CN110270375B - Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof - Google Patents
Unsaturated carbon-carbon triple bond selective hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN110270375B CN110270375B CN201910586139.1A CN201910586139A CN110270375B CN 110270375 B CN110270375 B CN 110270375B CN 201910586139 A CN201910586139 A CN 201910586139A CN 110270375 B CN110270375 B CN 110270375B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
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- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
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- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
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- 238000006243 chemical reaction Methods 0.000 abstract description 35
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2286—Alkynes, e.g. acetylides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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Abstract
The invention provides an unsaturated carbon-carbon triple bond selective hydrogenation catalyst and a preparation method thereof. The catalyst takes functionalized carbon nanofibers as a carrier to load precious metal active components, and is characterized in that the active metal surface is coated with a permeable carbon layer with controllable thickness, the thickness is 0.5-3 nm, the active components are stably dispersed on the carrier, the size is uniform, and the particle size is 1-3 nm. The preparation method adopted by the invention is that one or two noble metal salts are dissolved in deionized water to prepare a mixed salt solution, the mixed salt solution is soaked on the surface of a carrier, and after reduction and heat treatment in a reaction atmosphere, CH with controllable carbon layer thickness and permeability is formed on the surface of an active metalx@ M/CNF-A noble metal catalyst. The catalyst can be applied to the selective hydrogenation reaction process of various unsaturated carbon-carbon triple bonds in the fields of petrochemical industry, fine chemical industry and the like, has outstanding catalytic performance, and has high activity and C-C double bond selectivity. The catalyst also has good recycling property and is easy to recycle and reuse.
Description
Technical Field
The invention belongs to the fields of petrochemical industry and fine chemical industry, and particularly relates to a noble metal/carbon nanofiber catalyst modified by a hydrocarbon intermediate species for unsaturated carbon-carbon triple bond selective hydrogenation reaction and a preparation method thereof.
Background
The selective hydrogenation reaction of unsaturated carbon-carbon triple bond is an important support for fine chemical industry and petrochemical industry, and is widely applied to industrial production such as chemical synthesis, pharmaceutical synthesis, agricultural chemical synthesis and the like. Earlier, supported monometallic Pd catalysts were often used to catalyze unsaturated carbon-carbon triple bond selective hydrogenation reactions. In order to obtain high selectivity, the general strategy in industry is to add lead acetate, quinoline and other substances to modify and poison the Pd catalyst (Lindlar catalyst) in the catalyst treatment process. However, with the increasing tightening of the requirements for sustainable development of the environment, the use of Lindlar catalysts is severely limited by lead species with higher toxicity.
In order to solve the problems, researchers improve the catalytic activity, selectivity and stability of the catalyst by regulating and controlling the composition and structure of active components, selecting a proper carrier and exploring a new synthesis method. In the Identification of non-noble metal catalysts for selective hydrogenation of acetylene, Science,2008,320,1320-1322, Au, Pt, Zn, Ni, Cu, etc. as active components, it was found that non-noble metal Ni-Zn alloys are more favorable for the directional conversion of acetylene to olefin than the monometallic Pd catalyst. For supported catalysts, the type of support and its interaction with the metal interface have also attracted attention from researchers. The carbon nano material, especially Carbon Nano Fiber (CNF), has the advantages of high specific surface, electron transfer, stable structure and the like, and shows excellent performance in the field of catalytic hydrogenation as a carrier.
In binary Co-Pd catalysts, student's of preparation methods and the same of selective hydrogenation of acetylene, J.Catal.2013,300,125-135, a supported Pd-Co catalyst is prepared and applied to the selective hydrogenation of acetylene. The catalytic evaluation results show that the catalyst is compared with Al2O3The supported PdCo catalyst, Pd-Co/C, has strong carrier-metal interaction and shows excellent ethylene selectivity. More importantly, the metal-carrier interface site has the characteristic of coordination unsaturation, so that a special electronic state is displayed, and the construction of a metal-carrier interface structure to realize the improvement of the selective hydrogenation reaction performance becomes a hotspot of research in the field. Zaera et al, Sub-monolayered control of Mixed-Oxide Support Composition in catalysis via Atomic laysis of Selective Hydrogenation of citraldehyde produced by(SiO2-ALD)-Pt/Al2O3ACS Catal.,2018,8,8513-2Deposited on the surface of Pt to construct Pt-SiO2The interface sites improve the electronic structure of the Pt particles, promote the activation of C ═ O bonds and improve the selectivity. However, in the process of constructing the interface, the thickness of the species deposited on the surface of the metal particles is difficult to control accurately and is impermeable, and the active sites are easily coated excessively, so that the catalytic activity is greatly reduced. Recently, Christopher et al used the reactant gas CO-in adsorbed-mediated interactions in oxide-supported Rh catalysts, Nat. chem.,2017,9, 120-channels 1272And H2And constructing an interface structure by an induction method. Research shows that compared with the traditional TiOxModified Rh catalyst, catalyst formed by atmosphere induction method and rich Rh-TiO formed in catalystx-HCOxThe interface sites promote the electronic state of Rh metal particles to change, and the surface coating layer has permeability, which is favorable for the diffusion and adsorption of reactant molecules and realizes CH4Selectivity and CO2The activity is improved together. However, no relevant report is found in the research on improving the performance of the catalyst in the unsaturated carbon-carbon triple bond selective hydrogenation reaction by regulating the nature and the structure of the interface.
In conclusion, constructing a coordination unsaturated metal-carrier interface site is an effective means for improving the product selectivity of the supported catalyst in the hydrogenation reaction, but the thickness of the species deposited on the surface of the metal particles is difficult to accurately control and has no permeability while the selectivity is improved by constructing an interface structure by a traditional method, so that the catalytic activity is seriously influenced. The invention uses carbon nano-fiber as a catalyst carrier, and adopts an atmosphere induction method to construct permeable CH with controllable coating thicknessxAnd (2) regulating and controlling a-Pd-CNF interface structure to obtain the single metal catalyst with optimal coating thickness and good permeability, thereby realizing the directional conversion of alkyne molecules to olefin molecules.
Disclosure of Invention
The invention aims to provide a thickness of a carbon coating layer on an active metal surfaceControllable and permeable CHxA @ M/CNF catalyst and a preparation method thereof. The catalyst is mainly used for selective hydrogenation reaction of unsaturated carbon-carbon triple bonds, and has the characteristics of high activity, selectivity and stability.
The catalyst provided by the invention is represented by CHx@ M/CNF-A, in which CHxIn the species, x is 1 or 2, M is a noble metal active component, and CNF-A is functionalized carbon nanofiber; m is one or two of noble metals Pd, Au, Ir, Rh and Ag, preferably Pd, Au or Ir, wherein the mass of the noble metals accounts for 0.5-5.0% of the total mass of the catalyst, preferably 0.5-2.0%; a in CNF-A is a functional group NO3、SO3H、Cl、PO3H, one of the groups.
The catalyst is characterized by comprising the following structural characteristics: m is loaded on CNF-A carrier and is subjected to heat treatment atmosphere to induce formed CHxThe layer is coated on the noble metal M, the thickness of the coating layer is controllable and has permeability, and the thickness is 0.5-3 nm; the active metal components are highly and stably dispersed on the surface of the carrier, and the carrier has uniform size, 1-3 nm of particle size and narrow particle size distribution range.
The preparation method of the catalyst comprises the steps of taking carbon nanofibers containing functional groups as carriers, taking noble metals as active components, and carrying out heat treatment under the induction of mixed gas of alkyne atmosphere and/or alkene atmosphere and hydrogen to obtain the hydrocarbon modified supported noble metal catalyst.
The preparation method of the unsaturated carbon-carbon triple bond selective hydrogenation catalyst provided by the invention comprises the following specific steps:
A. roasting the carbon nanofiber precursor at 2000-3000 ℃ for 2-6 h, dispersing the carbon nanofiber precursor in an acid solution with the concentration of 30-60% for acidification, refluxing at 60-160 ℃ for 3-48 h, discharging, filtering, centrifuging, washing to be neutral, and vacuum drying the precipitate at the constant temperature of 60-120 ℃ for 10-24 h to obtain the carbon nanofiber containing the functional group A, namely CNF-A;
the carbon nanofiber precursor is one of PR24-HHT, PR24-XT-HHT and SD2240 models, the particle size is 80-300 nm, and the specific surface is 300-1000 m2/g；
The above-mentionedThe acid solution is one of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid, and the carbon nanofiber surface is acidified to be provided with a specific functional group A; the functional group A is NO3、SO3H、Cl、PO3H;
B. dissolving soluble noble metal salt in deionized water to prepare a dipping solution with the concentration of 10-50 mmol/L;
the noble metal salt is Na2PdCl4、Pd(NH3)2Cl2、Pd(NO3)2、NaAuCl4、HAuCl4、H2IrCl6、Na2IrCl6、RhCl3·3H2O、Rh(CH3COO)3、Rh(NO3)3、AgNO3、AgC2H3O2One or two of them;
C. at room temperature, fully dispersing the CNF-A carrier in the step A into the impregnation solution in the step B according to the mass of the noble metal accounting for 0.5-5.0% of the carrier, continuously stirring for 0.5-2 h, filtering, and drying at the constant temperature of 60-120 ℃ for 6-24 h; then H is added2Volume fraction of 10% of H2In the mixed gas of/Ar at 2-10 deg.C/min-1Heating to 200-400 ℃ at the speed, and reducing for 2-6 h to obtain the functionalized carbon nanofiber loaded with the noble metal, wherein the functionalized carbon nanofiber is expressed as M/CNF-A, and M represents the noble metal; wherein the mass of the noble metal accounts for 0.5-2.0% of the mass of the carrier.
D. Placing the M/CNF-A obtained in the step C in a reactor, introducing heat treatment atmosphere, keeping the temperature for 5-50 h, keeping the flow rate at 10-50 mL/min, and keeping the temperature at 2-10 ℃ per min-1Heating to 50-350 ℃, keeping for 15-50 h, cooling to room temperature, taking out to obtain CH with controllable coating thickness and permeabilityx@ M/CNF-A catalyst;
the heat treatment atmosphere is alkyne, alkene and H containing unsaturated carbon-carbon bond2The mixed gas of (3); the alkyne and the alkene are C2H2、C2H4、C3H4、C3H6、C4H6、C4H8One or two ofSeed growing; wherein H2The molar ratio of the catalyst to alkyne is 2-10; when the alkyne and the olefin are simultaneously selected, the molar ratio of the alkyne to the olefin is 0.01-0.1.
The preparation method is characterized in that: reaction atmosphere induces the formation of CH on the surface of the active metal MxSpecies, promoting the electronic state of the active metal particles to change, and forming the permeable CH with controllable thickness by regulating and controlling the type, proportion and treatment time of the induction atmospherex@ M-CNF is favorable for diffusion and adsorption of reactant molecules, so that the catalyst has higher activity and product selectivity; in addition, CHxthe-M-CNF interface action enables the catalytically active metal particles to be small in size, inhibits migration and agglomeration in the reaction process, is beneficial to stable dispersion of active components, and has excellent stability.
FIG. 1 shows example 1 at C2H2/C2H4/H2Preparation of CH under an atmospherex@Pd/CNF-NO3High Resolution Transmission Electron Microscopy (HRTEM) pictures of the catalyst. According to the HRTEM photograph, the active metal components are uniformly dispersed on the surface of the carrier, the particle size range is 1-3 nm, the average particle size is 2.2nm, and a carbon coating layer is formed on the surface of the active metal and has the thickness of 1 nm.
In FIG. 2, C is the number of instances 12H2/C2H4/H2Preparation of CH under an atmospherex@Pd/CNF-NO3The picture of the catalyst dissolving process in the acid solution shows that the coating layer on the surface of the active metal has permeability and the permeability is good.
FIG. 3 shows example 2 at C4H6/H2Preparation of CH under an atmospherex@Pd/CNF-NO3High Resolution Transmission Electron Microscopy (HRTEM) pictures of the catalyst. From the HRTEM photograph, it can be seen that the active metal is uniformly distributed, the range is 1.5-7.0 nm, and the average particle size is 5.0 nm. The active metal surface forms a carbon coating with a thickness of 2 nm.
In FIG. 4 is C for example 24H6/H2Preparation of CH under an atmospherex@Pd/CNF-NO3Photograph of catalyst dissolution process in acid solution, from photographIt can be seen that the coating layer on the active metal surface is permeable.
FIG. 5 is CH prepared in example 1x@Pd/CNF-NO3The experimental result of the catalyst in the acetylene selective hydrogenation reaction shows that a is the curve of acetylene conversion rate to reaction temperature and b is the curve of ethylene selectivity to reaction temperature. When the reaction temperature is 250 ℃, the acetylene conversion is close to 100%, corresponding to an ethylene selectivity of 90%.
FIG. 6 is CH prepared in example 1x@Pd/CNF-NO3Stability of the catalyst in the selective hydrogenation of acetylene is bar chart. The catalyst continuously reacts for 25 hours, points are taken every 0.5 hour, the acetylene conversion rate is 100%, the ethylene selectivity is 90% +/-3%, and no obvious change exists.
FIG. 7 is CH prepared in example 2x@Pd/CNF-NO3The experimental result of the catalyst in the acetylene selective hydrogenation reaction shows that a is the curve of acetylene conversion rate to reaction temperature and b is the curve of ethylene selectivity to reaction temperature. When the reaction temperature was 250 ℃, the acetylene conversion was 100%, corresponding to an ethylene selectivity of 80%.
FIG. 8 is CH prepared in example 2x@Pd/CNF-NO3Stability of the catalyst in the selective hydrogenation of acetylene is bar chart. The catalyst continuously reacts for 25 hours, points are taken every 0.5 hour, the acetylene conversion rate is 100%, the ethylene selectivity is 80% +/-3%, and no obvious change exists.
The invention has the beneficial effects that:
the preparation method provided by the invention is characterized in that: carbon nano-fiber treated by acid solution is taken as a carrier, and after noble metal active components are loaded by adopting a traditional impregnation method, the carbon nano-fiber is subjected to heat treatment in a mixed atmosphere containing alkyne, so that CH is formed on the surface of active noble metal nano-particlesxCoating to obtain CHx@ M/CNF catalyst. The preparation condition is mild, the preparation process does not need to add a surfactant, and the process is simple and convenient.
The prepared catalyst has the advantages of small active metal particle size, high dispersity and narrow particle size distribution, and the carbon layer coated on the surface of the active metal has controllable thickness and permeability, so that rich CH is formedx-M-CNF worldThe surface sites solve the problems that the thickness of a coating layer of an interface structure constructed by the traditional method is difficult to accurately control, the coating layer does not have permeability, the active sites are extremely easy to excessively coat, and the like.
The catalyst can be applied to the selective hydrogenation reaction process of various unsaturated carbon-carbon triple bonds, has excellent C ≡ C bond hydrogenation activity and C ≡ C bond selectivity, has outstanding catalytic performance, is easy to recycle and reuse, and has good stability.
Description of the drawings:
FIG. 1 shows example 1 at C2H2/C2H4/H2Preparation of CH under an atmospherex@Pd/CNF-NO3High Resolution Transmission Electron Microscopy (HRTEM) pictures of the catalyst.
FIG. 2 shows example 1 at C2H2/C2H4/H2Preparation of CH under an atmospherex@Pd/CNF-NO3Photograph of the catalyst dissolved in acid solution.
FIG. 3 shows example 2 at C4H6/H2Preparation of CH under an atmospherex@Pd/CNF-NO3High Resolution Transmission Electron Microscopy (HRTEM) pictures of the catalyst.
In FIG. 4 is C for example 24H6/H2Preparation of CH under an atmospherex@Pd/CNF-NO3Photograph of the catalyst dissolved in acid solution.
FIG. 5 is CH prepared in example 1x@Pd/CNF-NO3The experimental result of the catalyst in the acetylene selective hydrogenation reaction shows that a is the curve of acetylene conversion rate to reaction temperature and b is the curve of ethylene selectivity to reaction temperature.
FIG. 6 is CH prepared in example 1x@Pd/CNF-NO3Stability profile of the catalyst in selective hydrogenation of acetylene.
FIG. 7 is CH prepared in example 2x@Pd/CNF-NO3The experimental result of the catalyst in the acetylene selective hydrogenation reaction shows that a is the curve of acetylene conversion rate to reaction temperature and b is the curve of ethylene selectivity to reaction temperature.
FIG. 8 is a preparation of example 2CH (A) ofx@Pd/CNF-NO3Stability profile of the catalyst in selective hydrogenation of acetylene.
The specific implementation mode is as follows:
example 1
A. 2g of carbon precursor with the model of PR24-HHT is roasted at 3000 ℃ for 2h, dispersed in nitric acid with the concentration of 50% for acidification, refluxed at 100 ℃ for 48h, discharged, filtered, centrifuged and washed to be neutral. Vacuum drying the obtained precipitate in a constant temperature dryer at 60 ℃ for 10h to obtain the product containing the functional group NO3Carbon nanofibers denoted as CNF-NO3The carrier size was 200 nm.
B. Weighing 0.6440g of PdCl20.4250g NaCl is dissolved in deionized water and the volume is adjusted to 100mL to prepare 36mmol/L Na2PdCl4And (3) solution.
C. 0.4g of the carbon nanofiber CNF-NO acid-treated in step A was added under continuous stirring at room temperature3Fully dispersed to 560 mu L of Na with the concentration of 36mmol/L prepared in the step B2PdCl4In the solution, the active metal Pd accounts for 1.0 wt% of the mass content of the carrier, the stirring is continuously carried out for 2H, the solution is placed in a constant temperature drier at 60 ℃ for drying for 24H, and then the solution is dried in 10% of H2In the mixed gas of/Ar at 10 ℃ for min-1The temperature is increased to 250 ℃ at the speed of (1) and the reduction is carried out for 2 hours to obtain the Pd/CNF-N catalyst.
D. Placing the Pd/CNF-N catalyst obtained in the step C into a reactor, and introducing a heat treatment atmosphere C2H2/C2H4/H2Keeping for 50H at a flow rate of 40mL/min, wherein the molar ratio of alkyne to alkene is 0.01, H2The molar ratio of the catalyst to the alkyne is 2, and the reaction temperature is 10 ℃ min-1Heating to 250 deg.C, maintaining for 50h, cooling to room temperature, and taking out to obtain CH with coating layer thickness of 1nm and permeabilityx@Pd/CNF-NO3A catalyst.
The catalyst prepared above was used in acetylene selective hydrogenation experiments:
0.05g of catalyst is weighed and fully mixed with 1.7mL of quartz sand with the particle size of 20-40 meshes, and then the mixture is loaded into a quartz reaction tube with the diameter of 7 mm. The gas components in the reaction feed gas are 0.6% of acetylene/1.2% of hydrogen/5.4% of ethylene/nitrogen balance gas, the test temperature of the catalytic performance is 50-250 ℃, the test temperature interval is 25 ℃, and the test pressure is 1 bar. The composition and content of reactants and products are analyzed by gas chromatography, the data processing mode is an internal standard method, and the internal standard substance is propane. In order to ensure the testing precision, the temperature is kept for 5h when the specified temperature is reached, and the point is taken for 1 time every 0.5h, and the result is shown in a figure 5; the catalyst was reacted continuously for 25h, taking 1 spot every 0.5h, and the results are shown in FIG. 6.
Example 2
A. 2g of carbon precursor with the model of PR24-XT-HHT is processed for 2h at 3000 ℃, dispersed in nitric acid with the concentration of 30 percent, refluxed for 48h at 100 ℃, discharged, filtered, centrifuged and washed to be neutral. Vacuum drying the obtained precipitate in a constant temperature drier at 100 deg.C for 10 hr to obtain the product containing functional group NO3Carbon nanofibers denoted as CNF-NO3The carrier size was 200 nm.
B. Weighing 0.6440g of PdCl20.4250g NaCl is dissolved in deionized water and the volume is adjusted to 100mL to prepare 36mmol/L Na2PdCl4And (3) solution.
C. 0.4g of the carbon nanofiber CNF-NO acid-treated in step A was added under continuous stirring at room temperature3Fully dispersed to 560 mu L of Na with the concentration of 36mmol/L prepared in the step B2PdCl4In the solution, the active metal Pd accounts for 1.0 wt% of the mass content of the carrier, the solution is continuously stirred for 2 hours, and is placed in a constant-temperature drier at 60 ℃ for drying for 24 hours, and then the solution is dried in H2Volume fraction of 10% of H2In the mixed gas of/Ar at 10 ℃ for min-1The temperature is increased to 250 ℃ at the speed of (1) and the reduction is carried out for 2 hours to obtain Pd/CNF-NO3A catalyst.
D. Placing the Pd/CNF-N catalyst obtained in the step C into a reactor, and introducing a heat treatment atmosphere C4H6/H2Keeping the reaction solution for 25H, wherein the flow rate is 50mL/min, the molar ratio of alkyne to olefin is 0.01, and H2The molar ratio of the catalyst to the alkyne is 2, and the reaction temperature is 10 ℃ min-1Heating to 250 deg.C, maintaining for 50h, cooling to room temperature, and taking out to obtain permeable CH with coating layer thickness of 2nmx@ Pd/CNF-N catalyst.
The catalyst prepared as described above was used in the experiment for the selective hydrogenation of acetylene according to the method of example 1, and the results are shown in fig. 7 and fig. 8.
Example 3
A. Treating 2g of carbon precursor with the model of SD2240 at 3000 ℃ for 6h, dispersing in 30% sulfuric acid for acidification, refluxing at 120 ℃ for 24h, discharging, filtering, centrifuging, and washing to neutrality. Vacuum drying the obtained precipitate in a constant temperature drier at 100 deg.C for 10h to obtain the product containing SO as functional group3Carbon nanofiber of H, noted CNF-SO3H, the size of the carrier is 100 nm.
B. Weighing 1g of AuCl3Dissolving in deionized water, diluting to 100mL, and preparing into 50mmol/L HAuCl4And (3) solution.
C. 1mL of 50mmol/L HAuCl4The solution was added to 110. mu.L of deionized water, and 0.2g of the acid-treated carbon nanofiber CNF-SO of step A was added under constant stirring at room temperature3Adding H into the above solution, wherein the active metal Au accounts for 5.0 wt.% of the mass content of the carrier, continuously stirring for 4H, placing in a constant temperature dryer at 80 ℃ for drying for 10H, and then drying in H2Volume fraction of 10% of H2In the mixed gas of/Ar at 2 ℃ for min-1The temperature is increased to 350 ℃ at the speed of (1) and the reduction is carried out for 4 hours to obtain Au/CNF-SO3And H, a catalyst.
D. The Au/CNF-SO obtained in the step C3Putting H catalyst in reactor, introducing heat treatment atmosphere C2H2/H2Keeping the reaction solution for 12H, the flow rate is 30mL/min, the molar ratio of alkyne to olefin is 0.1, and H2The molar ratio of the catalyst to the alkyne is 10, and the reaction temperature is 2 ℃ min-1Heating to 350 ℃, keeping the temperature for 20 hours, cooling to room temperature, and taking out to obtain the permeable CH with the coating layer thickness of 2.5nmx@Au/CNF-SO3And H, a catalyst.
Example 4
A. 2g of carbon precursor with the model of PR24-HHT is treated at 2000 ℃ for 6h, dispersed in 50% sulfuric acid for acidification, refluxed at 60 ℃ for 18h, discharged, filtered, centrifuged and washed to be neutral. The obtained precipitate is dried in a constant temperature dryer at 120 ℃ for 12 hours in vacuum to obtain the product containing the functional groupSO3Carbon nanofiber of H, noted CNF-SO3H, the size of the carrier is 150 nm.
B. Weighing 1g of AuCl3Dissolving in deionized water, diluting to 100mL, and preparing into 50mmol/L HAuCl4And (3) solution.
C. 1mL of 50mmol/L HAuCl4The solution was added to 110. mu.L of deionized water, and 0.2g of the acid-treated carbon nanofiber CNF-SO of step A was added under constant stirring at room temperature3H is added into the solution, wherein the active metal Au accounts for 5.0 wt% of the mass content of the carrier, the stirring is continuously carried out for 1.5H, the solution is placed in a constant temperature drier at 80 ℃ for drying for 20H, and then the solution is dried in H2Volume fraction of 10% of H2In the mixed gas of/Ar at 2 ℃ for min-1The temperature is increased to 300 ℃ at the speed of (1) and the reduction is carried out for 4 hours to obtain Au/CNF-SO3And H, a catalyst.
D. The Au/CNF-SO obtained in the step C3H catalyst is placed in a reactor, and the pulse heat treatment atmosphere is C3H4/C3H6/H2Keeping the reaction solution for 25H, the flow rate is 10mL/min, the molar ratio of alkyne to olefin is 0.1, and H2The molar ratio of the catalyst to the alkyne is 10 at 5 ℃ min-1Heating to 50 ℃, keeping the temperature for 15h, cooling to room temperature, and taking out to obtain the permeable CH with the coating layer thickness of 1nmx@Au/CNF-SO3And H, a catalyst.
Example 5
A. 2g of carbon precursor with the model of PR24-XT-HHT is processed for 4h at 2500 ℃, dispersed in phosphoric acid with the concentration of 30 percent for acidification, refluxed for 24h at 120 ℃, discharged, filtered, centrifuged and washed to be neutral. Vacuum drying the obtained precipitate in a constant temperature dryer at 80 ℃ for 10h to obtain PO containing the functional group3Carbon nanofiber of H, denoted as CNF-PO3H, the size of the carrier is 200 nm.
B. 0.26g of RhCl was weighed out3·3H2Dissolving O in deionized water, and metering to 100mL to prepare a precursor solution of 25mmol/L Rh.
C. 1.0ml of 25mmol/L RhCl3The solution was added to 150. mu.L of deionized water and 0.0858g of the acid-treated carbon of step A was added with constant stirring at room temperatureNanofiber CNF-PO3H is added into the solution, wherein the active metal Rh accounts for 3.0 wt.% of the mass content of the carrier, the stirring is continued for 1H, the solution is placed in a constant-temperature drier at 100 ℃ for drying for 24H, and then the drying is carried out in a H mode2Volume fraction of 10% of H2In the mixed gas of/Ar at 5 ℃ for min-1The temperature is increased to 350 ℃ at the speed of (1) and the reduction is carried out for 6 hours to obtain Rh/CNF-PO3And H, a catalyst.
D. The Rh/CNF-PO obtained in the step C3Putting H catalyst in reactor, introducing heat treatment atmosphere C2H2/C2H4/H2Keeping the reaction solution for 5 hours, wherein the flow rate is 50mL/min, the molar ratio of alkyne to olefin is 0.01, and H2The molar ratio of the catalyst to the alkyne is 5, and the reaction temperature is 5 ℃ min-1Heating to 100 deg.C, maintaining for 50h, cooling to room temperature, and taking out to obtain CH with coating layer thickness of 0.5nm and permeabilityx@Rh/CNF-PO3And H, a catalyst.
Example 6
A. 2g of carbon precursor PR24-HHT is treated at 2000 ℃ for 3h, dispersed in hydrochloric acid with the concentration of 50% for acidification, refluxed at 60 ℃ for 18h, discharged, filtered, centrifuged and washed to be neutral. And (3) drying the obtained precipitate in a constant-temperature dryer at 90 ℃ for 12h in vacuum to obtain the carbon nanofiber containing the functional group Cl, which is marked as CNF-Cl, and the size of the carrier is 100 nm.
B. 0.3878g Ir is weighed and dissolved in aqua regia and the volume is determined to be 100mL, and 20mmol/L Na is prepared2IrCl6A solution; weighing 0.6440g of PdCl2And 0.4250g NaCl is dissolved in deionized water and the volume is 100mL, so as to prepare 36mmol/LNa2PdCl4And (3) solution.
C. 5.0ml of 20mmol/L Na2IrCl6And 36mmol/L Na2PdCl4Adding the solution into 150 mu L of deionized water, adding 1.0g of the carbon nanofiber CNF-Cl subjected to acid treatment in the step A into the solution under the condition of constant stirring at room temperature, continuously stirring for 0.5H, wherein the active metals Pd and Ir respectively account for 2.0 wt.% of the mass content of the carrier, placing the solution into a constant-temperature dryer at 90 ℃ for drying for 6H, and then drying the dried solution in H2Volume fraction of 10% of H2In the mixed gas of/Ar at 10 ℃ for min-1Heating to 400 ℃ at the rate of the reaction, reducing, and keeping for 6 hours to obtain the PdIR/CNF-Cl catalyst.
D. Placing the PdIR/CNF-Cl catalyst obtained in the step C into a reactor, and introducing a heat treatment atmosphere C4H6/C4H8/H2Keeping the flow rate at 20mL/min for 45H, the molar ratio of alkyne to olefin at 0.1, and H2The molar ratio of the catalyst to the alkyne is 8, and the reaction temperature is 10 ℃ min-1Heating to 250 deg.C, maintaining for 45 hr, cooling to room temperature, and taking out to obtain permeable CH with coating layer thickness of 3nmx@ PdIr/CNF-Cl catalyst.
Claims (4)
1. A preparation method of an unsaturated carbon-carbon triple bond selective hydrogenation catalyst comprises the following specific steps:
A. roasting the carbon nanofiber precursor at 2000-3000 ℃ for 2-6 h, dispersing the carbon nanofiber precursor in an acid solution with the concentration of 30-60% for acidification, refluxing at 60-160 ℃ for 3-48 h, discharging, filtering, centrifuging, washing to be neutral, and vacuum drying the precipitate at the constant temperature of 60-120 ℃ for 10-24 h to obtain the carbon nanofiber containing the functional group A, namely CNF-A;
the carbon nanofiber precursor is one of PR24-HHT, PR24-XT-HHT and SD2240 models, the particle size is 80-300 nm, and the specific surface is 300-1000 m2/g；
The acid solution is one of nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid, and the carbon nanofiber surface is acidified to be provided with a specific functional group A; the functional group A is NO3、SO3H、Cl、PO3H;
B. dissolving soluble noble metal salt in deionized water to prepare a dipping solution with the concentration of 10-50 mmol/L;
the noble metal salt is Na2PdCl4、Pd(NH3)2Cl2、Pd(NO3)2、NaAuCl4、HAuCl4、H2IrCl6、Na2IrCl6、RhCl3·3H2O、Rh(CH3COO)3、Rh(NO3)3、AgNO3、AgC2H3O2One or two of them;
C. at room temperature, fully dispersing the CNF-A carrier in the step A into the impregnation solution in the step B according to the mass of the noble metal accounting for 0.5-5.0% of the carrier, continuously stirring for 0.5-2 h, filtering, and drying at the constant temperature of 60-120 ℃ for 6-24 h; then H is added2Volume fraction of 10% of H2In the mixed gas of/Ar at 2-10 deg.C/min-1Heating to 200-400 ℃ at the speed, and reducing for 2-6 h to obtain the functionalized carbon nanofiber loaded with the noble metal, wherein the functionalized carbon nanofiber is expressed as M/CNF-A, and M represents the noble metal;
D. placing the M/CNF-A obtained in the step C in a reactor, introducing heat treatment atmosphere, keeping the temperature for 5-50 h, keeping the flow rate at 10-50 mL/min, and keeping the temperature at 2-10 ℃ per min-1Heating to 50-350 ℃, keeping for 15-50 h, cooling to room temperature, taking out to obtain CH with controllable coating thickness and permeabilityx@ M/CNF-A catalyst;
the heat treatment atmosphere is alkyne, alkene and H containing unsaturated carbon-carbon bond2The mixed gas of (3); the alkyne and the alkene are C2H2、C2H4、C3H4、C3H6、C4H6、C4H8One or two of them; wherein H2The molar ratio of the catalyst to alkyne is 2-10; when the alkyne and the olefin are simultaneously selected, the molar ratio of the alkyne to the olefin is 0.01-0.1.
2. The preparation method of the unsaturated carbon-carbon triple bond selective hydrogenation catalyst according to claim 1, characterized in that the concentration of the dipping solution in the step B is 20-30 mmol/L; the noble metal salt is Na2PdCl4、HAuCl4And Na2IrCl6One of (1); c, the noble metal accounts for 0.5-2.0% of the mass of the carrier; step D wherein the heat treatment atmosphere is C2H2/C2H4/H2、C3H4/C3H6/H2And C4H6/H2One kind of (1).
3. An unsaturated carbon-carbon triple bond selective hydrogenation catalyst, represented as CH, prepared according to the process of claim 1x@ M/CNF-A, in which CHxIn the species, x is 1 or 2, M is a noble metal active component, and CNF-A is functionalized carbon nanofiber; m is one or two of noble metals Pd, Au, Ir, Rh and Ag, wherein the mass of the noble metals accounts for 0.5-5% of the total mass of the catalyst; a is a functional group NO3、SO3H、Cl、PO3One of H; the catalyst is characterized by comprising the following structural characteristics: m is loaded on CNF-A carrier and is subjected to heat treatment atmosphere to induce formed CHxThe layer is coated on the noble metal M, the thickness of the coating layer is controllable and has permeability, and the thickness is 0.5-3 nm; the active metal components are highly and stably dispersed on the surface of the carrier, the size is uniform, and the particle size is 1-3 nm.
4. The unsaturated carbon-carbon triple bond selective hydrogenation catalyst according to claim 3, characterized in that M is a noble metal Pd, Au or Ir, wherein the mass of the noble metal accounts for 0.5-2.0% of the total mass of the catalyst.
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