KR101825907B1 - Catalyst for preparing hydrogen peroxide having core-shell structure and method for preparing hydrogen peroxide using the same - Google Patents
Catalyst for preparing hydrogen peroxide having core-shell structure and method for preparing hydrogen peroxide using the same Download PDFInfo
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- KR101825907B1 KR101825907B1 KR1020160033257A KR20160033257A KR101825907B1 KR 101825907 B1 KR101825907 B1 KR 101825907B1 KR 1020160033257 A KR1020160033257 A KR 1020160033257A KR 20160033257 A KR20160033257 A KR 20160033257A KR 101825907 B1 KR101825907 B1 KR 101825907B1
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- hydrogen peroxide
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000011258 core-shell material Substances 0.000 title claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000002105 nanoparticle Substances 0.000 claims abstract description 104
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 59
- 239000010931 gold Substances 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 68
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 21
- -1 halogen anions Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011162 core material Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 101100202428 Neopyropia yezoensis atps gene Proteins 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- BSYLOTSXNQZYFW-UHFFFAOYSA-K trichlorogold;hydrate Chemical compound O.Cl[Au](Cl)Cl BSYLOTSXNQZYFW-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 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
- B01J23/38—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
-
- 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
- B01J23/38—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
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/006—
-
- B01J35/008—
-
- B01J35/0086—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The present invention relates to a catalyst for the production of hydrogen peroxide having a core-shell structure and a process for producing hydrogen peroxide using the same. More particularly, the present invention relates to a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as a core and core-shell nanoparticles in which a noble metal surrounds the core, and a process for producing hydrogen peroxide using the same. The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an effect showing excellent hydrogen peroxide selectivity and production rate.
Description
The present invention relates to a catalyst for the production of hydrogen peroxide having a core-shell structure and a process for producing hydrogen peroxide using the same. More particularly, the present invention relates to a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as a core and core-shell nanoparticles in which a noble metal surrounds the core, and a process for producing hydrogen peroxide using the same.
Hydrogen peroxide is used as a bleaching agent for pulp and fiber, disinfectant disinfectant, semiconductor cleaning liquid, oxidizer for water treatment process, and environmentally friendly oxidizer for chemical reaction (propylene oxide synthesis). As of 2009, 2.2 million tons of hydrogen peroxide are being produced annually, and the demand for hydrogen peroxide is expected to rise along with the increase in propylene oxide demand.
At present, hydrogen peroxide is generated through continuous oxidation and hydrogenation processes starting from anthraquinone-based compounds. In this case, a large amount of organic solvent is used and generated as waste. In addition, there is also a problem that the production of hydrogen peroxide requires a lot of energy consumption through a multi-stage continuous process and purification and concentration process after production.
Direct manufacturing process of synthesizing hydrogen peroxide by directly reacting hydrogen and oxygen has been attracting attention. This direct manufacturing process has been studied as an alternative process of commercial process because water is produced as a reaction by-product and use of organic solvent is low. The direct manufacturing process is simple in construction and can be manufactured where hydrogen peroxide is needed, thus greatly reducing the risk of explosion when storing and transporting hydrogen peroxide (Korean Patent Laid-Open Publication No. 2002-0032225).
In the direct production process of hydrogen peroxide, in the case of palladium catalyst, a halogen anion is added to the solvent to increase the selectivity of hydrogen peroxide. However, in the case of a halogen anion, it may not be necessary to add a halogen anion to the solvent since separation purification may be necessary later. In order to solve this problem, studies have been reported to increase the selectivity of hydrogen peroxide by using palladium-gold (Pd-Au) alloy as a catalyst.
The inventors of the present invention have found out that when using a catalyst for producing hydrogen peroxide in which a palladium (Pd) nanoparticle is used as a core and a noble metal includes core-shell nanoparticles surrounding the core, hydrogen and oxygen The present inventors confirmed that the hydrogen peroxide was excellent in hydrogen peroxide selectivity and production rate without adding a halogen anion to the solvent in the production of hydrogen peroxide.
Accordingly, the present invention provides a catalyst for the production of hydrogen peroxide, which comprises palladium (Pd) nanoparticles as core and core-shell nanoparticles in which a noble metal surrounds the core, and a method for producing the same.
Accordingly, the present invention provides a process for producing hydrogen peroxide, which comprises reacting and supplying hydrogen and oxygen to a reactor comprising the catalyst for the production of hydrogen peroxide and a solvent.
In order to achieve the above object,
The present invention
There is provided a catalyst for producing hydrogen peroxide comprising palladium (Pd) nanoparticles as cores and noble metals as core-shell nanoparticles surrounding the cores.
In addition,
(1) preparing a core of palladium (Pd) nanoparticles;
(2) preparing a core (palladium) -shell (noble metal) nanoparticle by coating a noble metal on the nanoparticle core; And
(3) preparing a core (palladium) -shell (noble metal) nanoparticle supported on silica by binding the core (palladium) -shell (precious metal) nanoparticles with silica to produce a catalyst for producing hydrogen peroxide .
In addition,
And supplying hydrogen and oxygen to the reactor containing the catalyst for the production of hydrogen peroxide and the solvent to react them.
Hereinafter, the present invention will be described in detail.
The present invention
There is provided a catalyst for producing hydrogen peroxide comprising palladium (Pd) nanoparticles as cores and noble metals as core-shell nanoparticles surrounding the cores.
The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is superior to conventional palladium nanoparticles or alloy nanoparticles of palladium and gold in that hydrogen peroxide is produced from hydrogen peroxide without adding a halogen anion to the solvent, Selectivity and production rate.
The palladium (Pd) nanoparticles may have an average size of 1 to 30 nm, and preferably 2 to 20 nm.
The weight ratio of the palladium to the noble metal may be 1: 0.05 to 1: 1, and preferably 1: 0.1 to 1: 0.5. When the weight ratio of palladium to noble metal (Pd / noble metal) is less than 1, the characteristics of noble metal are strongly expressed on the core-shell surface and the selectivity of hydrogen peroxide is not high. .
The noble metal may be gold (Au), silver (Ag), platinum (Pt), or gold (Au).
The core-shell nanoparticles may be controlled in size and shape, and the shape thereof may be in the shape of a cube, an octahedron, or a dodecahedron.
The core-shell nanoparticles may be supported on a support. The support and the like, silica, alumina, titania, zirconia, it is preferable that the silica (SiO 2).
The hydrogen peroxide may be prepared by direct reaction of hydrogen and oxygen.
The present invention also relates to a method for preparing a palladium (Pd) nanoparticle comprising: (1) preparing a core of palladium (Pd) nanoparticles; (2) preparing a core (palladium) -shell (noble metal) nanoparticle by coating a noble metal on the nanoparticle core; And (3) preparing core (palladium) -chelled (noble metal) nanoparticles supported on silica by bonding the core (palladium) -shell (precious metal) nanoparticles with silica to produce a catalyst for the production of hydrogen peroxide. ≪ / RTI >
The present invention also provides a method for producing hydrogen peroxide, comprising supplying hydrogen and oxygen to a reactor containing the catalyst for producing hydrogen peroxide and a solvent and reacting the hydrogen peroxide.
The solvent may be one or more solvents selected from the group consisting of methanol, ethanol and water. Specifically, it may be methanol, ethanol or a mixture of water and alcohol, preferably a mixture of ethanol and water.
In the direct production process of hydrogen peroxide, in the case of palladium catalyst, a halogen anion is added to the solvent to increase the selectivity of hydrogen peroxide. However, in the case of a halogen anion, it may not be necessary to add a halogen anion to the solvent since separation purification may be necessary later. Therefore, the solvent does not include a halogen element, and may further include an acid. When an acid is included, the hydrogen peroxide yield can be greatly increased by suppressing the decomposition of the produced hydrogen peroxide. The acid may be sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), phosphoric acid (H 3 PO 4 ), nitric acid (HNO 3 ) and the like, preferably phosphoric acid.
The concentration of the acid in the solvent may be 0 to 1 M, preferably 0.01 to 0.05 M.
The reactants, hydrogen and oxygen, may be in a gaseous form and may be preferably fed directly to the solvent using a Dip Tube which may be contained in a solvent to improve the solubility in the solvent. The hydrogen gas may be flowed at a flow rate of 1 to 4 mL / min, and the oxygen gas may be flowed at a flow rate of 10 to 40 mL / min. More preferably, the hydrogen gas may be maintained at 1.5 to 2.5 ml / min, and the oxygen gas may be maintained at 15 to 25 ml / min, and the hydrogen to oxygen molar ratio may be 1: 5 to 1:15. If the ratio of oxygen to hydrogen is 1: 1, but the ratio of hydrogen to oxygen is lower than 1: 5, there is a risk of explosion. If oxygen is more than 1:15, The range of the hydrogen: oxygen molar ratio is preferable.
Preferably, the reactor is further reacted by supplying nitrogen as a reactant. When using nitrogen, it is possible to deviate from the explosion range even if the ratio of hydrogen to oxygen is set to 1: 1, and there is an advantage that it can be used without additional nitrogen separation when using oxygen in the air in the future.
While the hydrogen gas and the oxygen gas are flowed at a constant flow rate, the entire reaction pressure is regulated using a BPR (Back Pressure Regulator), and the reaction pressure can be measured through a pressure gauge connected to the reactor. The reaction pressure is preferably maintained at 1 to 40 atm, preferably at normal pressure, and it may be preferable to conduct the reaction while maintaining the reaction temperature at 10 to 30 ° C.
The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an advantage of showing excellent hydrogen peroxide selectivity and production rate.
The core (palladium) -cheller (noble metal) nanoparticle catalyst according to the present invention is advantageous over conventional palladium (Pd) nanoparticles, or from alloyed nanoparticles of palladium and gold, by adding halogen anions to the solvent during hydrogen peroxide production from hydrogen and oxygen , There is an effect showing excellent hydrogen peroxide selectivity and production rate.
1 is a TEM (Transmission Electron Microscope) image of (a) silica (SiO 2 ) nanoparticles, (b) palladium (Pd) nanoparticles, and (c) core (Pd) Fig.
2 is a scanning transmission electron microscope (STEM) image showing the distribution of Pd and Au in core (Pd) @ shell (Au) nanoparticles according to Example 1. FIG.
FIG. 3 is a diagram showing a high-angle annular dark-field transmission electron microscope (HAADF-STEM) image showing the distribution of Pd and Au in core (Pd) @ shell (Au) nanoparticles according to Example 1. FIG.
4 shows Pd nanoparticles supported on silica, (b) Pd-Au alloy nanoparticles supported on silica, and (c) core supported on silica (Pd) according to Example 1 and Comparative Examples 1 and 2, ≪ RTI ID = 0.0 > (TEM) < / RTI > images of @ shell (Au) nanoparticles.
5 is a graph showing hydrogen conversion and hydrogen peroxide selectivity when hydrogen peroxide is directly produced from hydrogen and oxygen according to Example 2 and Comparative Examples 3 and 4. FIG.
FIG. 6 is a graph showing the rate of generation of hydrogen peroxide when hydrogen peroxide is directly produced from hydrogen and oxygen according to Example 2 and Comparative Examples 3 and 4. FIG.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited by the examples.
Example 1. Silica ( SiO 2 )on Supported core( Pd ) @ Shell ( Au ) Preparation of nanoparticles
1-1. Palladium ( Pd) Of nanoparticles Produce
105 mg of polyvinylpyrrolidone (PVP), 60 mg of L-ascorbic acid, 185 mg of potassium bromide (KBr) and 5 mg of potassium chloride (KCl) were dissolved in 8 mL of distilled water, Lt; / RTI > Then, a solution of 57 mg of disodium tetrachloropalladate (Na 2 PdCl 4 ) dissolved in 3 mL of distilled water was added to the mixture, followed by stirring at 80 rpm for 3 hours at 800 rpm. After completion of the reaction, the reaction solution and acetone were mixed at a ratio of 1:10, the nanoparticles were collected through a centrifuge (3500 rpm, 10 minutes), washed with distilled water, and the palladium (Pd) The nanocube particles were redispersed in 8 mL of distilled water.
1-2. core( Pd ) @ Shell ( Au ) Of nanoparticles Produce
1 mL of Pd nanoparticles dispersed in distilled water according to Example 1-1 and 3 mg of L-ascorbic acid were dissolved in 8 mL of distilled water and then preheated at 95 DEG C for 30 minutes. Thereafter, a solution of 0.82 mg of gold (III) chloride hydrate (HAuCl 4 ) dissolved in 2 mL of distilled water was added to the mixture, and the mixture was stirred at 95 rpm for 15 minutes at 800 rpm. After completion of the reaction, the reaction solution and acetone were mixed at a ratio of 1:10, the nanoparticles produced through a centrifuge (3500 rpm, 10 minutes) were collected, washed with distilled water, @ Shell (Au) nanocube particles were redispersed in 8 mL of distilled water.
1-3. Amine group The treated silica ( SiO 2 ) Preparation of nanoparticles
First, 10 mL of distilled water and 3.15 mL of ammonia water were mixed with 74 mL of ethanol, 6 mL of a silica precursor (tetraethyl orthosilicate, Si (OC 2 H 5 ) 4 ) was added, and the mixture was stirred for 12 hours to prepare silica nanoparticles. The prepared silica nanoparticles were washed with distilled water and propanol, and dispersed in 320 mL of propanol. The dispersed solution was preheated to 80 DEG C and amine groups were treated on the silica surface by adding 3-aminopropyltriethoxysilane (ATPS). Thereafter, the mixture was stirred at 80 DEG C for 2 hours, collected by a centrifuge, and dispersed in ethanol.
1-4. Silica ( SiO 2 )on Supported core( Pd ) @ Shell ( Au ) Preparation of nanoparticles
The dispersion solution of the core (Pd) @ shell (Au) nanocube according to the above Example 1-2 was mixed with the silica (SiO 2 ) dispersion solution according to Example 1-3 and stirred for 2 hours. Thereafter, core (Pd) @ shell (Au) nanocube particles supported on silica (SiO 2 ) produced through a centrifugal separator were recovered and dried to be used as a catalyst.
Comparative Example 1. Silica ( SiO 2 )on Supported Palladium ( Pd ) Preparation of nanoparticles
A support to the above-described embodiment in the first core (Pd) @ shell (Au) nanoparticles instead of palladium (Pd) in the same manner as in the method described in Example 1, except that nanoparticles of silica (SiO 2) palladium ( Pd) nanocube particles were prepared.
Comparative Example 2. Silica ( SiO 2 )on Supported Palladium and gold alloys ( Pd - Au ) Preparation of nanoparticles
First, silica (SiO 2 ) nanoparticles were prepared in the same manner as in Example 1-3. Thereafter, the silica nanoparticles were mixed with Na 2 PdCl 4 and AuCl 3 dissolved in distilled water and coprecipitated. The prepared product was recovered, heat-treated at 500 ° C for 6 hours, and then reduced at 350 ° C under a hydrogen atmosphere to prepare palladium-gold (Pd-Au) alloy nanoparticles supported on silica.
Example 2. On silica Supported core( Pd ) @ Shell ( Au Production of hydrogen peroxide using nanoparticles
A double jacketed reactor was charged with 0.2 g of core (Pd) @ shell (Au) nanoparticles supported on the silica according to Example 1 and 30 ml of a reaction solvent (distilled water, 120 ml; ethanol) containing no halogen anion; Phosphoric acid (H 3 PO 4 ) 0.03 M) was added thereto, and the reaction was carried out for 3 hours. The reaction temperature was maintained at 20 ° C and the pressure was maintained at 1 atm. The reaction gas (H 2 / O 2 = 1/10) was flowed constantly at 22 mL per minute. Then, hydrogen peroxide produced after the reaction was collected.
Comparative Example 3. To silica Supported Palladium ( Pd Production of hydrogen peroxide using nanoparticles
Hydrogen peroxide was collected in the same manner as in Example 2, except that palladium (Pd) nanoparticles were used in place of the core (Pd) @ shell (Au) nanoparticles in Example 2. [
Comparative Example 4. To silica Supported Palladium and gold alloys ( Pd - Au Production of hydrogen peroxide using nanoparticles
Hydrogen peroxide was collected in the same manner as described in Example 2 except that palladium and gold alloy (Pd-Au) alloy nanoparticles were used in place of the core (Pd) @ shell (Au) nanoparticles in Example 2 .
Experimental Example 1. Electron microscopic observation
Each catalyst prepared according to Example 1 and Comparative Examples 1 and 2 was observed using an electron microscope.
(TEM) image of (a) silica (SiO 2 ) nanoparticles, (b) palladium (Pd) nanoparticles and (c) core (Pd) @ shell (Au) nanoparticles according to Example 1 1, scanning electron microscopy (STEM) and high-angle annular dark-field transmission electron microscope (HAADF-STEM) images showing the distribution of Pd and Au in Pd @ Au nanoparticles are shown in FIG. 2 and FIG.
As shown in FIG. 1, the silica (SiO 2 ) nanoparticles showed a spherical shape having a diameter of about 200 to 300 nm, and the palladium (Pd) nanoparticles showed a cube shape having a size of 5 to 10 nm . In addition, core (Pd) @ shell (Au) nanoparticles have a size of 20 to 30 nm and are similar to palladium (Pd) nanoparticles.
As shown in FIG. 2, it can be seen that palladium (Pd) and gold (Au) form a core (Pd) @ shell (Au) structure.
As shown in FIG. 3, it can be seen that palladium (Pd) and gold (Au) are evenly distributed. The red dot indicates the point at which a certain amount or more of palladium (Pd) is detected, and the green dot indicates the point at which a certain amount or more of gold (Au) is detected.
Pd nanoparticles supported on silica, (b) Pd-Au alloy nanoparticles supported on silica, and (c) Pd supported on silica (shell) according to Example 1 and Comparative Examples 1 and 2 Transmission electron microscope (TEM) images of Au nanoparticles are shown in FIG.
As shown in FIG. 4, it can be confirmed that the Pd nanoparticles and the core (Pd) @ shell (Au) nanoparticles are uniformly distributed and supported on the silica.
Since Pd nanoparticles and core (Pd) @ shell (Au) nanoparticles are chemically reduced, they can be synthesized without heat treatment, so that the size of the nanoparticles is small and uniform. However, in the case of Pd-Au nanoparticles, And it is possible to confirm that the particle size is irregular by the TEM image.
Experimental Example 2. Inductively coupled plasma An atomic emission spectrometer (ICP-AES) Used palladium ( Pd ) And gold Au ) Content measurement
Palladium (Pd) and gold (Au) contents were measured by ICP-AES analysis for each catalyst prepared according to Example 1 and Comparative Examples 1 and 2, and the results are shown in Table 1.
As shown in Table 1, Pd and Au in the core (Pd) @ shell (Au) nanoparticles were contained in 0.64 wt% and 0.09 wt%, respectively, and Pd-Au alloy showed similar contents .
Experimental Example 3. Production of hydrogen peroxide
The concentration of hydrogen peroxide collected in Example 2 and Comparative Examples 3 and 4 was measured by the following Equation 1 using iodometric titration. The amount of hydrogen peroxide produced was calculated by the following equation (2).
[Equation 1]
&Quot; (2) "
Hydrogen conversion and hydrogen peroxide selectivity when hydrogen peroxide was directly produced from hydrogen and oxygen are shown in FIG. 5 and the production rate of hydrogen peroxide is shown in FIG.
As shown in FIG. 5, when the core (Pd) @ shell (Au) nanoparticle catalyst was used, the hydrogen peroxide selectivity was much higher than that in the case of using the palladium (Pd) nanoparticles and the Pd-Au alloy nanoparticle catalyst Can be confirmed. It has been known that the selectivity of hydrogen peroxide greatly increases when Pd-Au alloy nanoparticles are used. However, when the core (Pd) @ shell (Au) nanoparticles of the present invention are used, hydrogen peroxide selectivity is further increased .
Further, as shown in FIG. 6, the hydrogen peroxide production rate also increased correspondingly to the increase of the hydrogen peroxide selectivity. That is, from the above results, it can be seen that when the core (Pd) @ shell (Au) nanoparticles are used in the direct hydrogen peroxide production reaction, the selectivity of hydrogen peroxide is greatly increased and the hydrogen peroxide production rate can be greatly increased.
Claims (13)
Wherein the palladium (Pd) nanoparticles have an average size of 1 to 30 nm.
Wherein the palladium-to-gold weight ratio is 1: 0.05 to 1: 1.
Wherein the core-shell nanoparticles are controlled in size and shape, and the shape thereof is in the shape of a cube, an octahedron, or a dodecahedron.
The core-shell nanoparticles, catalyst for hydrogen peroxide, characterized in that the support for the silica (SiO 2).
Characterized in that the hydrogen peroxide is produced by direct reaction of hydrogen and oxygen.
(2) coating gold (Au) on the nanoparticle core to prepare core (palladium) -cell (gold) nanoparticles; And
(3) preparing a core (palladium) -chelled (gold) nanoparticle supported on silica by bonding the core (palladium) -chelle (gold) nanoparticle with silica .
Wherein the solvent is at least one solvent selected from the group consisting of methanol, ethanol and water.
Wherein the solvent does not contain a halogen element and further comprises at least one acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid.
Wherein the hydrogen and oxygen molar ratio is between 1: 5 and 1:15.
Wherein the reaction is carried out at a pressure of from 1 to 40 atm and at a temperature of from 10 to 30 < 0 > C.
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