KR20180082891A - A catalyst for synthesis of hydrogen reroxide and the synthesis of hydrogen reroxide using them - Google Patents
A catalyst for synthesis of hydrogen reroxide and the synthesis of hydrogen reroxide using them Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title description 10
- 229910052739 hydrogen Inorganic materials 0.000 title description 10
- 239000001257 hydrogen Substances 0.000 title description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 117
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000010948 rhodium Substances 0.000 claims description 78
- 230000002194 synthesizing effect Effects 0.000 claims description 23
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 5
- 239000011258 core-shell material Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 101710134784 Agnoprotein Proteins 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- -1 halogen ion Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
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Classifications
-
- 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
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/002—Catalysts characterised by their physical properties
- B01J35/0073—Distribution of the active metal ingredient
-
- B01J35/396—
-
- 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
Abstract
Description
본 발명은 과산화수소 합성용 촉매 및 이를 이용한 과산화수소 합성 방법에 관한 것으로, 기존 팔라듐(Pd) 촉매를 대체하면서도 활성이 우수한 과산화수소 합성용 촉매 및 이를 이용한 과산화수소 합성 방법에 관한 것이다.The present invention relates to a catalyst for synthesizing hydrogen peroxide and a method for synthesizing hydrogen peroxide using the same, and more particularly, to a catalyst for synthesizing hydrogen peroxide which is excellent in activity while replacing conventional palladium (Pd) catalysts and a method for synthesizing hydrogen peroxide.
과산화수소(H202)는 광택제, 소독제, 의약품, 로켓 연료, 친환경 산화제 등 다양한 분야에서 사용되고 있는 범용 화학제품으로, 그 수요는 지속적으로 증가하는 추세이다. Hydrogen peroxide (H 2 O 2 ) is a general-purpose chemical used in various fields such as polishes, disinfectants, medicines, rocket fuels, environmentally friendly oxidizers, and the demand is continuously increasing.
과산화수소의 제조방법으로서 수소와 산소를 이용한 과산화수소의 직접 합성 방법은 1914년 Hankel과 Weber가 미국등록특허 제1,108,752호에서 처음 제안한 이래로 다수의 기업들이 반응의 단순화 및 비용 절감 차원에서 다양한 연구를 계속해왔다. 그 대표적인 기업이 듀퐁, 에보닉, 헤드워터스, 다우케미칼 등이며, 이들 기업을 팔라듐(Pd)을 기본으로 하는 촉매 및 반응 시스템을 주로 개발하였다. Since the direct synthesis of hydrogen peroxide using hydrogen and oxygen as a process for the production of hydrogen peroxide was first proposed by Hankel and Weber in the United States Patent No. 1,108,752 in 1914, many companies have continued to conduct various studies in order to simplify the reaction and reduce costs. DuPont, Ebonic, Head Waters, Dow Chemical, and others, have developed catalysts and reaction systems based on palladium (Pd).
듀퐁은 미국등록특허제4,681,751호, 제4,772,458 및 제5,352,645호 등에서 Pd-Pt 금속을 카본, 실리카, 알루미나, 이온교환수지 등에 담지하여 과산화수소 직접 합성용 촉매를 개발하였다. 또한 수용성 용매에서의 할로겐 이온이 과산화수소 생산에 미치는 영향, 그리고, 인산계 첨가제가 과산화수소의 안정성에 미치는 영향 등을 연구하였다. 한편, 듀퐁은 1980년대 세계 최초로 파일럿플랜트 개발을 시도하였으나, 그 과정에서 잦은 폭발 사고로 인한 안정성의 이유 등으로 상용화 공정 개발에는 실패하였다. DuPont developed a catalyst for direct synthesis of hydrogen peroxide by supporting Pd-Pt metal on carbon, silica, alumina, ion exchange resin, etc. in U.S. Patent Nos. 4,681,751, 4,772,458 and 5,352,645. The effect of halogen ion on the production of hydrogen peroxide in water - soluble solvents and the effect of phosphate additives on the stability of hydrogen peroxide were studied. Meanwhile, DuPont attempted to develop a pilot plant for the first time in the world in the 1980s, but in the process, it failed to develop the commercialization process because of frequent explosion and safety reasons.
헤드워터스는 미국등록특허 제6,168,775호, 제6,576,214호, 제7,144,565호 및 제7,011,807호 등에서 Pd 계열의 활성금속에 다양한 종류의 금속을 증진제로 사용하여 활성금속 입자의 크기 및 흡착 배위수 제어를 통해 과산화수소의 선택성을 높이는 기술을 개발하였으며, 할로겐화물을 용매에 첨가해 선택성과 생산성을 높이는 기술을 개발하였다. 또한, 미국등록특허 제7,105,143호에서는 반응기 내부로 공급되는 수소의 양을 단계별로 조정하여, 반응기 내의 수소/산소의 비율을 화학량론적으로 유지시킴으로써, 과산화수소 선택성을 증가시켜 81% 과산화수소 수율을 얻을 수 있는 방법을 개시하고 있다. 그러나 이렇게 높은 수소/산소 비율은 반응 안정성 측면에서 선호되지 않는 반응 조건이다.Head Waters, in U.S. Patent Nos. 6,168,775, 6,576,214, 7,144,565, and 7,011,807, disclose a method of controlling the size and adsorption coordination number of active metal particles by using various kinds of metal as an enhancer on Pd- And developed a technique to increase the selectivity and productivity by adding halides to the solvent. In addition, U.S. Patent No. 7,105,143 discloses that by regulating the amount of hydrogen supplied to the inside of the reactor in stages to stoichiometrically maintain the hydrogen / oxygen ratio in the reactor, the hydrogen peroxide selectivity can be increased to obtain 81% hydrogen peroxide yield / RTI > However, such a high hydrogen / oxygen ratio is a reaction condition that is not preferred in terms of reaction stability.
그 밖에도 미쓰비시 가스케미칼은 미국등록특허 제5,292,496호에서 세슘을 함유하는 복합금속산화물 담지촉매를 이용하여 할로겐이온을 포함하지 않는 반응 매질 내에서 고농도의 과산화수소를 직접 합성하는 기술을 개시하고 있으나, 생성되는 과산화수소 농도가 0.5 중량% 이하로 생산성이 매우 낮아 여전히 개선이 요구되는 실정이다. In addition, Mitsubishi Gas Chemical discloses a technique for directly synthesizing hydrogen peroxide at a high concentration in a reaction medium containing no halogen ion by using a composite metal oxide supported catalyst containing cesium in U.S. Patent No. 5,292,496, The hydrogen peroxide concentration is 0.5% by weight or less, and the productivity is still very low.
본 발명은 과산화수소의 직접 합성 공정에서 고 활성 및 고 효율성을 가지는 신규 촉매와 이를 이용한 과산화수소 합성 방법을 제공하는 것을 목적으로 한다. The present invention aims to provide a novel catalyst having high activity and high efficiency in a process for directly synthesizing hydrogen peroxide and a method for synthesizing hydrogen peroxide using the same.
상기 과제를 해결하기 위하여, 본 발명의 일 구현예에 따르면, 하기 화학식 1의 과산화수소 합성용 촉매가 제공된다:According to one embodiment of the present invention, there is provided a catalyst for synthesizing hydrogen peroxide represented by the following general formula:
[화학식 1][Chemical Formula 1]
RhxAg(1-x) Rh x Ag (1-x)
여기서, x는 0 ＜x ＜1 이다.Here, x is 0 < x < 1.
다른 구현예에 따라, 상기 상기 화학식 1의 촉매는 고체 로듐(Rh)과 고체 은(Ag)이 혼합된 고용체 혹은 코어-쉘(core-shell) 형태일 수 있다.According to another embodiment, the catalyst of Formula 1 may be in the form of solid solution or core-shell mixed with solid rhodium (Rh) and solid silver (Ag).
다른 구현예에 따라, 상기 화학식 1의 전체 원자수 비율 100%에 대하여, 로듐(Rh)의 원자수 비율은 2 내지 50%일 수 있다. According to another embodiment, the ratio of the number of atoms of rhodium (Rh) may be from 2 to 50%, for 100% of the total number of atoms in the formula (1).
다른 구현예에 따라, 상기 화학식 1의 전체 원자수 비율 100%에 대하여, 로듐(Rh)의 원자수 비율은 2 내지 7%일 수 있다. According to another embodiment, the ratio of the number of atoms of rhodium (Rh) may be 2 to 7% with respect to 100% of the total number of atoms in the formula (1).
또한, 본 발명은 다른 구현예에 따라, 전술한 어느 하나의 구현예에 따른 촉매를 이용한 과산화수소 합성 방법이 제공된다. Further, the present invention provides, in accordance with another embodiment, a method for synthesizing hydrogen peroxide using a catalyst according to any one of the above-described embodiments.
본 발명에 따른 촉매는 수소와 산소로부터 직접 과산화수소를 합성하는 반응에 사용되어 높은 촉매 활성을 나타내어 과산화수소의 수율을 높게 유지할 수 있는 이점이 있다. The catalyst according to the present invention is used in a reaction for synthesizing hydrogen peroxide directly from hydrogen and oxygen, and exhibits high catalytic activity, so that the yield of hydrogen peroxide can be kept high.
도 1은 본 발명의 일 실시예에 따른 Rh0 . 5Ag0 .5를 주사 투과 전자 현미경-에너지분산형 분광분석법(scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX)으로 촬영한 사진이다.
도 2는 본 발명의 다른 실시예에 따른 Rh0 . 03Ag0 . 97를 주사 투과 전자 현미경-에너지분산형 분광분석법(scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX)으로 촬영한 사진이다. 1 is Rh 0, according to one embodiment of the present invention. It is a picture taken by energy dispersive spectroscopy (scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX) - 5 to 0 .5 Ag scanning transmission electron microscope.
FIG. 2 is a schematic diagram of an embodiment of Rh 0 . 03 Ag 0 . 97 was photographed by scanning electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX).
이하, 본 발명에 대하여 상세히 설명하기로 한다. 이에 앞서 본 명세서 및 특허청구범위에 사용된 용어 또는 단어는 통상적이거나 사전적인 의미로 해석되어서는 안되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 명세서상에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고, 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에서 이를 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다. Hereinafter, the present invention will be described in detail. Prior to that, terms and words used in the present specification and claims should not be construed in a conventional or dictionary sense, and the inventor can appropriately define the concept of a term in order to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and not all of the technical ideas of the present invention are described. Therefore, It should be understood that various equivalents and modifications may be present.
본 발명의 일 실시예에 따른 과산화수소 합성용 촉매는 하기 화학식 1의 화합물이다;The catalyst for synthesizing hydrogen peroxide according to one embodiment of the present invention is a compound of the following formula 1:
[화학식 1][Chemical Formula 1]
RhxAg(1-x) Rh x Ag (1-x)
여기서, x는 0 ＜x ＜1이다. Here, x is 0 < x < 1.
이때, 상기 화학식 1의 RhxAg(1-x)는 고체 로듐(Rh)과 고체 은(Ag)이 혼합된 고용체(solid solution alloy) 혹은 코어-쉘(core-shell) 형태일 수 있다. 이는 주기율표에서 팔라듐(Pd)과 인접한 로듐(Rh)과 은(Ag) 각각은 수소 흡착 특성이 없지만, 이 두 원소를 solid solution alloy 상태로 만들면, 팔라듐과 전자구조가 유사해지고, 따라서, 팔라듐의 화학적·물질적 특성과 비슷해져서 수소 흡착이 가능하기 때문이다. The Rh x Ag (1-x) of the above formula (1 ) may be in the form of a solid solution alloy or a core-shell in which solid rhodium (Rh) and solid (Ag) are mixed. In the periodic table, palladium (Pd) and adjacent rhodium (Rh) and silver (Ag) have no hydrogen adsorption property. However, if the two elements are made into a solid solution alloy state, the palladium and the electron structure become similar, · It is similar to the material properties and it is possible to adsorb hydrogen.
즉, 본 발명은 팔라듐(Pd) 촉매 대신, 로듐(Rh)과 고체 은(Ag)이 혼합된 촉매를 사용함으로써, 기존의 팔라듐 기반의 촉매의 폭발의 위험성과 과산화수소의 생산성이 낮은 문제를 해결하였다.That is, the present invention solves the problem of low explosion risk and low hydrogen peroxide productivity of a conventional palladium-based catalyst by using a catalyst in which rhodium (Rh) and solid silver (Ag) are mixed instead of palladium (Pd) .
도 1은 본 발명의 일 실시예에 따른 Rh0 . 5Ag0 .5를 주사 투과 전자 현미경-에너지분산형 분광분석법(scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX)으로 촬영한 사진이다. 1 is Rh 0, according to one embodiment of the present invention. It is a picture taken by energy dispersive spectroscopy (scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX) - 5 to 0 .5 Ag scanning transmission electron microscope.
도 1에서 녹색 입자는 은(Ag) 원소이고, 적색 입자는 로듐(Rh)을 나타내는 것으로써, 두 입자가 분산된 고용체 상태임을 확인할 수 있다. In Fig. 1, the green particles are silver (Ag) elements and the red particles are rhodium (Rh), so that it can be confirmed that the two particles are dispersed solid solution state.
또한, 도 2는 본 발명의 다른 실시예에 따른 Rh0 . 03Ag0 . 97를 주사 투과 전자 현미경-에너지분산형 분광분석법(scanning transmission electron microscope-energy dispersive X-ray spectroscopy, STEM-EDX)으로 촬영한 사진으로, 입자의 비율을 다르게 적용한 경우에도 고용체를 형성하고 있음을 확인할 수 있다. FIG. 2 is a graph showing the relationship between Rh 0 . 03 Ag 0 . 97 was photographed by scanning electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX). It was confirmed that solid particles were formed even when the particle ratio was varied .
이때, 본 발명에 따른 상기 화학식 1의 촉매는 전체 원자수 비율 100%에 대하여, 로듐(Rh)의 원자수 비율은 2 내지 50%이고, 바람직하게는 2 내지 7%일 수 있으며, 상기 원자수 비율의 범위를 만족하는 경우, 우수한 과산화수소 합성 효율을 가질 수 있다. At this time, the ratio of the number of atoms of rhodium (Rh) is 2 to 50%, preferably 2 to 7%, relative to 100% of the total number of atoms, When the range of the ratio is satisfied, excellent hydrogen peroxide synthesis efficiency can be obtained.
이하, 본 발명을 구체적으로 설명하기 위하여 실시예를 들어 상세히 설명하기로 한다. 그러나 본 발명에 따른 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어서는 안된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가지는 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.
촉매 합성Catalyst synthesis
[실시예 1- Rh50Ag50 의 제조][Example 1 - Rh 50 Ag 50 Gt;
1.526g의 폴리(N-비닐-2-피롤리딘)(Poly(N-vinyl-2-pyrrolidone)) (PVP; MW=55000)을 200mL의 에틸렌글리콜(ethylene glycol)에 녹인 후, magnetic stirring 500rpm으로 섞어주며 170℃까지 air 분위기에서 온도를 올렸다. 8.4mg의 질산은(AgNO3) 0.05mmol과 14.1mg의 아세트산로듐(Rh(CH3COO)3) 0.05mmol을 20mL의 증류수(DI-water)에 녹인 후, 170℃까지 올라간 PVP-ethylene glycol에 넣고 1시간 반응 및 환원시켜 Rh50Ag50을 제조하였다. Poly (N-vinyl-2-pyrrolidone) (PVP; MW = 55000) was dissolved in 200 mL of ethylene glycol, followed by magnetic stirring at 500 rpm And the temperature was raised to 170 ° C in an air atmosphere. 0.05 mmol of silver nitrate (AgNO 3 ) and 14.1 mg of rhodium acetate (Rh (CH 3 COO) 3 ) (0.05 mmol) were dissolved in 20 mL of distilled water (DI water), and the solution was added to PVP- And reacted and reduced for 1 hour to prepare Rh 50 Ag 50 .
[실시예 2- Rh30Ag70 의 제조][Example 2 - Preparation of Rh 30 Ag 70 ]
0.763g의 PVP (MW=55000), 5.88mg의 AgNO3(0.035mmol)와 4.23mg의 Rh(CH3COO)3(0.015mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 5.88 mg of AgNO 3 (0.035 mmol) and 4.23 mg of Rh (CH 3 COO) 3 (0.015 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 3- Rh10Ag90 의 제조][Example 3 - Preparation of Rh 10 Ag 90 ]
0.763g의 PVP (MW=55000), 7.56mg의 AgNO3(0.045mmol)와 1.41mg의 Rh(CH3COO)3(0.005mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 7.56 mg of AgNO 3 (0.045 mmol) and 1.41 mg of Rh (CH 3 COO) 3 (0.005 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 4- Rh7Ag93 의 제조][Example 4 - Preparation of Rh 7 Ag 93 ]
0.763g의 PVP (MW=55000), 7.812mg의 AgNO3(0.0465mmol)와 0.987mg의 Rh(CH3COO)3(0.0035mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 7.812 mg of AgNO 3 (0.0465 mmol) and 0.987 mg of Rh (CH 3 COO) 3 (0.0035 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 5- Rh5Ag95 의 제조][Example 5 - Preparation of Rh 5 Ag 95 ]
0.763g의 PVP (MW=55000), 7.98mg의 AgNO3(0.0475mmol)와 0.705mg의 Rh(CH3COO)3(0.0025mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 7.98 mg of AgNO 3 (0.0475 mmol) and 0.705 mg of Rh (CH 3 COO) 3 (0.0025 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 6- Rh4Ag96 의 제조][Example 6 - Preparation of Rh 4 Ag 96 ]
0.763g의 PVP (MW=55000), 8.064mg의 AgNO3(0.048mmol)와 0.564mg의 Rh(CH3COO)3(0.002mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 8.064 mg of AgNO 3 (0.048 mmol), 0.564 mg of Rh (CH 3 COO) 3 (0.002 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 7- Rh3Ag97 의 제조][Example 7-Rh 3 Ag 97 Gt;
0.763g의 PVP (MW=55000), 8.148mg의 AgNO3(0.0485mmol)와 0.423mg의 Rh(CH3COO)3(0.0015mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 8.148 mg of AgNO 3 (0.0485 mmol) and 0.423 mg of Rh (CH 3 COO) 3 (0.0015 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[실시예 8- Rh2Ag98 의 제조][Example 8 - Preparation of Rh 2 Ag 98 ]
0.763g의 PVP (MW=55000), 8.232mg의 AgNO3(0.049mmol)와 0.282mg의 Rh(CH3COO)3(0.001mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 8.232 mg of AgNO 3 (0.049 mmol) and 0.282 mg of Rh (CH 3 COO) 3 (0.001 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[비교예 1- Rh90Ag10 의 제조][Comparative Example 1 - Preparation of Rh 90 Ag 10 ]
0.763g의 PVP (MW=55000), 0.84mg의 AgNO3(0.005mmol)와 12.69mg의 Rh(CH3COO)3(0.045mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 0.84 mg of AgNO 3 (0.005 mmol) and 12.69 mg of Rh (CH 3 COO) 3 (0.045 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[비교예 2- Rh70Ag30 의 제조][Comparative Example 2 - Production of Rh 70 Ag 30 ]
0.763g의 PVP (MW=55000), 2.52mg의 AgNO3(0.015mmol)와 9.87mg의 Rh(CH3COO)3(0.035mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 2.52 mg of AgNO 3 (0.015 mmol), 9.87 mg of Rh (CH 3 COO) 3 (0.035 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
[비교예 3- Rh1Ag99 의 제조][Comparative Example 3 - Rh 1 Ag 99 Gt;
0.763g의 PVP (MW=55000), 8.316mg의 AgNO3(0.0495mmol)와 0.141mg의 Rh(CH3COO)3(0.0005mmol), 100mL의 ethylene glycol, 10mL의 DI-water을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 과산화수소 합성용 촉매를 제조하였다. Except that 0.763 g of PVP (MW = 55000), 8.316 mg of AgNO 3 (0.0495 mmol) and 0.141 mg of Rh (CH 3 COO) 3 (0.0005 mmol), 100 mL of ethylene glycol and 10 mL of DI water Was prepared in the same manner as in Example 1, except that the catalyst for synthesizing hydrogen peroxide was prepared.
과산화수소 합성Hydrogen peroxide synthesis
[실시예 9][Example 9]
실시예 1에서 제조된 촉매를 사용하여, 0.158mg의 촉매와 2mL의 DI water-ethanol(20%), 0.02M H3PO4과 0.9mM NaBr을 사용하여 총 가스유량 22mL/min (부피비 산소:수소=10:1)으로 과산화수소를 합성하였다. Using the catalyst prepared in Example 1, a total gas flow rate of 22 mL / min (volume ratio oxygen: hydrogen (ppm)) was obtained using 0.158 mg of the catalyst, 2 mL of DI water-ethanol (20%), 0.02 MH 3 PO 4 and 0.9 mM NaBr. = 10: 1) to synthesize hydrogen peroxide.
[실시예 10][Example 10]
실시예 2에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 2 was used.
[실시예 11][Example 11]
실시예 3에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 3 was used.
[실시예 12][Example 12]
실시예 4에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 4 was used.
[실시예 13][Example 13]
실시예 5에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 5 was used.
[실시예 14][Example 14]
실시예 6에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 6 was used.
[실시예 15][Example 15]
실시예 7에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 7 was used.
[실시예 16][Example 16]
실시예 8에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Example 8 was used.
[비교예 4][Comparative Example 4]
Ag(은) 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the Ag (silver) catalyst was used.
[비교예 5][Comparative Example 5]
Rh(로듐) 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that Rh (rhodium) catalyst was used.
[비교예 6][Comparative Example 6]
별도의 촉매를 제조하지 않고, Rh(로듐) 및 Ag(은)을 물리적으로 1:1로 혼합한 촉매를 사용한 것으로 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that a catalyst in which Rh (rhodium) and Ag (silver) were physically mixed at a ratio of 1: 1 was used instead of a separate catalyst.
[비교예 7][Comparative Example 7]
비교예 1에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Comparative Example 1 was used.
[비교예 8][Comparative Example 8]
비교예 2에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다. Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Comparative Example 2 was used.
[비교예 9][Comparative Example 9]
비교예 3에서 제조된 촉매를 사용한 것을 제외하고, 실시예 9와 동일한 방법으로 과산화수소를 합성하였다.Hydrogen peroxide was synthesized in the same manner as in Example 9, except that the catalyst prepared in Comparative Example 3 was used.
상기 표 1은 실시예 9-16 및 비교예 4-8의 방법에 따라 합성되는 과산화수소 양을 30분 반응시간으로 측정하여 기록한 표이다. Table 1 is a table in which the amount of hydrogen peroxide synthesized according to the method of Example 9-16 and Comparative Example 4-8 was measured by a reaction time of 30 minutes.
비교예 4와 같이 Ag(은)만을 촉매로 사용하는 경우, 과산화수소가 전혀 합성되지 않는 것을 확인할 수 있었으며, 비교예 5와 같이 Rh(로듐)만을 촉매로 사용하는 경우, 과산화수소 수득률이 매우 낮은 것을 확인할 수 있다.It was confirmed that when only Ag (silver) was used as a catalyst as in Comparative Example 4, hydrogen peroxide was not synthesized at all. When only Rh (rhodium) was used as a catalyst as in Comparative Example 5, the yield of hydrogen peroxide was very low .
또한, 비교예 7, 비교예 8 및 비교예 9에서와 같이, Rh(로듐)을 50 원자수비 초과, 2 원자수비 미만으로 포함하는 경우, 과산화수소 수득률이 급격히 감소하는 것을 확인할 수 있다. In addition, as in Comparative Example 7, Comparative Example 8 and Comparative Example 9, it is confirmed that the yield of hydrogen peroxide is drastically reduced when Rh (rhodium) is contained in a ratio of more than 50 atomic ratios and less than 2 atomic ratios.
아울러, 본 발명에 따른 촉매를 사용하는 경우, 고가의 Rh(로듐)을 단독으로 사용하는 것보다, Rh(로듐)보다 가격이 저렴한 Ag(은)을 50 내지 98 원자수비의 포함하는 경우 오히려 과산화수소 수득률이 현저히 증가하고 있으므로, 본 발명에 따른 촉매를 이용하여, 과산화수소를 합성하는 경우, 제조 비용을 절감할 수 있어, 상업적으로 대량 생산을 기대할 수 있다. Further, in the case of using the catalyst according to the present invention, when Ag (silver), which is less expensive than Rh (rhodium), contains 50 to 98 atomic ratio than the expensive Rh (rhodium) alone, When the hydrogen peroxide is synthesized by using the catalyst according to the present invention, the production cost can be reduced and commercial mass production can be expected since the yield is remarkably increased.
이상과 같이 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술 사상과 아래에 기재될 특허청구범위의 균등 범위 내에서 다양한 수정 및 변형이 가능함은 물론이다. While the present invention has been described with reference to the exemplary embodiments and the drawings, it is to be understood that the present invention is not limited thereto and that various changes and modifications will be apparent to those skilled in the art. It will be understood that various modifications and changes may be made without departing from the scope of the appended claims.
Claims (5)
[화학식 1]
RhxAg(1-x)
여기서, x는 0＜x＜1 이다. A catalyst for synthesizing hydrogen peroxide of the following formula (1)
[Chemical Formula 1]
Rh x Ag (1-x)
Here, x is 0 < x < 1.
상기 화학식 1의 촉매는 고체 로듐(Rh)과 고체 은(Ag)이 혼합된 고용체 혹은 코어-쉘 형태인 것을 특징으로 하는 과산화수소 합성용 촉매. The method according to claim 1,
Wherein the catalyst of Formula 1 is a solid solution or a core-shell type in which solid rhodium (Rh) and solid (Ag) are mixed.
상기 화학식 1의 전체 원자수 비율 100%에 대하여, 로듐(Rh)의 원자수 비율은 2 내지 50%인 것을 특징으로 하는 과산화수소 합성용 촉매. The method according to claim 1,
Wherein the ratio of the number of atoms of rhodium (Rh) is 2 to 50% with respect to 100% of the total number of atoms in the formula (1).
상기 화학식 1의 전체 원자수 비율 100%에 대하여, 로듐(Rh)의 원자수 비율은 2 내지 7%인 것을 특징으로 하는 과산화수소 합성용 촉매. The method according to claim 1,
Wherein the ratio of the number of atoms of rhodium (Rh) is 2 to 7% with respect to 100% of the total number of atoms in the formula (1).
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| US10265682B2 (en) | 2017-01-11 | 2019-04-23 | Korea Institute Of Science And Technology | Catalyst for synthesis of hydrogen peroxide and synthesis of hydrogen peroxide using same |
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| US10265682B2 (en) | 2017-01-11 | 2019-04-23 | Korea Institute Of Science And Technology | Catalyst for synthesis of hydrogen peroxide and synthesis of hydrogen peroxide using same |
| KR20190018911A (en) * | 2017-08-16 | 2019-02-26 | 한국과학기술연구원 | A catalyst for synthesis of hydrogen peroxide and the synthesis of hydrogen peroxide using them |
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