CN110560108B - Ternary layered MAX phase ceramic material catalyst and preparation method and application thereof - Google Patents
Ternary layered MAX phase ceramic material catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ternary layered MAX phase ceramic material catalyst, a preparation method and application thereof, wherein the preparation method of the ternary layered MAX phase ceramic material catalyst comprises the following steps: under the action of a fluorinating agent, fluorinating an A atomic layer in the MAX phase ceramic material to prepare the ternary layered MAX phase ceramic material catalyst; wherein the MAX phase ceramic material is Ti3AlC2、Cr2AlC、V2AlC、Nb2At least one of AlC. The method for preparing the ternary layered MAX phase ceramic material catalyst has short period and simple operation, and the prepared catalyst is a ternary layered transition metal catalyst which has good catalytic activity and stability in the reaction of preparing fluorine-containing olefin by removing HF from fluorine-containing alkane.
Description
Technical Field
The invention relates to a ternary layered MAX phase ceramic material catalyst and a preparation method and application thereof.
Background
The MAX phase ceramic is a ternary layered compound, wherein M represents a transition metal element, A represents a IIIA or IVA group element, and X represents a C or N element; the MAX phase ceramic may be divided into 211, 312, and 413 phases, which are equal, depending on the value of n. The MAX phase ceramic has excellent performances of metal and ceramic, has the characteristics of high electrical and thermal conductivity similar to metal, machinability, high damage tolerance, excellent thermal shock resistance and the like, and also has excellent characteristics of high modulus, high temperature resistance, oxidation resistance, corrosion resistance and the like similar to ceramic. In the MAX crystal structure, M-X bonds mainly comprise covalent bonds and ionic bonds, and the strength of the bonding bonds is very high; the M-A bond and the A-A bond have a relatively weak metal bond component. Thus, the A atomic layer reactivity of MAX phase ceramics is also highest.
Since fluorinated alkanes (HFCs) widely used in the refrigerant, fire extinguishing agent, foaming agent, and other industries have a damaging effect on the ozone layer and a greenhouse effect, the production of hydrofluorocarbons having zero Ozone Depletion Potential (ODP) and low Global Warming Potential (GWP) has become an increasingly important issue in the world. The most straightforward and simple process for the manufacture of fluorine-containing olefins from fluorine-containing alkanes, particularly hydrofluoroalkanes, by HF removal. Such as 1, 1-difluoroethane and 1,1,1,3, 3-pentafluoropropane, to produce fluoroethylene, 1,1,1, 3-tetrafluoropropene, and the like, all of which have zero ODP values and low GWP values. Therefore, the method is very important for the research on the process for dehydrofluorination of fluorine-containing alkane. However, at present, the common catalyst for preparing fluorine-containing olefin by catalyzing the fluorine-containing alkane to remove HF has the problems of quick deactivation, easy carbon deposition, low conversion rate of fluorine-containing alkane, low selectivity of fluorine-containing olefin and the like.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a ternary layered MAX phase ceramic material catalyst, and a preparation method and application thereof. The method for preparing the ternary layered MAX phase ceramic material catalyst has short period and simple operation, and the prepared catalyst is a ternary layered transition metal catalyst. The ternary layered MAX phase ceramic material catalyst has good catalytic activity and stability in the reaction of preparing fluorine-containing olefin by removing HF from fluorine-containing alkane.
The preparation method of the ternary layered MAX phase ceramic material catalyst is characterized in that an A atomic layer in the MAX phase ceramic material is fluorinated under the action of a fluorinating agent to prepare the ternary layered MAX phase ceramic material catalyst; wherein the MAX phase ceramic material is Ti3AlC2、Cr2AlC、V2AlC、Nb2At least one of AlC.
The preparation method of the ternary layered MAX phase ceramic material catalyst is characterized by comprising the following specific steps of: in the presence of alpha-Al2O3Putting MAX phase ceramic material into a tubular furnace made of the material, introducing fluorinating agent gas, roasting for 3-5 h at 200-350 ℃, and then switching the atmosphere in the tubular furnace to N2Naturally cooling to room temperature to obtain the ternary layered MAX phase ceramic material catalyst; wherein the fluorinating agent is CHFCl2Or CHClF2。
The preparation method of the ternary layered MAX phase ceramic material catalyst is characterized by comprising the following specific steps of: mixing a fluoridizing agent solid and a MAX phase ceramic material, placing the mixture into a ball milling tank for ball milling, wherein the ball milling rotating speed is 200-400 r/min, the ball milling time is 1-4 h, and filling the ball-milled mixture into alpha-Al2O3And (3) roasting the mixture in a tubular furnace made of the material at a high temperature in a nitrogen atmosphere to obtain the ternary layered MAX phase ceramic material catalyst.
The preparation method of the ternary layered MAX-phase ceramic material catalyst is characterized in that the molar ratio of the fluorinating agent to the MAX-phase ceramic material is 1: 1-3: 1.
The preparation method of the ternary layered MAX phase ceramic material catalyst is characterized in that the fluorinating agent is NH4F, performing high-temperature roasting at the temperature of 250-400 ℃ for 3-5 hours.
The preparation method of the ternary layered MAX phase ceramic material catalyst is characterized in that the fluorinating agent is NH4BF4The high-temperature roasting temperature is 150-300 ℃, and the high-temperature roasting time is 3-5 h.
The ternary layered MAX phase ceramic material catalyst prepared by the method is provided.
The ternary layered MAX phase ceramic material catalyst is applied to the reaction for preparing fluorine-containing olefin by removing HF from fluorine-containing alkane.
The application of the ternary layered MAX-phase ceramic material catalyst in the reaction for preparing fluorine-containing olefin by removing HF from fluorine-containing alkane is characterized in that the fluorine-containing alkane is 1, 1-difluoroethane or 1,1,1,3, 3-pentafluoropropane, the reaction temperature for preparing fluorine-containing olefin by removing HF from fluorine-containing alkane is 300-350 ℃, the reaction pressure is normal pressure, and the prepared fluorine-containing olefin is vinyl fluoride or 1,1,1, 3-tetrafluoropropene.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the atomic layer A with the highest activity in the ternary layered MAX-phase ceramic material is fluorinated by a gas-phase fluorinating agent or a solid-phase fluorinating agent, so that the ternary layered MAX-phase ceramic material catalyst is obtained. MAX phase material is used as catalyst precursor, and transition metal carbide or nitride layer and pure A atom sheet layer are formed according to the formulan+1Xn]/A/[Mn+1Xn]A. is arranged alternately, during fluorination, the M atom gradually binds to F, and the A atom binds to F to form an unsaturated coordinated AlF3The catalyst is stable monomolecular AlF containing carbon3And (3) a layer. Thus, the useful carbon layer inhibits AlF3Ensures the AlF sheetThe distribution of the molecular layer shows extremely high activity and stability in the reaction of preparing fluorine-containing olefin by removing HF from fluorine-containing alkane. When the catalyst is used for catalyzing the reaction of removing HF from fluorine-containing alkane to prepare fluorine-containing olefin, the catalyst has the characteristics of high conversion rate of fluorine-containing alkane, good selectivity of fluorine-containing olefin, prolonged service life of the ternary layered MAX phase ceramic material catalyst, and difficult carbon deposition and inactivation.
2) The ternary layered MAX phase ceramic material catalyst prepared by the method can adopt a gas phase fluorination method or a solid phase fluorination method. When the gas phase fluorination method is adopted, the gas phase fluorination agent is CHFCl2Or CHClF2Will react with the Al atomic layer in the MAX phase to form AlF3And HCl to prepare the ternary layered MAX phase ceramic material catalyst. When a solid phase fluorination method is adopted, a solid phase fluorinating agent NH4F or NH4BF4Thoroughly mixed with MAX in a ball mill and then N in a tube furnace2High-temperature roasting is carried out in the atmosphere, HF gas is released by a solid phase fluorinating agent to fluorinate an A atomic layer in MAX, and penta-coordinate or tetra-coordinate AlF is formed after Al and F in MAX are combined3Thereby doping the F element into the A atomic layer of the MAX phase ceramic material to prepare the ternary layered MAX phase ceramic material catalyst. HF gas, alpha-Al, which is extremely corrosive, is released during the fluorination2O3Corrosion resistance, so alpha-Al is adopted2O3The material is calcined in a tubular furnace at high temperature.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
5.31g of Ti3AlC2Put in with alpha-Al2O3Introducing CHClF into a tube furnace made of the material2Gas (CHClF)2Gas flow is 30mL/min), the temperature is raised from room temperature to 300 ℃ at the speed of 3 ℃/min, then the mixture is roasted at the constant temperature of 300 ℃ for 3h for gas phase fluorination, and the atmosphere in the tube furnace is switched to N after the gas phase fluorination is finished2Until naturally cooled to room temperature, stable product III is obtainedA catalyst of an elementary laminar MAX phase ceramic material.
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing 1,1,1,3, 3-pentafluoropropane (HFC-245fa) to crack to prepare 1,3,3, 3-tetrafluoropropene (HFO-1234ze), and the reaction formula is as follows:
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas of HFC-245fa, N2The flow rate is 20mL/min, the HFC-245fa flow rate is 5mL/min, and the reaction temperature is 350 ℃. The sampling reaction result of the reaction 2h is as follows: the conversion of reactant 1,1,1,3, 3-pentafluoropropane was 89.6%, the selectivity to product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) was 99.3%, and the catalyst remained stable after 15h (i.e., reactant conversion and selectivity to the target product remained essentially unchanged). After 150h of reaction, the conversion rate of the reactant 1,1,1,3, 3-pentafluoropropane is reduced to 68.9%, and the selectivity of the product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) is basically kept unchanged.
Example 2
5.12g of Ti3AlC2Put in with alpha-Al2O3Introducing CHClF into a tube furnace made of the material2Gas (CHClF)2Gas flow is 30mL/min), the temperature is raised to 350 ℃ from room temperature at the speed of 3 ℃/min, then the mixture is roasted at the constant temperature of 350 ℃ for 5h for gas phase fluorination, and the atmosphere in the tube furnace is switched to N after the gas phase fluorination is finished2And naturally cooling to room temperature to obtain the stable ternary layered MAX phase ceramic material catalyst.
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing 1,1,1,3, 3-pentafluoropropane (HFC-245fa) to crack to prepare 1,3,3, 3-tetrafluoropropene (HFO-1234ze), and the reaction formula is as follows:
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 2mL, and N is introduced2Mixed gas of HFC-245fa, N2The flow rate is 20mL/min, the HFC-245fa flow rate is 5mL/min, and the reaction temperature is 350 ℃. The sampling reaction result of the reaction 2h is as follows: the conversion of the reactant 1,1,1,3, 3-pentafluoropropane was 98.1%, the selectivity of the product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) was 99.7%, and the catalyst remained stable after 10h (i.e., the reactant conversion and the selectivity to the target product remained essentially unchanged). After 130h of reaction, the conversion rate of the reactant 1,1,1,3, 3-pentafluoropropane is reduced to 68.9%, and the selectivity of the product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) is basically kept unchanged.
Example 3
6.18g of Cr2Placing AlC in alpha-Al2O3The CHFCl is introduced into a tube furnace made of the material2Gas (CHFCl)2Gas flow is 30mL/min), the temperature is raised to 350 ℃ from room temperature at the speed of 3 ℃/min, then the mixture is roasted at the constant temperature of 350 ℃ for 5h for gas phase fluorination, and the atmosphere in the tube furnace is switched to N after the gas phase fluorination is finished2And naturally cooling to room temperature to obtain the stable ternary layered MAX phase ceramic material catalyst.
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing 1, 1-difluoroethane (HFC-152a) to crack to prepare vinyl fluoride, and the reaction formula is as follows:
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 1mL, and N is introduced2Mixed gas of HFC-152a, N2The flow rate is 5mL/min, the flow rate of HFC-152a is 5mL/min, and the reaction temperature is 300 ℃. Reaction 2h the sampling reaction results were: the conversion of the reactant HFC-152a was 89.3%, the selectivity to the product Vinyl Fluoride (VF) was 98.1%, and the catalyst remained stable after 9h (i.e., the reactant conversion and the selectivity to the target product remained essentially unchanged). After 135 hours of reaction, the conversion rate of the reactant HFC-152a is reduced to 55.1 percent, and the product of Vinyl Fluoride (VF)) The selectivity of (a) remains substantially unchanged.
Example 4
Reacting NH4F and Ti3AlC2Mixing at a 2:1 molar ratio (Ti)3AlC2The mass is 3.13g), the obtained mixture is placed in a ball milling tank to be ball milled for 2 hours at the rotating speed of 300r/min, and the ball milled mixture is put in alpha-Al2O3And (2) carrying out high-temperature roasting in a tubular furnace (the high-temperature roasting process is that the temperature is raised to 350 ℃ from room temperature at the speed of 3 ℃/min under the atmosphere of nitrogen, then the temperature is kept for 3h, and then the temperature is naturally lowered to the room temperature) to obtain the stable ternary laminar MAX phase ceramic material catalyst.
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing 1, 1-difluoroethane (HFC-152a) to crack to prepare vinyl fluoride, and the reaction formula is as follows:
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 1mL, and N is introduced2And HFC-152a, N2The flow rate is 5mL/min, the flow rate of HFC-152a is 5mL/min, and the reaction temperature is 300 ℃. The sampling reaction result of the reaction 2h is as follows: the conversion of the reactant HFC-152a was 85.9%, the selectivity to the product Vinyl Fluoride (VF) was 97.1%, and the catalyst remained stable after 10h (i.e., the reactant conversion and the selectivity to the target product remained essentially unchanged). After 160h of reaction, the conversion rate of reactant HFC-152a is reduced to 51.9%, and the selectivity of product Vinyl Fluoride (VF) is basically kept unchanged.
Example 5
Reacting NH4BF4And V2Mixing of AlC in a molar ratio of 2:1 (V)2The mass of AlC is 3.51g), the obtained mixture is put into a ball milling tank to be ball milled for 2 hours at the rotating speed of 300r/min, and the ball milled mixture is put into alpha-Al2O3High-temperature roasting in a tubular furnace (the high-temperature roasting process is that the temperature is raised to 350 ℃ from room temperature at 3 ℃/min under the nitrogen atmosphere, then the temperature is preserved for 3h, and then the temperature is naturally reduced to room temperature) to obtain the stable tris (hydroxymethyl) amineA catalyst of an elementary laminar MAX phase ceramic material.
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing 1, 1-difluoroethane (HFC-152a) to crack to prepare vinyl fluoride, and the reaction formula is as follows:
the reaction conditions are as follows: the catalyst is filled into a fixed bed reactor, the filling amount of the catalyst is 1mL, and N is introduced2And HFC-152a, N2The flow rate is 5mL/min, the flow rate of HFC-152a is 5mL/min, and the reaction temperature is 300 ℃. The sampling reaction result of the reaction 2h is as follows: the conversion of the reactant HFC-152a was 91.2%, the selectivity of the product Vinyl Fluoride (VF) was 98.3%, and the catalyst remained stable after 11h (i.e., the reactant conversion and the selectivity of the target product remained essentially unchanged). After 150h of reaction, the conversion rate of reactant HFC-152a is reduced to 54.9%, and the selectivity of the product Vinyl Fluoride (VF) is basically kept unchanged.
Example 6
Reacting NH4BF4And Nb2AlC is mixed in a molar ratio of 3:1 (Nb)2The mass of AlC is 3.49g), the obtained mixture is put into a ball milling pot to be ball milled for 2 hours at the rotating speed of 300r/min, and the ball milled mixture is put into alpha-Al2O3And (2) carrying out high-temperature roasting in a tubular furnace for obtaining the stable ternary laminar MAX phase ceramic material catalyst (the high-temperature roasting process is that the temperature is raised to 350 ℃ from the room temperature at the speed of 3 ℃/min under the nitrogen atmosphere, then the temperature is kept for 3h, and then the temperature is naturally reduced to the room temperature).
The stable ternary layered MAX phase ceramic material catalyst prepared by the method is used for catalyzing cracking of 1,1,1,3, 3-pentafluoropropane (HFC-245fa) to prepare 1,3,3, 3-tetrafluoropropene (HFO-1234ze), and the reaction formula is as follows:
the reaction conditions are as follows: filling catalyst into fixed bed reactor, and filling catalystFilling 2mL, introducing N2Mixed gas of HFC-245fa, N2The flow rate is 20mL/min, the HFC-245fa flow rate is 5mL/min, and the reaction temperature is 350 ℃. Reaction 2h the sampling reaction results were: the conversion of the reactant 1,1,1,3, 3-pentafluoropropane was 90.3%, the selectivity to the product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) was 99.9%, and the catalyst remained stable after 8h (i.e., the reactant conversion and the selectivity to the target product remained essentially unchanged). After 145h of reaction, the conversion rate of the reactant 1,1,1,3, 3-pentafluoropropane is reduced to 50.3%, and the selectivity of the product cis-trans 1,3,3, 3-tetrafluoropropene (HFO-1234ze) is kept basically unchanged.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (7)
1. A preparation method for preparing a fluorine-containing olefin reaction catalyst by removing HF from fluorine-containing alkane is characterized in that an A atomic layer in a MAX phase ceramic material is fluorinated under the action of a fluorinating agent to prepare the catalyst; wherein the MAX phase ceramic material is Ti3AlC2、Cr2AlC、V2AlC、Nb2At least one of AlC;
under the action of the fluorinating agent, the specific process of fluorinating the A atomic layer in the MAX phase ceramic material is one of the following two modes:
mode 1: in the presence of alpha-Al2O3Putting MAX phase ceramic material into a tubular furnace made of the material, introducing fluorinating agent gas, roasting for 3-5 h at 200-350 ℃, and then switching the atmosphere in the tubular furnace to N2Naturally cooling to room temperature to obtain the catalyst; wherein the fluorinating agent is CHFCl2Or CHClF2；
Mode 2: mixing a fluoridizing agent solid and a MAX phase ceramic material, placing the mixture into a ball milling tank for ball milling, wherein the ball milling rotating speed is 200-400 r/min, the ball milling time is 1-4 h, and filling the ball-milled mixture into alpha-Al2O3The catalyst is prepared by high-temperature roasting in a tubular furnace made of the material under the nitrogen atmosphere.
2. The method for preparing the catalyst for the reaction of preparing the fluorine-containing olefin by removing HF from the fluorine-containing alkane according to claim 1, wherein in the mode 2, the molar ratio of the fluorinating agent to the MAX-phase ceramic material is 1:1 to 3: 1.
3. The method according to claim 1, wherein in the embodiment 2, the fluorinating agent is NH4F, performing high-temperature roasting at the temperature of 250-400 ℃ for 3-5 h.
4. The method according to claim 1, wherein in the embodiment 2, the fluorinating agent is NH4BF4The high-temperature roasting temperature is 350 ℃, and the high-temperature roasting time is 3-5 h.
5. A catalyst prepared by the process of any one of claims 1 to 4.
6. The use of the catalyst of claim 5 in the catalysis of HF-removal from a fluorine-containing alkane to produce a fluorine-containing alkene.
7. The method of claim 6, wherein the fluorine-containing alkane is 1, 1-difluoroethane or 1,1,1,3, 3-pentafluoropropane, the reaction temperature for removing HF from the fluorine-containing alkane to prepare the fluorine-containing alkene is 300-350 ℃, the reaction pressure is normal pressure, and the prepared fluorine-containing alkene is vinyl fluoride or 1,1,1, 3-tetrafluoropropene.
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