CN114160158A - Transition metal modified palladium nanocluster loaded on cerium oxide catalytic material, and preparation method and application thereof - Google Patents
Transition metal modified palladium nanocluster loaded on cerium oxide catalytic material, and preparation method and application thereof Download PDFInfo
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- CN114160158A CN114160158A CN202111496225.7A CN202111496225A CN114160158A CN 114160158 A CN114160158 A CN 114160158A CN 202111496225 A CN202111496225 A CN 202111496225A CN 114160158 A CN114160158 A CN 114160158A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 63
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 46
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 41
- -1 Transition metal modified palladium Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 79
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000001294 propane Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000003795 desorption Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 229910021069 Pd—Co Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 229910021065 Pd—Fe Inorganic materials 0.000 description 2
- 229910021076 Pd—Pd Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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Abstract
The invention discloses a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material, and a preparation method and application thereof, wherein a palladium source and a transition metal salt are added into a hydrochloric acid solution, the mixture is uniformly stirred, then a cerium oxide carrier is added, the pH value is adjusted to 9-9.5, the palladium salt is loaded on the cerium oxide carrier by stirring, the mixture is kept stand to separate solid from liquid, the solid is washed, dried and roasted to obtain the transition metal modified palladium nanocluster loaded on the cerium oxide catalytic material, the mass percent of palladium in the transition metal modified palladium nanocluster loaded on the cerium oxide catalytic material is 1.0-2.0%, and the mass percent of transition metal is 0.5-1.0%. The material has rich oxygen vacancies, high palladium dispersity, and better oxidation property of low-carbon alkane, better water resistance and stability, regeneration and lower cost compared with an unmodified pure palladium supported catalyst.
Description
Technical Field
The invention relates to a catalytic material for eliminating low-carbon alkane oxidation, in particular to a cerium oxide catalytic material loaded with transition metal modified palladium nanoclusters, a preparation method and application thereof.
Background
With the rapid development of economy, the increasing industrialization of human causes great damage to the ecological environment, the problem of atmospheric pollution becomes serious, and the sustainable development of human beings is threatened. Volatile Organic Compounds (VOCs) are a major atmospheric pollutant, and in industrial production, they are mainly derived from processes such as production of liquid fuels, special chemicals, industrial solvents, and organic polymers. In addition, in indoor environments, building materials, interior materials, and office supplies, such as paints, wood board adhesives, household fuels, detergents, etc., also often tend to produce VOCs. VOCs are various in types, most of the VOCs are toxic and some of the VOCs are carcinogenic, photochemical smog can be generated legally under the illumination condition, the ozone layer can be damaged, great harm is brought to human bodies, and irreparable damage is caused to the global environment. Therefore, air pollution control becomes a problem to be solved at present. The low-carbon alkane is one of important VOCs, and mainly comes from the emission of automobile exhaust, incomplete combustion of fuel, petrochemical industry and the like. The treatment methods commonly used at present include combustion, adsorption, absorption, condensation, biological, membrane separation, photocatalytic oxidation, and the like. In the combustion method, catalytic combustion is the current popular research direction because of the characteristics of good safety, low combustion temperature, small limit on the concentration and heat value of combustible components, high combustion efficiency and the like.
In catalytic oxidation reactions, the performance of the catalyst plays a crucial role in combustion efficiency. At present, the catalyst commonly used in industry is a noble metal catalyst, such as Pt, Pd, Ru, Rh and the like, and the outermost layer of the catalyst has more valence electrons and can effectively activate C-H bonds. However, noble metal catalysts are expensive and the use of a pure noble metal as an active component tends to result in higher catalyst costs. The non-noble metal catalyst, especially the transition metal of the VIII main group, such as Fe, Co, Ni and the like, has stronger electron gain and loss capacity and also shows excellent initial activity because the outermost layer is an unsaturated 3d orbit. However, such non-metallic catalysts are generally less stable and have a shorter service life than noble metal catalysts.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material comprises the following steps:
adding a palladium source and a transition metal salt into a hydrochloric acid solution, uniformly stirring, then adding a cerium oxide carrier, adjusting the pH value to 9-9.5, stirring to load the palladium salt on the cerium oxide carrier, standing to separate solid from liquid, washing the solid, drying, and then roasting to obtain a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material, wherein the mass percent of palladium in the transition metal modified palladium nanocluster loaded on the cerium oxide catalytic material is 1.0-2.0%, and the mass percent of transition metal is 0.5-1.0%.
Further, the palladium source is palladium acetate or palladium chloride.
Further, the transition metal salt is iron salt, cobalt salt or nickel salt.
Further, the iron salt is ferric nitrate or ferric chloride, the cobalt salt is cobalt nitrate or cobalt chloride, and the nickel salt is nickel nitrate or nickel chloride.
Further, the mass concentration of the hydrochloric acid solution is 37%, and the mass ratio of the palladium source to the hydrochloric acid is 1: 2.
Furthermore, the pH value is adjusted by adopting a sodium carbonate solution.
Further, the specific conditions of roasting are as follows: heating from room temperature to 500-600 ℃ at a heating rate of 2-5 ℃/min, and roasting for 4-6 hours.
The transition metal modified palladium nanocluster prepared by the method is loaded on a cerium oxide catalytic material.
The application of the transition metal modified palladium nanocluster loaded on the cerium oxide catalytic material in alkane oxidation elimination is disclosed.
Further, loading 300mg of transition metal modified palladium nanocluster on a cerium oxide catalytic material, placing the cerium oxide catalytic material into a quartz tube, introducing reaction gas, wherein the flow rate is 100mL/min, and the reaction space velocity is 20000mL/h/gcatReacting at 200-400 ℃; wherein the volume percentage of propane in the reaction gas is 0.1 percent, and O2The volume percentage of (A) is 21 percent, and the rest is N2。
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the transition metal is adopted to modify the Pd nanoclusters, and because the outermost layer orbit of the transition metal is an unsaturated 3d orbit, the Pd nanoclusters have strong electron gain and loss capacity, and the performance of the catalyst can be effectively improved. And part of the palladium is replaced by transition metal, when the content of Pd is 1.0-2.0%, and the content of transition metal is 0.5-1.0%, the Pd-Pd bond is favorable for activating C-H bond, and the Pd and transition metal bond are favorable for activating C-C bond. Therefore, under the condition of not influencing the C-H bond activation capability of the catalyst, the C-C bond activation capability of the catalyst can be effectively enhanced through partial substitution, so that the low-carbon alkane oxidation activity and the stability of the catalyst are improved.
Furthermore, the cheap transition metal (Fe, Co and Ni) is adopted to modify the Pd nanocluster, so that the cost of the catalyst can be effectively reduced.
Furthermore, the calcination temperature of the catalyst is 500-600 ℃, and the calcination temperature is too low, so that the catalyst is not easy to form a crystalline phase; the calcination temperature is too high, and the catalyst nanoparticles are easy to aggregate, which is not favorable for catalytic reaction performance.
The material prepared by the invention has rich oxygen vacancies, the dispersion degree of palladium is higher, compared with an unmodified pure palladium-loaded catalyst, the transition metal-substituted catalyst has better low-carbon alkane oxidation performance, better water resistance and stability, renewability and lower cost, and provides a guiding idea for designing and preparing the high-efficiency and low-cost low-carbon alkane oxidation catalyst.
Drawings
FIG. 1 shows Pd-3DTM/CeO of the present invention2X-ray diffraction pattern of the catalyst.
FIG. 2 shows Pd-3DTM/CeO of the present invention2The propane catalytic oxidation activity of the catalyst is shown.
FIG. 3 shows Pd-Co/CeO according to the present invention2The results of the catalyst stability and water resistance tests, wherein (a) is a propane conversion rate graph, and (b) is a carbon dioxide yield graph.
FIG. 4 shows Pd-3DTM/CeO of the present invention2O of catalyst2The attached drawing is sucked and removed.
Detailed Description
The following examples and drawings will help to understand the present invention, but do not limit the content of the present invention.
According to the invention, the VIII main group transition metal (Fe, Co, Ni) is adopted to modify the Pd nanocluster, and because the outermost layer orbit of the group elements is an unsaturated 3d orbit, the Pd nanocluster has strong electron gain and loss capacity, and can effectively improve the performance of the catalyst. The method comprises the steps of adopting a transition metal modified palladium nanocluster catalytic material, and replacing partial palladium with transition metal, wherein the total mass fraction of Pd and the transition metal is preferably 2%, the content of Pd is 1.5%, the content of the transition metal is 0.5%, Pd-Pd bonds are favorable for activating C-H bonds, and Pd-3DTM (DTM is a 3 d-group transition metal) bonds are favorable for activating C-C bonds. Therefore, under the condition of not influencing the C-H bond activation capability of the catalyst, the C-C bond activation capability of the catalyst can be effectively enhanced through partial substitution, so that the low-carbon alkane oxidation activity and the stability of the catalyst are improved. In addition, the cheap transition metal (Fe, Co and Ni) is adopted to modify the Pd nanocluster, so that the cost of the catalyst can be effectively reduced.
The invention discloses a preparation method of a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material, which comprises the following steps:
ammonia water is used as a precipitator, cerium nitrate is used as a cerium source, and a cerium oxide carrier is obtained by a precipitation method; the specific process is as follows: 20mmol of Ce (NO)3)3·6H2Dissolving O in 50mL of deionized water, stirring until the solution is clear, then dropwise adding ammonia water, adjusting the pH value to 9-9.5, stirring for 2 hours, carrying out suction filtration for 3 times, washing, putting the solution into an oven at 80 ℃ for drying for 12 hours, finally transferring the solution into a muffle furnace, heating the solution from room temperature to 500 ℃ at the heating rate of 2 ℃/min, and roasting the solution in the air for 5 hours to obtain the cerium oxide carrier.
The cerium oxide carrier in the embodiment of the invention is prepared by the method.
Dissolving a palladium source and a transition metal salt in a hydrochloric acid solution, stirring and clarifying to obtain a solution, adding the prepared cerium oxide carrier into the solution, then adding a precipitator (sodium carbonate solution) to adjust the pH value to 9-9.5, stirring for 2-4 hours to load the palladium salt on the cerium oxide carrier, enabling the load to be more uniform, standing to separate solid from liquid, washing the solid with deionized water for three times, drying for 12 hours, roasting the obtained solid in a muffle furnace, heating from room temperature to 500-600 ℃ at the heating rate of 2-5 ℃/min, and roasting for 4-6 hours to obtain the cerium oxide supported palladium nanocluster catalytic material, namely the transition metal modified palladium nanocluster supported on the cerium oxide catalytic material.
Wherein the palladium source is palladium acetate or palladium chloride.
The mass concentration of the hydrochloric acid solution is 37%. The mass ratio of the palladium source to the hydrochloric acid was 1: 2.
The transition metal salt is ferric salt, cobalt salt or nickel salt.
The ferric salt is ferric nitrate or ferric chloride, and the mass percentage of the ferric in the catalyst is 0.5-1.0%.
The cobalt salt is cobalt nitrate or cobalt chloride, and the mass percentage of the cobalt in the catalyst is 0.5-1.0%.
The nickel salt is nickel nitrate or nickel chloride, and the mass percentage of nickel in the catalyst is 0.5-1.0%.
The mass percentage content of the palladium in the cerium oxide catalytic material loaded with the transition metal modified palladium nanocluster is 1.0-2.0%.
The loading amount in the invention is the mass percentage content.
The transition metal modified palladium nanocluster is loaded on a cerium oxide catalytic material and is applied to oxidation and elimination of low-carbon alkane.
The specific application method comprises the following steps: loading 300mg of transition metal modified palladium nanocluster screened from 40 meshes to 60 meshes on cerium oxide catalytic material, putting the cerium oxide catalytic material into a quartz tube, introducing reaction gas, wherein the flow rate is 100mL/min, and the reaction space velocity is 20000mL/h/gcatReacting at 200-400 ℃; wherein the volume percentage of propane in the reaction gas is 0.1 percent, and O2The volume percentage of (A) is 21 percent, and the rest is N2。
Example 1
First 0.0632g of palladium acetate Pd (OAC)2Dissolved in a 37% strength by mass hydrochloric acid solution (amount of substance ratio Pd (OAC))2Hydrochloric acid 1:2, stirring for clarification, adding 0.0721g Fe (NO)3)3 .9H2O, stirring and clarifying, adding 1.96g of the prepared CeO2The carrier was stirred for 30 minutes and then 2mol/L Na was added dropwise2CO3The solution was adjusted to pH 9, stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, drying the obtained precipitate in an oven at 80 ℃ for 12 hours, then transferring to a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and roasting for 4 hours to obtain Pd-Fe/CeO2A catalyst.
The supported amount of Pd was 1.5% and the supported amount of Fe was 0.5%. The catalyst was noted as 1.5Pd +0.5Fe/CeO2。
Example 2
First 0.05g of PdCl2Dissolved in a hydrochloric acid solution with a mass concentration of 37% (the ratio of the amount of the substances PdCl)2Hydrochloric acid 1:2, stirring for clarification, adding 0.0740g of Co (NO)3)2 .6H2O, stirring and clarifying, adding 1.96g of the prepared CeO2The carrier was stirred for 30 minutes and then 2mol/L Na was added dropwise2CO3The solution was adjusted to pH 9, stirred for 2 hours and then allowed to stand for 2 hours. Then useWashing with deionized water, extracting for 3 times, drying the obtained precipitate in an oven at 80 deg.C for 12 hr, transferring to a muffle furnace, heating to 500 deg.C at a heating rate of 2 deg.C/min, and calcining for 4 hr to obtain Pd-Co/CeO2A catalyst.
The loading amount of Pd was 1.5%, and the loading amount of Co was 0.5%. The catalyst was noted as 1.5Pd +0.5Co/CeO2。
Example 2 differs from example 1 in that the transition metal element is Co.
Example 3
First 0.0632g of palladium acetate Pd (OAC) are weighed2Dissolved in a 37% strength by mass hydrochloric acid solution (amount of substance ratio Pd (OAC))2Hydrochloric acid 1:2, stirring to clarify, adding Ni (NO) 0.0744g3)2 .6H2O, stirring and clarifying, adding 1.96g of the prepared CeO2The carrier is stirred for 30 minutes, and then 2mol/L NaCO is added dropwise3The solution was adjusted to pH 9, stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, drying the obtained precipitate in an oven at 80 ℃ for 12 hours, then transferring to a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and roasting for 4 hours to obtain Pd-Ni/CeO2A catalyst.
The amount of Pd supported was 1.5%, and the amount of Ni supported was 0.5%. The catalyst was noted as 1.5Pd +0.5Ni/CeO2。
Example 3 differs from examples 1 and 2 in that the transition metal element is Ni.
Comparative example 1
First, 0.0843g of palladium acetate Pd (OAC) was weighed2Dissolving in hydrochloric acid solution (Pd (OAC)2Hydrochloric acid 1:2), stirring to clarify, adding 1.96g of the prepared CeO2The carrier was stirred for 30 minutes and then 2mol/L Na was added dropwise2CO3The pH of the solution was adjusted to about 9, and the solution was stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, drying the obtained precipitate in an oven at 80 ℃ for 12 hours, then transferring to a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, and roasting for 4 hours to obtain Pd/CeO2A catalyst.
The supported amount of Pd was 2%. The catalyst was noted as 2Pd/CeO2。
The propane oxidation activity test of example 1, example 2, example 3 and comparative example 1 was carried out in a fixed reaction bed, 300mg of a catalyst having a particle size of 40-60 mesh was weighed into a quartz tube, and 1000ppm of C was passed through the quartz tube3H8+21％O2/N2Reaction gas (100 mL/min; GHSV: 20000 mL/h/g)cat) The test temperature range is 200-400 ℃, and the tail gas is detected by adopting a gas chromatography with an FID detector.
Examples 1, 2, 3 and comparative example 1 were variously characterized by an X-ray diffractometer and a chemisorption meter.
The X-ray diffraction patterns of examples 1, 2, 3 and 1 are shown in FIG. 1, together with pure CeO2Compared with the carrier, the catalyst loaded with Pd has no obvious characteristic diffraction peak of other substances, and CeO is used2Mainly the crystalline phase of (A), indicating that Pd species are highly dispersed in CeO2A carrier surface. The degree of dispersion of the active metal is generally closely related to the performance of the catalyst, with higher degrees of dispersion being more favorable for the catalyst reactivity.
The propane oxidation activities of example 1, example 2, example 3 and comparative example 1 are shown in FIG. 2, 2Pd/CeO compared to pure Pd2The catalyst and the transition metal substituted catalyst all show better propane oxidation performance, and the activity is as follows: 1.5Pd +0.5Co/CeO2>1.5Pd+0.5Ni/CeO2>1.5Pd+0.5Fe/CeO2>2Pd/CeO2Wherein 1.5Pd +0.5Co/CeO2The catalyst exhibited an optimum propane elimination capacity with a propane conversion of 90% (T)90) At a temperature of 260 ℃ and 1.5Pd +0.5Ni/CeO2T of catalyst90At 290 ℃ and 1.5Pd +0.5Fe/CeO2And 2Pd/CeO2T of90300 c is reached. The results of the propane catalytic oxidation test show that the performance of the catalyst can be effectively improved while the use cost of the catalyst is reduced by the substitution of the transition metal.
Oxidation stability and Water resistance of propane in example 2The results of the sexual test are shown in FIGS. 3 (a) and (b), and T is selected90The temperature of (1) is the stability test temperature, and the optimal catalyst in the group of catalysts is 1.5Pd +0.5Co/CeO2The catalyst was tested for stability and water resistance at 260 ℃. According to the stability and water resistance test results, 1.5Pd +0.5Co/CeO2The propane conversion of the catalyst had reached more than 90% in the initial 30 minutes, the propane conversion did not drop significantly after 5% and 10% steam was added, and the propane conversion returned to more than 90% of the previous conversion after the steam addition was stopped, and did not drop significantly after the 20 hour test. 1.5Pd +0.5Co/CeO2The stability and water resistance test results of the catalyst show that the catalyst shows better water resistance and stability.
Example 4
First 0.0632g of palladium acetate Pd (OAC)2Dissolved in a 37% strength by mass hydrochloric acid solution (amount of substance ratio Pd (OAC))2Hydrochloric acid 1:2), adding ferric chloride after stirring and clarifying, adding the prepared CeO after stirring and clarifying2The carrier was stirred for 30 minutes and then 2mol/L Na was added dropwise2CO3The pH of the solution was adjusted to 9.5, and the solution was stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, drying the obtained precipitate in an oven at 80 ℃ for 12 hours, then transferring to a muffle furnace, heating to 600 ℃ at the heating rate of 2 ℃/min, and roasting for 4 hours to obtain Pd-Fe/CeO2A catalyst. The mass percent of palladium and iron in the transition metal modified palladium nanocluster loaded in the cerium oxide catalytic material is 1.0%, and the mass percent of iron is 0.5%.
Example 5
First 0.05g of PdCl2Dissolved in a hydrochloric acid solution with a mass concentration of 37% (the ratio of the amount of the substances PdCl)2Hydrochloric acid 1:2), adding cobalt chloride after stirring and clarifying, adding the prepared CeO after stirring and clarifying2The carrier was stirred for 30 minutes and then 2mol/L Na was added dropwise2CO3The solution was adjusted to pH 9, stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, and collecting precipitate at 8Drying in an oven at 0 ℃ for 12 hours, transferring to a muffle furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, and roasting for 6 hours to obtain Pd-Co/CeO2A catalyst.
The mass percent of palladium and cobalt in the transition metal modified palladium nanocluster loaded in the cerium oxide catalytic material is 1.5%, and the mass percent of cobalt is 1.0%.
Example 6
First 0.0632g of palladium acetate Pd (OAC) are weighed2Dissolved in a 37% strength by mass hydrochloric acid solution (amount of substance ratio Pd (OAC))2Hydrochloric acid 1:2), stirring to clarify, adding nickel chloride, stirring to clarify, adding the above-mentioned prepared CeO2The carrier is stirred for 30 minutes, and then 2mol/L NaCO is added dropwise3The pH of the solution was adjusted to 9.5, and the solution was stirred for 2 hours and then allowed to stand for 2 hours. Then washing with deionized water and pumping for 3 times, drying the obtained precipitate in an oven at 80 ℃ for 12 hours, then transferring to a muffle furnace, heating to 550 ℃ at the heating rate of 2 ℃/min, and roasting for 5 hours to obtain Pd-Ni/CeO2A catalyst.
The mass percent of palladium and nickel in the transition metal modified palladium nanocluster loaded in the cerium oxide catalytic material is 2.0%, and the mass percent of nickel is 0.7%.
For the oxidation elimination reaction, the adsorption capacity of the catalyst to oxygen generally affects the use performance of the catalyst, and in order to further investigate the adsorption capacity of the catalyst to oxygen, O was performed on example 1, example 2, example 3 and comparative example 12The adsorption and desorption tests showed the results shown in FIG. 4. Different desorption temperatures indicate that the adsorption capacity of the catalyst to oxygen is different, and the higher the desorption temperature is, the stronger the adsorption capacity of the catalyst to oxygen is. The types of desorption peaks are divided into three types of alpha, beta and gamma according to the desorption temperature from low to high, and the three types of desorption peaks are weakly adsorbed oxygen, moderately adsorbed oxygen and strongly adsorbed oxygen respectively. The amount of oxygen adsorbed was quantified from the peak areas obtained by integrating the three peak areas. According to the oxygen absorption and desorption result, 2Pd/CeO2The area of the oxygen desorption peak is the largest, namely the oxygen desorption peak has the strongest oxygen absorption and desorption capacity. But in propane oxidationThe peak area of the catalyst substituted by the transition metal is larger than that of the unsubstituted 2Pd/CeO within the reaction temperature range (beta peak)2Catalyst, this portion of the oxygen centers is more active in the propane oxidation reaction. O is2The absorption and desorption test results show that the active oxygen center of the catalyst can be effectively increased by the substitution of the transition metal, so that the propane oxidation reaction performance of the catalyst can be improved.
The invention reduces the use cost of the catalyst by replacing partial noble metal with transition metal under the condition of not reducing the performance of the catalyst. The properties of the carrier also deeply influence the performance and stability of the catalyst and active components, and the rare earth metal oxide CeO2Due to the highly localized and surface relaxation properties of the 4f electrons, the surfaces of the materials have special electronic structures. Because the Ru nanoparticles on different carriers have slightly different sizes, CeO2The carrier has smaller Ru particles, so that the performance of the catalyst is improved. Therefore, the invention selects the rare earth metal oxide CeO2The catalyst is prepared by using Pd as a main active metal as a carrier and substituting part of Pd by transition metals Fe, Co and Ni, and the catalyst has low cost and does not influence the performance of the catalyst.
Claims (10)
1. A preparation method of a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material is characterized by comprising the following steps:
adding a palladium source and a transition metal salt into a hydrochloric acid solution, uniformly stirring, then adding a cerium oxide carrier, adjusting the pH value to 9-9.5, stirring to load the palladium salt on the cerium oxide carrier, standing to separate solid from liquid, washing the solid, drying, and then roasting to obtain a transition metal modified palladium nanocluster loaded on a cerium oxide catalytic material, wherein the mass percent of palladium in the transition metal modified palladium nanocluster loaded on the cerium oxide catalytic material is 1.0-2.0%, and the mass percent of transition metal is 0.5-1.0%.
2. The method for preparing a cerium oxide catalytic material loaded with transition metal modified palladium nanoclusters according to claim 1, wherein the palladium source is palladium acetate or palladium chloride.
3. The method for preparing a transition metal modified palladium nanocluster supported on a cerium oxide catalytic material as claimed in claim 1, wherein the transition metal salt is iron salt, cobalt salt or nickel salt.
4. The method for preparing a cerium oxide catalytic material loaded with transition metal modified palladium nanoclusters according to claim 3, wherein iron salt is ferric nitrate or ferric chloride, cobalt salt is cobalt nitrate or cobalt chloride, and nickel salt is nickel nitrate or nickel chloride.
5. The method for preparing a cerium oxide catalytic material loaded with transition metal-modified palladium nanoclusters according to claim 1, wherein the mass concentration of the hydrochloric acid solution is 37%, and the mass ratio of the palladium source to the hydrochloric acid is 1: 2.
6. The method for preparing a transition metal modified palladium nanocluster supported on a cerium oxide catalytic material as claimed in claim 1, wherein the pH adjustment is performed by using a sodium carbonate solution.
7. The method for preparing the transition metal modified palladium nanocluster supported on the cerium oxide catalytic material as claimed in claim 1, wherein the specific conditions of calcination are as follows: heating from room temperature to 500-600 ℃ at a heating rate of 2-5 ℃/min, and roasting for 4-6 hours.
8. A transition metal modified palladium nanocluster prepared according to the method of any one of claims 1 to 7 supported on a cerium oxide catalytic material.
9. Use of the transition metal-modified palladium nanoclusters as recited in claim 8 supported on a ceria catalytic material for alkane oxidation elimination.
10. The method of claim 9The method is characterized in that 300mg of transition metal modified palladium nanocluster is loaded on a cerium oxide catalytic material and placed in a quartz tube, reaction gas is introduced, the flow rate is 100mL/min, and the reaction airspeed is 20000mL/h/gcatReacting at 200-400 ℃; wherein the volume percentage of propane in the reaction gas is 0.1 percent, and O2The volume percentage of (A) is 21 percent, and the rest is N2。
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