alcohol at 70 DEG C, then is centrifugated and uses gained sample at 70 DEG C
500mL NH4F aqueous solution (NH4The amount of the substance of F is 30mmol) washing 12h, finally with deionized water centrifuge washing 3 times to remove
Remove NH4F.Gained sample is placed at 80 DEG C and is dried overnight up to presoma MIL-101.
Resulting presoma MIL-101 is placed in N2The lower 450 DEG C of roastings 3h, N of atmosphere2Flow is 30mL/min, wait roast knot
By N after beam2It is switched to gaseous mixture (N2/O2=1/99, volume ratio), roasting removes carbon 10h at 400 DEG C, after roasting except carbon
Atmosphere is switched to N2Until be naturally cooling to room temperature obtain confinement formula structure nano-scale carbon it is chromium-doped composite material it is (right
The composite material carries out SEM characterization, and characterization result is as shown in Figure 2, it can be seen that carries out the surface of MIL-101 after calcination processing
Become coarse, skeleton has a degree of collapsing, but still remains the skeleton structure of part MIL-101).Composite material is set
Gas phase fluorination is carried out in the lower 350 DEG C of roasting 3h of fluoroform atmosphere, fluoroform gas flow is 20mL/min, to gas phase fluorination
After atmosphere is switched to N2Chrome catalysts are fluorinated until being naturally cooling to room temperature to get to the nanoscale of confinement formula structure.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1,3,3- pentafluoropropane (HFC-245fa) cracking preparation 1,
3,3,3- tetrafluoropropenes (HFO-1234ze), reaction equation is as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 245fa, N2Flow 20mL/min, HFC-245fa flow 5mL/min, N2It is always empty with HFC-245fa mixed gas
Speed is 750/h, and reaction temperature is 350 DEG C.5h sampling analysis is reacted, as a result are as follows: the conversion of 1,1,1,3,3- pentafluoropropane of reactant
Rate is 94.1%, selectivity 90% of the product along anti-1,3,3,3- tetrafluoropropene (HFO-1234ze).
Embodiment 3
By 3.02g benzene tricarbonic acid's triethyl (C15H18O6) and nine water aluminum nitrate (Al (NO of 6.67g3)3·9H2O it) is dissolved in
In 50mL deionized water, 10mL HNO is added3Aqueous solution (4mol/L), magnetic agitation 10min obtain solution, by above-mentioned solution
It is placed in the stainless steel autoclave of 250mL polytetrafluoroethyllining lining, and the crystallization 72h at 210 DEG C in air dry oven, instead
After answering, stainless steel autoclave is taken out, after its cooled to room temperature, the reaction product in stainless steel autoclave is mixed
Liquid removes.Reaction product mixed liquor is centrifugated, obtained solid is dried overnight at 80 DEG C after deionized water is washed to obtain the final product
To yellow powder, as presoma MIL-110.
Resulting presoma MIL-101 is placed in N2The lower 400 DEG C of roastings 3h, N of atmosphere2Flow is 30mL/min, wait roast knot
By N after beam2It is switched to gaseous mixture (N2/O2=1/99, volume ratio), roasting removes carbon 2h at 330 DEG C, after roasting except carbon
Atmosphere is switched to N2Until being naturally cooling to the composite material that room temperature obtains the nano-scale carbon adulterated al of confinement formula structure.It will
The composite material is placed in gaseous mixture (HF/N2=1/4, volume ratio) the lower 200 DEG C of roasting 3h progress gas phase fluorination of atmosphere, HF/N2It is mixed
The total flow for closing gas is 20mL/min, to gas phase fluorination after atmosphere is switched to N2Until be naturally cooling to room temperature to get
To the nanoscale aluminum fluoride catalyst of confinement formula structure.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1,3,3- pentafluoropropane (HFC-245fa) cracking preparation 1,
3,3,3- tetrafluoropropenes (HFO-1234ze), reaction equation is as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 245fa, N2Flow 20mL/min, HFC-245fa flow 5mL/min, N2It is always empty with HFC-245fa mixed gas
Speed is 750/h, and reaction temperature is 350 DEG C.5h sampling analysis is reacted, as a result are as follows: the conversion of 1,1,1,3,3- pentafluoropropane of reactant
Rate is 97.6%, selectivity 92% of the product along anti-1,3,3,3- tetrafluoropropene (HFO-1234ze).
Embodiment 4
By 2.22g benzene tricarbonic acid's triethyl (C15H18O6) and nine water aluminum nitrate (Al (NO of 6.56g3)3·9H2O it) is dissolved in
In 100mL deionized water, 10mLNaOH aqueous solution (4mol/L) is added, magnetic agitation 10min obtains solution, by above-mentioned solution
It is placed in the stainless steel autoclave of 250mL polytetrafluoroethyllining lining, and the crystallization 3h at 210 DEG C in air dry oven, instead
After answering, stainless steel autoclave is taken out, after its cooled to room temperature, the reaction product in stainless steel autoclave is mixed
Liquid removes.Reaction product mixed liquor is centrifugated, obtained solid is dried overnight at 80 DEG C after deionized water is washed to obtain the final product
To yellow powder, as presoma MIL-110.
Resulting presoma MIL-101 is placed in N2The lower 400 DEG C of roastings 3h, N of atmosphere2Flow is 30mL/min, wait roast knot
By N after beam2It is switched to gaseous mixture (N2/O2=1/99, volume ratio), roasting removes carbon 2h at 330 DEG C, after roasting except carbon
Atmosphere is switched to N2Until being naturally cooling to the composite material that room temperature obtains the nano-scale carbon adulterated al of confinement formula structure.It will
The composite material is placed in the lower 250 DEG C of roasting 5h of monochlorodifluoromethane atmosphere and carries out gas phase fluorination, the gas of monochlorodifluoromethane
Flow is 20mL/min, to gas phase fluorination after atmosphere is switched to N2Until being naturally cooling to room temperature to get confinement formula is arrived
The nanoscale aluminum fluoride catalyst of structure.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1,3,3- pentafluoropropane (HFC-245fa) cracking preparation 1,
3,3,3- tetrafluoropropenes (HFO-1234ze), reaction equation is as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 245fa, N2Flow 20mL/min, HFC-245fa flow 5mL/min, N2It is always empty with HFC-245fa mixed gas
Speed is 750/h, and reaction temperature is 350 DEG C.5h sampling analysis is reacted, as a result are as follows: the conversion of 1,1,1,3,3- pentafluoropropane of reactant
Rate is 99.5%, selectivity 93% of the product along anti-1,3,3,3- tetrafluoropropene (HFO-1234ze).
Embodiment 5
By 1.424g magnesium nitrate hexahydrate (Mg (NO3)2·6H2) and 0.334g 2,5- dihydric para-phthalic acid's solid powder O
End be dissolved in N,N-dimethylformamide (67.5mL), ethyl alcohol (4.5mL) and water (4.5mL) in the mixed solvent (volume ratio:
15:1:1), and being ultrasonically treated 20min dissolves it sufficiently, and the solution being disposed is poured into 250mL polytetrafluoroethyllining lining
In stainless steel autoclave, and crystallization 28h pours out reaction under high pressure after reaction at 125 DEG C in air dry oven
Supernatant in kettle, then yellow powder is obtained with after 500mL methanol filtering and washing 3 times.Finally, sample is placed in N2Under atmosphere
After 120 DEG C of activation 6h, the presoma Mg-MOF-74 sample of dark yellow is obtained.
Resulting presoma Mg-MOF-74 is placed in N2The lower 400 DEG C of roastings 3h, N of atmosphere2Flow is 30mL/min, wait roast
After by N2It is switched to gaseous mixture (N2/O2=1/99, volume ratio), roasting removes carbon 2h at 330 DEG C, to the end of roasting except carbon
Atmosphere is switched to N afterwards2Until being naturally cooling to the magnesium-doped composite material of nano-scale carbon that room temperature obtains confinement formula structure.
The composite material is placed in gaseous mixture (HF/N2=1/4, volume ratio) the lower 200 DEG C of roasting 3h progress gas phase fluorination of atmosphere, HF/N2
The total flow of gaseous mixture is 20mL/min, to gas phase fluorination after atmosphere is switched to N2Until being naturally cooling to room temperature, i.e.,
Obtain the nanoscale fluorination Mg catalyst of confinement formula structure.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1- Difluoroethane (HFC-152a) cracking preparation vinyl fluoride, instead
Answer formula as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 152a, N2Flow 10mL/min, HFC-152a flow 10mL/min, N2With the total air speed of HFC-152a mixed gas
For 600/h, reaction temperature is 300 DEG C.5h sampling analysis is reacted, as a result are as follows: reactant HFC-152a conversion ratio is 90.3%, is produced
The selectivity 99.8% of object vinyl fluoride (VF).
Embodiment 6
By 7.8g aluminium hydroxide (Al (OH)3) and 7.2g cyclobutyl amine (C4H10N it) is dissolved in 144mL deionized water, then
9.8g phosphoric acid (H is added3PO4) it is used as mineralizer, acquired solution is placed in 250mL polytetrafluoroethyllining lining by magnetic agitation 10min
Stainless steel autoclave in, and the crystallization 240h at 180 DEG C in air dry oven takes out stainless after reaction
Steel autoclave removes the reaction product mixed liquor in stainless steel autoclave after its cooled to room temperature.By reaction product
Mixed liquor is centrifugated to obtain solid product, and 12h is washed with deionized in solid product at 70 DEG C, then centrifuge separation and
It is dried in vacuo at 100 DEG C, obtaining white powder is presoma MIL-34.
Resulting presoma MIL-34 is placed in the lower 350 DEG C of roastings 4h of argon atmosphere, flow 30mL/min, carbon to be calcined
Argon gas is switched to air after change, the Calcination for removing carbon 5h at 400 DEG C, to Calcination for removing carbon after atmosphere is switched to argon
Gas, until being naturally cooling to room temperature to get the composite material of the nano-scale carbon adulterated al of confinement formula structure is arrived.By the composite wood
Material is placed in gaseous mixture (HF/N2=1/4, volume ratio) the lower 300 DEG C of roasting 5h progress gas phase fluorination of atmosphere, HF/N2The gas of gaseous mixture
Flow is 20mL/min, to gas phase fluorination after atmosphere is switched to argon gas until being naturally cooling to room temperature to get to confinement
The nanoscale aluminum fluoride catalyst of formula structure.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1,2- tetrafluoroethane (HFC-134a) cracking and prepares trifluoro
Ethylene, reaction equation are as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 134a, N2Flow 15mL/min, HFC-134a flow 5mL/min, N2It is with the total air speed of HFC-134a mixed gas
600/h, reaction temperature are 400 DEG C.5h sampling analysis is reacted, as a result are as follows: reactant HFC-134a conversion ratio is 30.8%, product
The selectivity 99.1% of trifluoro-ethylene (TrFE).
Embodiment 7
By 0.5g aluminium carbide (Al4C3) and 6.93g terephthalic acid (TPA) (C8H6O4) it is dissolved in 75mL N,N-dimethylformamide
(DMF), acquired solution is ultrasonically treated 5min by magnetic agitation 10min.Above-mentioned solution is placed in 250mL polytetrafluoroethyllining lining
Stainless steel autoclave in, and in air dry oven at 220 DEG C crystallization for 24 hours, after reaction, take out stainless steel
Autoclave removes the reaction product mixed liquor in stainless steel autoclave after room temperature.Reaction product is mixed
Liquid is centrifugated to obtain solid product.Resulting solid product is respectively washed three times with DMF and methanol respectively, then by solid product
Be placed at 110 DEG C be dried in vacuo pale powder is presoma MIL-53.
Resulting presoma MIL-53 is placed in the lower 400 DEG C of roastings 4h of helium atmosphere, flow 30mL/min, carbon to be calcined
Helium is switched to carbon dioxide after change, the Calcination for removing carbon 10h at 400 DEG C, to Calcination for removing carbon after atmosphere is switched
For helium, until being naturally cooling to room temperature to get to the composite material of the nano-scale carbon adulterated al of confinement formula structure.It will be described multiple
Condensation material is placed in the lower 250 DEG C of roasting 3h of fluoroform atmosphere and carries out gas phase fluorination, and the gas flow of fluoroform is 20mL/min,
Atmosphere is switched to helium until being naturally cooling to room temperature to get the nanoscale fluorine of confinement formula structure is arrived after to gas phase fluorination
Change Al catalysts.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1- trifluoroethane (HFC-143a) cracking and prepares inclined fluorine second
Alkene, reaction equation are as follows:
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 143a, N2Flow 20mL/min, HFC-143a flow 5mL/min, N2It is with the total air speed of HFC-143a mixed gas
750/h, reaction temperature are 400 DEG C.5h sampling analysis is reacted, as a result are as follows: reactant HFC-143a conversion ratio is 90.5%, product
The selectivity 94.4% of vinylidene (VDF).
Embodiment 8
By 7.5g tri- (2- aminoethyl) amine (C6H22N4) and 10.2g aluminium isopropoxide (C9H21AlO3) it is dissolved in 36mL deionization
In water, 0.49g phosphoric acid (H is added3PO4) it is used as mineralizer, acquired solution is placed in 250mL polytetrafluoro by magnetic agitation 10min
In the stainless steel autoclave of ethylene liner, and crystallization 72h takes after reaction at 180 DEG C in air dry oven
Stainless steel autoclave out removes the reaction product mixed liquor in stainless steel autoclave after its cooled to room temperature.It will be anti-
It answers product mixture to be centrifugated to obtain solid product, 12h is washed with deionized in solid product at 70 DEG C, then centrifugation point
It is dried in vacuo at from and 100 DEG C, obtaining white powder is presoma MIL-32.
Resulting presoma MIL-32 is placed in the lower 450 DEG C of roastings 5h of argon atmosphere, flow 30mL/min, carbon to be calcined
Argon gas is switched to gaseous mixture (N after change2/O2=1/99, volume ratio), the Calcination for removing carbon 5h at 400 DEG C, to Calcination for removing carbon
After atmosphere is switched to argon gas, until being naturally cooling to room temperature to get to the nano-scale carbon adulterated al of confinement formula structure
Composite material.The composite material is placed in gaseous mixture (HF/N2=1/4, volume ratio) the lower 300 DEG C of roasting 3h progress gas phase of atmosphere
Fluorination, HF/N2The total flow of gaseous mixture be 20mL/min, to gas phase fluorination after by atmosphere be switched to argon gas until naturally drop
It warms to room temperature to get the nanoscale aluminum fluoride catalyst of confinement formula structure is arrived.
The above-mentioned catalyst being prepared is used to be catalyzed 1,1,1,2- tetrafluoroethane (HFC-134a) cracking and prepares trifluoro
Ethylene, reaction equation are as follows:
CF3CH2F→CF2=CHF+HF
Reaction condition are as follows: Catalyst packing enters in fixed bed reactors, and loaded catalyst 2mL is passed through N2And HFC-
The mixed gas of 134a, N2Flow 15mL/min, HFC-134a flow 5mL/min, N2It is with the total air speed of HFC-134a mixed gas
600/h, reaction temperature are 400 DEG C.5h sampling analysis is reacted, as a result are as follows: reactant HFC-134a conversion ratio is 40%, product three
The selectivity 99.5% of vinyl fluoride (TrFE).
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure, it is characterised in that including following step
It is rapid:
1) in the case where mineralizer has effect, metal salt and organic ligand carry out crystallization in a solvent, and MOF material, institute is made
Stating metal salt is at least one of Cr salt, Mg salt, Al salt；
2) MOF material obtained by step 1) is placed under inert atmosphere, calcining at constant temperature handles 3-5h, MOF material at 300 ~ 450 DEG C
Organic matter in material gradually decomposes carbonization, is then naturally cooling to room temperature, obtains carbon doping metals composite material；
3) carbon doping metals composite material obtained by step 2 is placed under oxidizing atmosphere, at 300~500 DEG C calcining at constant temperature 1 ~
10h carries out carbon removal treatment, and extra part carbon is removed in carbon doping metals composite material, exposes part metals component
Come, is then naturally cooling to room temperature, obtains the nano-scale carbon doping metals composite material of confinement formula structure；
4) nano-scale carbon doping metals composite material obtained by step 3) is placed under fluorination atmosphere, constant temperature is forged at 200~300 DEG C
It burns 2 ~ 5h and carries out gas phase fluorination processing, be naturally cooling to room temperature then to get the nano level metal fluorine of the confinement formula structure is arrived
Compound catalyst.
2. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure according to claim 1,
It is characterized in that in step 1), MOF material obtained is at least one in MIL-101, MIL-32, MIL-34, MIL-53, MIL-74
Kind；The temperature of the crystallization is 180 ~ 220 DEG C, and the time of crystallization is 3~240h.
3. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure according to claim 1,
It is characterized in that in step 1), the metal salt is nine water chromic nitrates, nine water aluminum nitrates, magnesium nitrate hexahydrate, aluminium isopropoxide, aluminium carbide
Or aluminium hydroxide；The organic ligand is terephthalic acid (TPA), benzene tricarbonic acid's triethyl, 2,5- dihydric para-phthalic acid, three (2-
Aminoethyl) amine or ring butylamine；The solvent is one or more mixtures of deionized water, DMF, ethyl alcohol；The mine
Agent is hydrofluoric acid, nitric acid, sodium hydroxide or phosphoric acid.
4. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure according to claim 1,
It is characterized in that in step 2, the gas of inert atmosphere is nitrogen, argon gas or helium.
5. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure according to claim 1,
It is characterized in that in step 3), the gas of oxidizing atmosphere is oxygen, air, carbon dioxide or nitrogen oxygen atmosphere, preferably nitrogen oxygen
Gaseous mixture；In the nitrogen oxygen atmosphere, the volume ratio of nitrogen and oxygen is 1:99.
6. a kind of preparation method of the nano level metal fluoride catalysts of confinement formula structure according to claim 1,
It is characterized in that in step 4), the gas for being fluorinated atmosphere is fluoroform, monochlorodifluoromethane or HF and N2Gaseous mixture；The HF and
N2In gaseous mixture, HF and N2Volume ratio be 1: 4.
7. the nano level metal fluoride catalysts of confinement formula structure prepared by the method as described in claim 1 ~ 6 is any.
8. the nano level metal fluoride catalysts of confinement formula structure according to claim 7 take off HF in fluorine-containing alkane cracking
Prepare the application of Fluorine containing olefine reaction.
9. application according to claim 8, it is characterised in that fluorine-containing alkane cracking takes off the temperature that HF prepares Fluorine containing olefine reaction
Degree is 200 ~ 500 DEG C, and reaction pressure is normal pressure.
10. application according to claim 8, it is characterised in that the fluorine-containing alkane be 1,1- Difluoroethane, 1,1,1- tri-
At least one of fluoroethane, 1,1,1,2- tetrafluoroethane, 1,1,1,3,3- pentafluoropropane；The Fluorine containing olefine be vinyl fluoride,
At least one of vinylidene, trifluoro-ethylene, 1,1,1,3- tetrafluoropropene.
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