CN114100607A - Pd-based catalyst and preparation method and application thereof - Google Patents
Pd-based catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 113
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 99
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 52
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 38
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 38
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 16
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 3
- 238000001354 calcination Methods 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
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- 238000006243 chemical reaction Methods 0.000 description 12
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- 229910052593 corundum Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
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- -1 manganese-aluminum Chemical compound 0.000 description 7
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 229910052697 platinum Inorganic materials 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 102100021935 C-C motif chemokine 26 Human genes 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 101000897493 Homo sapiens C-C motif chemokine 26 Proteins 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 241000033695 Sige Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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Abstract
本发明提供了一种Pd基催化剂及其制备方法和用途，所述Pd基催化剂包括金属氧化物的载体以及负载在所属金属氧化物上的Pd催化中心，所述Pd基催化剂的表面及内部含有氮化碳，所述制备方法包括以下步骤：将金属氧化物粉末、二水硝酸钯溶液和三聚氰胺，溶解于溶液中、搅拌并烘干后，氮气气氛下焙烧，得到含有氮化碳的所述Pd基催化剂，可用于低温下甲苯的催化氧化；本发明通过原料中加入三聚氰胺以及在氮气气氛下焙烧，免高温氢还原、无需过滤就可以得到相比现有方案性能略优或持平的甲苯催化剂，所述方法无需复杂设备，简便易操作，节能环保，适合工业大规模生产。
The present invention provides a Pd-based catalyst and a preparation method and use thereof. The Pd-based catalyst comprises a metal oxide carrier and a Pd catalytic center supported on the metal oxide. The surface and interior of the Pd-based catalyst contain Carbon nitride, the preparation method includes the following steps: dissolving metal oxide powder, palladium nitrate dihydrate solution and melamine in the solution, stirring and drying, and calcining in nitrogen atmosphere to obtain the carbon nitride-containing Pd-based catalyst can be used for the catalytic oxidation of toluene at low temperature; in the present invention, by adding melamine to the raw material and calcining in a nitrogen atmosphere, a toluene catalyst with slightly better or equal performance than the existing solution can be obtained without high-temperature hydrogen reduction and without filtration The method does not require complex equipment, is simple and easy to operate, energy-saving and environmentally friendly, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the field of catalyst synthesis, and particularly relates to a Pd-based catalyst, and a preparation method and application thereof.
Background
The emission of Volatile Organic Compounds (VOCs) in the atmosphere is increasing year by year, and the VOCs are important precursors for forming near-ground ozone pollution and atmospheric haze, and seriously threaten the ecological environment. The catalytic oxidation technology is considered to be one of the most feasible technologies for removing VOCs due to the advantages of high efficiency, energy conservation, environmental protection and the like. The development of the catalyst is the core of a catalytic oxidation method and catalytic decomposition, and the improvement of the activity of the catalyst and the reduction of the cost of the catalyst are hot spots in the research field of VOCs and ozone catalysis. Wherein, the Pd catalyst has better oxidation capability and is a very effective catalyst for removing formaldehyde, toluene and dichloromethane at present. It is widely believed that the reduced Pd in metallic state is the active center of the catalyst and has high O content2The nanometer Pd particle with the activation capability has higher catalytic activity.
CN107159202A discloses a manganese-doped palladium supported catalyst, the preparation method of which is: PdCl2Adding into propylene carbonate, and performing reduction reaction for 0.5-3h under the conditions of hydrogen pressure of 1-4MPa and temperature of 20-60 ℃ to obtain Pd nano solution; mixing Al2O3Carrier addition to Mn (NO)3)2Soaking the solution for 5-15min by an equal-volume soaking method, drying, calcining for 3h at the temperature of 200-500 ℃, then adding the dried solution into a Pd nano solution for soaking for 5-15min, drying, and calcining for 2h at the temperature of 200-500 ℃ to obtain the catalyst, wherein the catalyst can be applied to the catalytic oxidation reaction of toluene; the catalyst prepared by the method has high active component dispersion degree and small particle size, can still keep higher activity and stability under the condition of lower load, but is reduced by using high-pressure hydrogen, so that the catalyst is dangerous and has high energy consumption.
CN104138756A discloses a supported mesoporous carbon catalyst RTCC-1 for low-temperature catalytic combustion of Volatile Organic Compounds (VOCs) and a preparation method thereof. The TSC-1 mesoporous carbon material with unique physicochemical properties is used as a carrier of the catalyst, so that the disadvantages of high active metal loading and high cost of the traditional catalytic combustion catalyst are eliminated. The active component of the load type low-temperature catalytic combustion catalyst prepared by the carrier is one of Pd or Pt noble metals combined with one or more oxides of copper oxide, cerium oxide, zirconium oxide, silicon oxide and aluminum oxide. The catalyst has very high catalytic combustion activity at room temperature, and can be used for completely catalytically combusting volatile organic compounds such as formaldehyde, toluene, benzene and the like at room temperature or lower temperature. The invention also adopts high-temperature hydrogen for reduction, and although the catalyst has good performance, the danger of the preparation process cannot be avoided.
CN101927162B discloses a supported catalyst for eliminating benzene series substances at low temperature, and preparation and application thereof, belonging to the technical field of catalytic combustion. The catalyst is Pt or Pd loaded on a manganese-aluminum pillared montmorillonite carrier, and the manganese-aluminum pillared montmorillonite carrier is prepared by inserting hydroxyl manganese-aluminum ions into the interlayer of sodium montmorillonite and then processing the mixture to prepare a composite material; the preparation method of the manganese aluminum pillared montmorillonite supported catalyst comprises the steps of adding a palladium nitrate or chloroplatinic acid solution into manganese aluminum pillared montmorillonite slurry, adjusting the pH to 8-10, and adding NaBH4The solution was stirred, washed with water to neutrality and dried. The catalyst has large specific surface area, ordered manganese-aluminum pillared structure and less loading of noble metals Pd and Pt; the catalyst is used for eliminating benzene series by low-temperature catalytic combustion, has extremely high efficiency and stability, but uses NaBH4The metal elements are reduced, ions in the reducing agent, such as boron ions and sodium ions, are easily adsorbed on the surface of the catalyst, so that the capacity of the catalyst for adsorbing and decomposing pollutants is reduced, and the method inevitably needs to be fully washed and filtered by a large amount of deionized water, so that a large amount of waste of resources is caused.
Therefore, there is a need to develop an energy-saving, environment-friendly and simple method for preparing Pd catalyst.
Disclosure of Invention
Aiming at the problems of poor safety, high energy consumption, high cost and the like in the prior art, the invention provides a Pd-based catalyst and a preparation method thereof, wherein the surface and the interior of the Pd-based catalyst have carbon nitride structures, and the method changes Pd/TiO by adding a proper amount of melamine2And Pd/Al2O3Physical and chemical properties, and roasting in nitrogen atmosphere to prepare the toluene catalyst with good activity. Said Pd-based catalysisThe catalyst is used for catalytically oxidizing toluene and removing VOCs in industrial tail gas.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a Pd-based catalyst comprising a metal oxide support and Pd catalytic sites supported on the metal oxide, the Pd-based catalyst comprising carbon nitride on the surface and in the interior.
The Pd-based catalyst provided by the invention has the carbon nitride structures on the surface and in the Pd-based catalyst, the carbon nitride can form a pi-electron conjugated system, and the Pd-based catalyst has good chemical stability and thermal stability, the carbon nitride is of a two-dimensional layered structure, so that the carbon nitride has high adsorption selectivity on toluene, the metallic Pd is used as the center of the catalyst, and the catalyst has good oxidation capacity on VOCs, so that the Pd-based catalyst which takes metal oxide as a carrier, takes Pd as a catalytic center, and has the carbon nitride structures on the surface and in the Pd-based catalyst has high catalytic activity on toluene.
In a preferred embodiment of the present invention, the Pd-based catalyst has a particle size of 40 to 60 mesh, for example, 40 mesh, 42 mesh, 45 mesh, 48 mesh, 50 mesh, 52 mesh, 55 mesh, 58 mesh or 60 mesh, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the metal oxide comprises TiO2And/or Al2O3。
Preferably, the mass fraction of the Pd element is 1-2% of the mass of the Pd-based catalyst, and may be, for example, 1%, 1.1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
In a second aspect, the present invention provides a method for preparing a Pd-based catalyst as set forth in the first aspect, comprising the steps of:
dissolving metal oxide powder, a palladium nitrate dihydrate solution and melamine in the solution, stirring and drying the solution, and roasting the solution in a nitrogen atmosphere to obtain the Pd-based catalyst containing carbon nitride.
The Pd/TiO is changed by adding a proper amount of melamine in the preparation method of the Pd-based catalyst provided by the invention2And Pd/Al2O3The catalyst has the advantages of good safety, cleanness, no pollution, suitability for large-scale popularization in industrial production, and avoidance of the safety problem of a hydrogen high-temperature reduction method and the environmental protection problem of a solvent reduction method.
In a preferred embodiment of the present invention, the metal oxide includes TiO2And/or Al2O3Further preferred is TiO2。
Preferably, the pore size of the metal oxide powder is 15-20nm, which may be, for example, 15nm, 16nm, 17nm, 18nm, 19nm or 20nm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferred technical solution of the present invention, the solvent of the palladium nitrate dihydrate solution is deionized water.
Preferably, the ratio of the volume of the palladium nitrate dihydrate solution to the mass of the metal oxide is (0.06-0.13) mL:1g, and may be, for example, 0.06mL:1g, 0.07mL:1g, 0.08mL:1g, 0.09mL:1g, 0.10mL:1g, 0.11mL:1g, 0.12mL:1g, or 0.13mL:1g, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the mass fraction of the Pd element is 1-2% of the catalyst mass, and may be, for example, 1%, 1.1%, 1.2%, 1.3%, 1.5%, 1.. 6%, 1.7%, 1.8%, 1.9%, or 2%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the concentration of the palladium nitrate dihydrate solution is 14-16 wt%, and may be, for example, 14 wt%, 14.2 wt%, 14.5 wt%, 14.8 wt%, 15 wt%, 15.2 wt%, 15.5 wt%, 15.8 wt%, or 16 wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
The mass ratio of melamine to metal oxide (0.05-0.2):1, preferably (0.05-0.1):1, can be, for example, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, 0.16:1, 0.17:1, 0.18:1, 0.19:1 or 0.2:1, but is not limited to the recited values, and other values not recited in this range of values are equally suitable.
As a preferred embodiment of the present invention, the solution includes deionized water.
Preferably, the ratio of the volume of the deionized water to the mass of the metal oxide is (18-22) mL:1g, and may be, for example, 18mL:1g, 19mL:1g, 20mL:1g, 21mL:1g, or 22mL:1g, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature of the drying is 80 to 120 ℃, preferably 90 to 110 ℃, and may be, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the temperature of the calcination is 450-550 ℃, preferably 480-520 ℃, and can be, for example, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃ or 550 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination time is 4-6h, preferably 4.5-5.5h, for example 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8h or 6h, but not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the initial melamine is added in an amount of 1-5% by mass of the final catalyst, for example 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, but not limited to the values recited, other values not listed in this range of values being equally applicable.
As a preferred embodiment of the present invention, the method comprises the steps of:
adding TiO into the mixture2And/or Al2O3Dissolving powder, 14-16 wt% of palladium nitrate dihydrate and melamine in deionized water, stirring, drying at 80-120 ℃, and roasting at 450-550 ℃ for 4-6h in nitrogen atmosphere to obtain the Pd-based catalyst containing carbon nitride.
Wherein, the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the mass ratio of the metal oxide powder are (0.06-0.13) mL, (0.05-0.2) g, (18-22) mL:1g, the mass fraction of the Pd element is 1-2% of the mass of the Pd-based catalyst, and the addition amount of the initial melamine is 1-5% of the mass of the final catalyst.
In a third aspect, the present invention provides the use of a Pd-based catalyst as described in the first aspect for the catalytic oxidation of toluene.
Compared with the prior art, the invention has the beneficial effects that:
(1) the Pd-based catalyst provided by the invention has a carbon nitride structure on the surface and in the interior, has very high catalytic activity on toluene, and has good chemical stability and thermal stability;
(2) the preparation method of the Pd-based catalyst provided by the invention has the advantages that the high-temperature hydrogen reduction is avoided, the catalyst with high activity and reusability can be obtained without filtration, complex equipment is not required, the operation is simple and convenient, the energy is saved, the environment is protected, and the preparation method is suitable for industrial large-scale production;
(3) the Pd-based catalyst provided by the invention is used for catalytic oxidation of toluene, and the prepared Pd/TiO2The conversion rate of 1000ppm toluene is close to 100 percent under the condition of 230 ℃ of the catalyst, and CO is2The selectivity reaches 100%, and the catalyst has good catalytic oxidation effect on toluene and VOCs.
Drawings
FIG. 1 is a graph comparing toluene conversion for example 1 and example 3 of the present invention;
FIG. 2 shows CO of examples 1 and 3 of the present invention2A yield comparison chart;
FIG. 3 is a graph comparing toluene conversion for example 1 and example 6 of the present invention;
FIG. 4 shows CO of examples 1 and 6 of the present invention2A yield comparison chart;
FIG. 5 is a graph comparing toluene conversion for examples 1, 4-5 of the present invention;
FIG. 6 shows CO of examples 1 and 4 to 5 of the present invention2A yield comparison chart;
FIG. 7 is a graph comparing toluene conversion for example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 8 is CO of example 1, comparative example 1 and comparative example 2 of the present invention2The yield is compared with the figure.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In one embodiment, the present invention provides a method for preparing a Pd-based catalyst, the method comprising the steps of:
adding TiO into the mixture2And/or Al2O3Dissolving 14-16 wt% of powder, 14-16 wt% of palladium nitrate dihydrate solution and melamine produced by Aladdin company in deionized water, stirring, drying at 80-120 ℃, and roasting at 450-550 ℃ for 4-6h in nitrogen atmosphere to obtain the Pd-based catalyst containing carbon nitride;
wherein the volume of the palladium nitrate dihydrate, the mass of the melamine, the mass ratio of the volume of the deionized water to the metal oxide powder are (0.06-0.13) mL, (0.05-0.2) g, (18-22) mL:1g, the mass fraction of the palladium element is 1-2% of the mass of the catalyst, and the addition amount of the initial melamine is 1-5% of the mass of the final catalyst.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
Example 1
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sigemou Aldrich and melamine produced by Aladdin company in deionized water, stirring with a magnetic stirrer until the mixture is fully mixed, drying at 100 ℃, and roasting at 550 ℃ for 5 hours in nitrogen atmosphere to obtain Pd/TiO2A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the metal oxide powder is 0.067g:0.068g:20ml:1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 5 percent of the mass of the final catalyst.
Example 2
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
al from Aladdin2O3Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sigemou Aldrich and melamine produced by Aladdin into deionized water, stirring with a magnetic stirrer until the mixture is fully mixed, drying at 100 ℃, and roasting at 550 ℃ for 5 hours in nitrogen atmosphere to obtain Pd/Al2O3A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the mass of the metal oxide powder is 0.067mL to 0.068g to 20mL to 1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 5 percent of the mass of the final catalyst.
Example 3
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sigemou Aldrich and melamine produced by Aladdin company in deionized water, stirring with a magnetic stirrer to mix thoroughly, drying at 80 deg.C, and roasting at 550 deg.C under nitrogen atmosphere for 5 hr to obtain Pd/TiO2A catalyst; wherein the volume of the palladium nitrate dihydrate, the mass of the melamine and the mass ratio of the volume of the deionized water to the metal oxide powder are 0.133mL to 0.0684g20ml of 1g, wherein the mass fraction of palladium element is 2 percent of the mass of the catalyst, and the addition amount of initial melamine is 5 percent of the mass of the final catalyst.
Example 4
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sigemou Aldrich and melamine produced by Aladdin company in deionized water, stirring with a magnetic stirrer until the mixture is fully mixed, drying at 100 ℃, and roasting at 550 ℃ for 5 hours in nitrogen atmosphere to obtain Pd/TiO2A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the mass of the metal oxide powder is 0.067mL to 0.014g to 20mL to 1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 1 percent of the mass of the final catalyst.
Example 5
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sigemou Aldrich and melamine produced by Aladdin company in deionized water, stirring with a magnetic stirrer until the mixture is fully mixed, drying at 100 ℃, and roasting at 550 ℃ for 5 hours in nitrogen atmosphere to obtain Pd/TiO2A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the mass of the metal oxide powder is 0.067mL to 0.37g to 20mL to 1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 2 percent of the mass of the final catalyst.
Example 6
This example provides a method for preparing a Pd-based catalyst, comprising the steps of:
rutile TiO produced by Aladdin corporation2Powder, 15 wt% palladium nitrate dihydrate solution from SigemoOodrich, raw AradinDissolving the produced melamine in deionized water, stirring the mixture by using a magnetic stirrer until the melamine is fully mixed, drying the mixture at the temperature of 120 ℃, and roasting the dried mixture for 5 hours at the temperature of 600 ℃ in nitrogen atmosphere to obtain Pd/TiO2A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the mass of the metal oxide powder is 0.067mL to 0.068g to 20mL to 1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 5 percent of the mass of the final catalyst.
Comparative example 1
This comparative example provides a method of preparing a Pd catalyst, the method comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving powder, 15 wt% palladium nitrate dihydrate solution produced by Sige bridge Oddrich and melamine produced by Aladdin company in deionized water, stirring by using a magnetic stirrer until the mixture is fully mixed, drying at 100 ℃, and roasting for 5 hours at 550 ℃ in air atmosphere to obtain a Pd/TiO2 catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the mass of the melamine, the volume of the deionized water and the metal oxide powder is 0.067mL to 0.068g to 20mL to 1g, the mass fraction of the palladium element is 1 percent of the mass of the catalyst, and the addition amount of the initial melamine is 5 percent of the mass of the final catalyst.
Comparative example 2
This comparative example provides a method of preparing a Pd catalyst, the method comprising the steps of:
rutile TiO produced by Aladdin corporation2Dissolving the powder and 15 wt% palladium nitrate dihydrate solution produced by SiGeqiao Oodrich in deionized water, stirring with a magnetic stirrer to mix thoroughly, drying at 100 deg.C, and calcining at 550 deg.C for 5 hr to obtain Pd/TiO2A catalyst; wherein the mass ratio of the volume of the palladium nitrate dihydrate, the volume of the deionized water and the metal oxide powder is 0.067g to 20ml to 1g, and the mass fraction of the palladium element is 1 percent of the mass of the catalyst.
The catalysts prepared by the methods of examples 1-6 and comparative examples 1-2 were put into a catalyst activity evaluation device, and activity evaluation was performed in a fixed bed reactor to simulate wasteThe gas composition was 1000ppm toluene, 20% O2，N2The total flow rate for the balance gas was 200mL/min, and the amount of catalyst was 0.1 g.
Toluene conversion ratio of examples 1 and 3 versus CO of examples 1 and 3 as shown in FIG. 12Yield vs. toluene conversion for examples 1 and 6 vs. CO for examples 1 and 6 as shown in FIG. 2 and FIG. 32Yield ratio as shown in FIG. 4, it can be seen from FIGS. 1 to 4 that the catalyst prepared by the present invention has high toluene conversion and CO2High yield.
Comparison of toluene conversion for examples 1 and 4-5 As shown in FIG. 5, CO for examples 1 and 4-52Yield ratio as shown in fig. 6, it can be seen that the mass ratio of melamine to metal oxide is less than 0.05:1, which has a significant inhibiting effect on the performance of the catalyst, and example 5, with a further increase in the amount of melamine used, the catalyst effect is not improved, so the mass ratio of melamine to metal oxide is preferably (0.05-0.2): 1.
Toluene conversion ratio of example 1 and comparative example 1 CO of example 1 and comparative example 1 as shown in FIG. 72The yield ratio is shown in figure 8, and it can be seen that adding a proper amount of melamine and roasting with nitrogen can obviously increase Pd/TiO2The activity of the catalyst can replace a treatment mode of hydrogen reduction, and the catalyst is more environment-friendly and industrially applied.
T for examples 1 to 6 and comparative examples 1 to 250(temperature for 50% VOC removal) and T90(temperature at which 90% of VOC was removed) is shown in Table 1.
TABLE 1
| T50(toluene)/[ deg.C | T90(toluene)/[ deg.C | |
| Example 1 | 183.0 | 195 |
| Example 2 | 213.3 | 230.2 |
| Example 3 | 179.8 | 195.0 |
| Example 4 | 213.2 | 239.2 |
| Example 5 | 182.2 | 195 |
| Example 6 | 182.5 | 198.4 |
| Comparative example 1 | 250.5 | 277.1 |
| Comparative example 2 | 213.7 | 233.6 |
From fig. 1-4 and table 1, the following points can be seen:
(1) as can be seen from examples 1-3 and 6, the Pd-based catalyst provided by the invention is prepared by roasting Pd with melamine and nitrogen2And Pd/Al2O3The catalyst has good catalytic oxidation performance to toluene, Pd/TiO2T of catalyst50≤183℃，T90≤198.4℃，Pd/Al2O3T of catalyst50At 213.3 ℃ and T90At 230.2 ℃ CO2The conversion rate of (a) is close to 100%, and therefore, the preparation method with higher safety can obtain the Pd-based catalyst with excellent catalytic oxidation effect;
(2) as can be seen from examples 1 and 4-5, the volume of palladium nitrate dihydrate, the mass of melamine, and the mass ratio of the volume of deionized water to the metal oxide powder in examples 4 and 5 were 0.067g:0.014g:20ml:1g and 0.067g:0.37g:20ml:1g, respectively, which are lower or higher than the mass of melamine in example 1, and Pd/TiO prepared by the method of example 12T of catalyst50And T90183 ℃ and 195 ℃ respectively, and Pd/TiO prepared by the methods of example 4 and example 52T of catalyst50213.2 ℃ and 182.2 ℃ respectively, T90The temperature is 239.2 ℃ and 195 ℃ respectively, which proves that the addition amount of melamine in the Pd-based catalyst provided by the invention is preferably in a certain range, and Pd/TiO with better toluene catalytic performance can be obtained2A catalyst;
(3) as can be seen from example 1 and comparative example 1, in comparative example 1, TiO is used2Calcination of a metal oxide substrate in an air atmosphere, comparative example 1 with TiO2Scheme for roasting metal oxide substrate with nitrogen, Pd/TiO obtained in comparative example 12T of catalyst50And T90250.5 ℃ and 277.1 ℃ respectively, and the Pd/TiO obtained in example 12T of catalyst50And T90183 ℃ and 195 ℃ respectively; therefore, the Pd-based catalyst with the toluene catalytic oxidation performance is prepared by adopting a nitrogen roasting method;
(4) as can be seen from example 1, comparative example 1 and comparative example 2, comparative example 1 employed air firing toAnd melamine is added, the comparative example 2 only adopts air roasting and does not add melamine, compared with the scheme that the nitrogen roasting is adopted and the melamine is added in the example 1, the Pd/TiO obtained in the example 12T of catalyst50And T90183 ℃ and 195 ℃ respectively; Pd/TiO obtained in comparative example 12T of catalyst50And T90250.5 ℃ and 277.1 ℃ respectively, Pd/TiO obtained in comparative example 22T of catalyst50And T90213.7 ℃ and 233.6 ℃ respectively, thus illustrating that the Pd-based catalyst with toluene catalytic oxidation performance can be prepared by the roasting method of adding melamine in the preferred range and combining nitrogen.
In conclusion, the method for roasting melamine and nitrogen can prepare Pd/TiO with toluene catalytic effect2And Pd/Al2O3The catalyst provided by the invention has the conversion rate of 1000ppm toluene close to 100 percent at 230 ℃, and CO2The selectivity reaches 100%, and the catalytic performance is far better than that of a catalyst prepared by air, which shows that the Pd catalyst has good catalytic performance due to the addition of melamine and roasting in nitrogen atmosphere.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
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