KR101602695B1 - Direct synthesis of hydrogen peroxide from hydrogen and oxygen using shape controlled Pd nanoparticle supported catalysts - Google Patents
Direct synthesis of hydrogen peroxide from hydrogen and oxygen using shape controlled Pd nanoparticle supported catalysts Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 title claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 22
- 239000001257 hydrogen Substances 0.000 title claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 15
- 239000001301 oxygen Substances 0.000 title claims description 15
- 229910052760 oxygen Inorganic materials 0.000 title claims description 15
- 238000003786 synthesis reaction Methods 0.000 title description 5
- 230000015572 biosynthetic process Effects 0.000 title description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 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
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- 239000003960 organic solvent Substances 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
본 발명은 형상 제어된 팔라듐 나노 입자 담지 촉매 및 이를 이용한 과산화수소 직접 생산방법에 관한 것이다.The present invention relates to a shape-controlled palladium nano-particle-supported catalyst and a method for directly producing hydrogen peroxide using the same.
Description
본 발명은 수소와 산소로부터 과산화수소를 직접 합성하는 방법으로, 구체적으로 과산화수소 직접생산을 위한 형상 제어된 팔라듐 나노 입자 담지 촉매 및 이의 제조 방법 및 상기 촉매를 이용한 과산화수소 직접 생성 방법에 관한 것이다.
The present invention relates to a method for directly synthesizing hydrogen peroxide from hydrogen and oxygen, specifically to a shape-controlled palladium nano-particle-supported catalyst for direct production of hydrogen peroxide, a process for producing the same, and a process for producing hydrogen peroxide directly using the catalyst.
과산화수소는 펄프 및 섬유의 표백제, 소독 살균제, 반도체 세정액, 수처리 공정의 산화제, 화학 반응의 친환경 산화제 (프로필렌 옥사이드 합성)로 사용되고 있다. 2009년 기준 연간 220만 톤의 과산화수소가 생산되고 있으며 프로필렌 옥사이드 수요의 증가와 함께 과산화수소의 수요 증가가 기대된다.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 produced annually, and demand for hydrogen peroxide is expected to rise along with an increase in demand for propylene oxide.
현재 과산화수소는 대한민국 공개특허 1999-0027774 호 및 대한민국 공개특허 2001-0076225 호에 공지된 바와 같이, 안트라퀴논(anthraquinone) 계열 화합물을 시작으로 연속적인 산화, 수소화 공정을 거쳐 생성되는데, 이때 많은 양의 유기 용매가 사용되고 폐기물로 발생한다는 문제점이 있다. At present, hydrogen peroxide is produced by successive oxidation and hydrogenation processes starting from anthraquinone-type compounds as disclosed in Korean Patent Laid-Open Publication No. 1999-0027774 and Korean Patent Laid-Open Publication No. 2001-0076225, There is a problem that a solvent is used and generated as waste.
또한 과산화수소의 생산이 다단의 연속 공정과 생산 후 정제 및 농축 과정을 거치며 많은 에너지의 소비가 필요하다는 문제점도 있다.In addition, there is 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.
이에 수소와 산소를 직접 반응시켜 과산화수소를 합성하는 직접 생산 공정이 주목 받고 있으며, 이러한 직접 생산 공정은 반응 부산물로 물이 생산되며 유기 용매의 사용이 적어 상용 공정의 대체 공정으로 많은 연구가 되어왔다.Direct production processes for the synthesis of hydrogen peroxide by directly reacting hydrogen and oxygen have been attracting attention. This direct production 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.
또한, 직접 생산 공정은 구성이 간단해 과산화수소를 필요로 하는 곳에서 생산 공급할 수 있어 과산화수소의 보관 및 운반시 폭발의 위험성이 크게 줄일 수 있다.In addition, the direct production process can be produced and supplied where hydrogen peroxide is needed because of its simple structure, so that the risk of explosion when storing and transporting hydrogen peroxide can be greatly reduced.
따라서 과산화수소 직접 생산을 위한 촉매 및 반응시스템에 대한 연구가 진행되고 있다.
Therefore, a catalyst and a reaction system for the direct production of hydrogen peroxide are being studied.
수소와 산소로부터 과산화수소를 직접생산하기 위한 촉매로 팔라듐을 이용한 다양한 촉매의 개발이 이루어지고 있는데, 특히 팔라듐의 크기 및 노출되는 결정면은 과산화수소의 선택도 및 수율에 영향을 미칠 수 있다.Various catalysts using palladium as a catalyst for directly producing hydrogen peroxide from hydrogen and oxygen have been developed. In particular, the size of palladium and exposed crystal faces may affect the selectivity and yield of hydrogen peroxide.
형상 제어된 나노입자는 표면에 노출된 표면적-부피 비율, 노출된 결정면의 종류 및 비율을 제어할 수 있으며, 이들의 변화는 촉매 활성에 큰 영향을 미친다.The shape-controlled nanoparticles can control the surface area-volume ratio of the surface exposed, the type and proportion of the exposed crystal faces, and these changes greatly affect the catalytic activity.
하지만 과산화수소 직접생산 공정의 중요성에도 불구하고 나노 입자를 제조 과산화수소 직접 합성 반응에 촉매로 활용한 연구는 많지 않으며, 상업화 단계까지는 아직 도달하지 못한 상태이다.In spite of the importance of direct hydrogen peroxide production process, there are not many studies using nanoparticles as a catalyst for direct hydrogen peroxide synthesis reaction.
특히 입자의 형상 제어를 통해 상이한 결정면을 노출시켜 과산화수소의 활성 및 선택도를 높이는 연구는 진행된 바 없다.In particular, research has not been conducted to increase the activity and selectivity of hydrogen peroxide by exposing different crystal faces through particle shape control.
이에, 본 발명은 수소와 산소로부터 과산화수소를 직접 생산공정에 사용되는 형상 제어된 팔라듐 나노 입자 담지 촉매를 개발하여 사용하는 것을 목적으로 한다.
Accordingly, it is an object of the present invention to develop and use a shape-controlled palladium nano-particle-supporting catalyst used for producing hydrogen peroxide directly from hydrogen and oxygen.
상기 목적을 달성하기 위해서, 본 발명은 수소와 산소를 이용한 과산화수소를 직접 생산하는 방법에 있어서, 옥타헤드론 (octahedron) 및 롬빅 도데카헤드론 (Rhombic dodecahedron) 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노 입자를 포함하는 형상 제어된 팔라듐 나노 입자 담지 촉매를 사용하는 과산화수소 직접 생산 방법을 제공한다.In order to accomplish the above object, the present invention provides a method for directly producing hydrogen peroxide using hydrogen and oxygen, comprising the steps of: preparing a palladium nano-oxide solution containing at least one selected from octahedron and Rhombic dodecahedron; The present invention provides a method of producing hydrogen peroxide directly using a shape-controlled palladium nano-particle-supported catalyst containing particles.
본 발명의 바람직한 일실시예에 따르면, 상기 형상 제어된 팔라듐 나노입자 담지 촉매는 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노 입자가 담지체에 담지된 것이고, 상기 팔라듐 나노 입자 크기는 1 nm ~ 30 nm 일 수 있다. According to a preferred embodiment of the present invention, the shape-controlled palladium nanoparticle-supporting catalyst is one in which palladium nanoparticles of any one or more selected from Octahedron and Lombic Dodecahedron are supported on a support, The nanoparticle size can be from 1 nm to 30 nm.
본 발명의 바람직한 일실시예에 따르면, 상기 형상 제어된 팔라듐 나노 입자 담지 촉매는 상기 팔라듐 나노입자를 0.1 ~ 20 중량% 포함할 수 있다. According to a preferred embodiment of the present invention, the shape-controlled palladium nano-particle-supporting catalyst may contain 0.1 to 20 wt% of the palladium nanoparticles.
본 발명의 다른 태양은 과산화수소 직접 생산용 촉매에 있어서, 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노입자가 담지체에 담지된 형상 제어된 팔라듐 나노입자 담지촉매를 제공한다.
In another aspect of the present invention, there is provided a catalyst for direct production of hydrogen peroxide, which comprises a shape-controlled palladium nano-particle-supporting catalyst in which palladium nanoparticles, which are at least one selected from octahedron and lomobic dodecahydroquinone, do.
본 발명을 통해 형상 제어된 팔라듐 나노입자 담지 촉매 및 이의 제조방법을 제공할 수 있다.The present invention can provide a palladium nano-particle-supported catalyst whose shape is controlled and a method for producing the same.
또한, 본 발명의 촉매를 사용하여, 과산화수소 직접 생산할 수 있는 방법을 제공할 수 있다. In addition, a method of directly producing hydrogen peroxide using the catalyst of the present invention can be provided.
따라서, 본 발명을 통해 과산화수소 직접 생산에 있어서, 과산화수소 선택도와 수율을 향상시킬 수 있다.
Therefore, the present invention can improve hydrogen peroxide selectivity and yield in direct production of hydrogen peroxide.
도 1은 실시예에서 제조된 팔라듐 나노 입자의 TEM 사진이다.
도 2는 실시예에서 제조된 팔라듐 담지 촉매의 TEM 사진이다.
도 3은 비교예에서 제조된 팔라듐 나노 입자의 TEM 사진이다.
도 4는 비교예에서 제조된 팔라듐 담지 촉매의 TEM 사진이다.
도 5는 제조예 및 비교제조예의 수소전환율과 과산화수소 선택도 그래프이다.
도 6은 제조예 및 비교제조예의 과산화수소 생산성 결과 그래프이다.1 is a TEM photograph of the palladium nanoparticles prepared in the examples.
2 is a TEM photograph of the palladium-supported catalyst prepared in the example.
3 is a TEM photograph of the palladium nanoparticles prepared in Comparative Example.
4 is a TEM photograph of the palladium-supported catalyst prepared in Comparative Example.
5 is a graph of hydrogen conversion and hydrogen peroxide selectivity for the preparation examples and comparative production examples.
Fig. 6 is a graph of the hydrogen peroxide productivity results of the production example and the comparative production example.
이하, 본 발명을 상세하게 설명한다. 하기의 구체적 설명은 본 발명의 일실시예에 대한 설명이므로, 비록 한정적 표현이 있더라도 특허청구범위로부터 정해지는 권리범위를 제한하는 것은 아니다.
Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.
현재 나노 입자 촉매를 이용해 과산화수소 직접 합성 반응에 적용한 연구는 많지 않으며, 상업화 단계까지는 아직 도달하지 못한 상태이다.Currently, few studies have been conducted on the direct synthesis of hydrogen peroxide using nanoparticle catalysts, and commercialization has not yet been achieved.
특히 입자의 형상 제어를 통해 상이한 결정면을 노출시켜 과산화수소의 활성 및 선택도를 높이는 연구는 진행된 바 없다.In particular, research has not been conducted to increase the activity and selectivity of hydrogen peroxide by exposing different crystal faces through particle shape control.
이에 본 발명자들은 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노 입자를 포함하는 형상 제어된 팔라듐 나노 입자 담지 촉매를 사용하여 과산화수소 직접 생산 방법을 발견하고 본 발명을 완성하였다.Accordingly, the inventors of the present invention have discovered a method of directly producing hydrogen peroxide using a shape-controlled palladium nano-particle-supporting catalyst comprising palladium nanoparticles, which is at least one selected from octahedron and lomobic dodecahedron, and completed the present invention .
즉, 본 발명에서는 수소와 산소를 이용한 과산화수소를 직접 생산하는 방법에 있어서, 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노 입자를 포함하는 형상 제어된 팔라듐 나노 입자 담지 촉매를 사용하여 생산하는 방법을 제공한다.That is, according to the present invention, there is provided a method for directly producing hydrogen peroxide using hydrogen and oxygen, comprising the steps of: controlling a shape-controlled palladium nano-particle supporting catalyst comprising palladium nanoparticles selected from octahedron and lomobic dodecahedron; To provide a method for producing.
본 발명의 바람직한 일실시예에 따르면, 상기 형상 제어된 팔라듐 나노 입자 담지 촉매 및 알코올 용매를 포함하는 반응기에 반응물인 수소 및 산소를 공급하여 반응시켜 과산화수소를 직접 생산할 수 있으며, 바람직하게는 상기 반응기에 반응물로 질소를 더 공급하여 반응시켜 생산할 수 있다.According to a preferred embodiment of the present invention, hydrogen peroxide can be directly produced by reacting hydrogen and oxygen as reactants to a reactor including the shape-controlled palladium nano-particle-supporting catalyst and an alcohol solvent, The reaction product can be produced by further supplying nitrogen as a reaction product.
보다 구체적으로 설명하면, 본 발명의 과산화수소 직접 생산 방법은 알코올 용매(반응매질)로 메탄올, 에탄올 또는 물을 사용하여 액상 반응으로 진행할 수 있으며, 바람직하게는 에탄올과 물의 혼합물을 사용할 수 있다. 그리고 용매는 과산화수소의 용도 따라 적합한 것을 사용할 수 있다.More specifically, the hydrogen peroxide direct production method of the present invention can be carried out in a liquid phase reaction using methanol, ethanol or water as an alcohol solvent (reaction medium), and preferably a mixture of ethanol and water can be used. The solvent may be any one suitable for the use of hydrogen peroxide.
그리고 상기 반응은 고온 고압 반응기(Autoclave)에서 진행될 수 있으며, 반응기 외벽을 둘러싼 가열 장치와 반응기 내부에 설치되어 있는 온도계 및 냉각 장치를 통해 일정한 반응 온도를 유지하는 것이 바람직할 수 있다.The reaction may be carried out in a high-temperature autoclave, and it may be desirable to maintain a constant reaction temperature through a heating device surrounding the outer wall of the reactor and a thermometer and a cooling device installed inside the reactor.
반응물인 수소 가스와 산소 가스는 용매에 대한 용해도를 향상시키기 위하여 용매에 담길 수 있는 관(Dip Tube)을 이용하여 용매에 직접 공급하는 것이 바람직할 수 있다. 수소 가스는 1 ~ 4 mL/min의 유속으로 흘려줄 수 있으며, 산소 가스는 10 ~ 40 mL/min의 유속으로 흘려주는 것이 바람직할 수 있다. 더욱 바람직하게는 수소 가스는 1.5 ~ 2.5 mL/min로, 산소 혼합 가스는 15 ~ 25 mL/min로 유지하여, 수소 : 산소 몰 비가 1 : 5 ~ 1 : 15일 수 있다.The hydrogen gas and the oxygen gas, which are the reactants, may be directly supplied to the solvent by using a pipe (Dip Tube) which can be contained in the 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: oxygen molar ratio may be from 1: 5 to 1:15 while the hydrogen gas is maintained at 1.5 to 2.5 mL / min and the oxygen mixed gas is maintained at 15 to 25 mL / min.
수소 가스와 산소 가스를 일정한 유속으로 흘려주면서 BPR(Back Pressure Regulator)을 사용하여 전체 반응압력을 조절하게 되며, 반응압력은 반응기에 연결되어 있는 압력계를 통하여 측정될 수 있다. 반응 압력은 1~40 기압, 바람직하게는 상압으로 유지하는 것이 바람직하며, 반응 온도는 10 ~ 30 ℃로 유지하면서 반응을 진행하는 것이 바람직할 수 있다.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.
또한, 본 발명의 바람직한 일실시예에 따르면, 상기 알코올 용매에는 산을 더 포함할 수 있으며, 상기 산은 황산 (H2SO4), 염산 (HCl), 인산 (H3PO4) 및 질산 (HNO3) 중 선택되는 어느 하나 이상일 수 있고, 바람직하게는 인산 (H3PO4)일 수 있다.According to a preferred embodiment of the present invention, the alcohol solvent may further include an acid, and the acid may be sulfuric acid (H 2 SO 4 ), hydrochloric acid (HCl), phosphoric acid (H 3 PO 4 ) 3 ), and preferably it may be phosphoric acid (H 3 PO 4 ).
상기 반응에 산의 농도는 용매 내에 0 ~ 1 M인 것이 바람직하며, 가장 바람직하게는 0.01 ~ 0.05 M로 설정하는 것이 더욱 바람직하다.The concentration of the acid in the reaction is preferably 0 to 1 M, and most preferably 0.01 to 0.05 M in the solvent.
한편, 본 발명에서는 옥타헤드론 및/또는 롬빅 도데카헤드론 형태인 팔라듐 나노입자를 포함하는 형상제어된 팔라듐 나노 입자 담지촉매를 사용하여 과산화수소를 직접 생산함으로써, 할로겐 화합물을 사용하지 않고도 충분한 과산화수소 선택도를 얻을 수 있고, 후처리 문제도 해결하였다.
Meanwhile, in the present invention, by directly producing hydrogen peroxide using a shape-controlled palladium nano-particle-supported catalyst comprising palladium nanoparticles in the form of octahedron and / or lomobic dodecaheadone, sufficient hydrogen peroxide can be obtained without using a halogen compound And the post-treatment problem was solved.
본 발명의 다른 태양은 과산화수소 직접 생산용 촉매에 있어서, 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노입자가 담지체에 담지된 형상 제어된 팔라듐 나노입자 담지 촉매를 제공한다.In another aspect of the present invention, there is provided a catalyst for direct production of hydrogen peroxide, which comprises a shape-controlled palladium nano-particle-supporting catalyst in which palladium nanoparticles, which are at least one selected from octahedron and lomobic dodecahydroquinone, do.
본 발명의 바람직한 일실시예에 따르면, 상기 팔라듐 나노 입자 크기는 1 nm ~ 30 nm 일 수 있고, 바람직하게는 5 ~ 30nm 일 수 있다.According to a preferred embodiment of the present invention, the size of the palladium nanoparticles may be 1 nm to 30 nm, preferably 5 to 30 nm.
이는 상기 범위의 크기인 팔라듐 나노 입자를 사용할 경우, 과산화수소 선택도와 수율이 가장 우수하기 때문에 바람직할 수 있다. The use of palladium nanoparticles having the above-mentioned range may be preferable since hydrogen peroxide selectivity and yield are most excellent.
그리고 상기 담지체는 금속 산화물계 및 탄소계 중 선택되는 어느 하나 이상을 포함할 수 있고, 상기 금속산화물계는 실리카, 알루미나, 타이타니아 및 지르코니아 중 선택되는 어느 하나 이상을 포함할 수 있으며, 상기 탄소계는 탄소나노튜브, 그래핀 및 메조포러스 탄소 중 선택되는 어느 하나 이상을 포함할 수 있다. The support may include at least one selected from the group consisting of a metal oxide series and a carbon series, and the metal oxide series may include at least one selected from silica, alumina, titania and zirconia, May include at least one selected from carbon nanotubes, graphene, and mesoporous carbon.
또한, 본 발명의 바람직한 일실시예에 따르면, 상기 형상 제어된 팔라듐 나노 입자 담지 촉매는 상기 팔라듐 나노입자를 0.1 ~ 20 중량% 포함할 수 있고, 바람직하게는 0.5 ~ 5중량%일 수 있다. 만약 상기 팔라듐 나노입자가 0.1 중량%미만을 포함하면, 과산화수소 수율이 낮을 수 있고, 반대로 20중량%를 초과하면, 과산화수소 선택도가 낮을 수 있다. Also, according to a preferred embodiment of the present invention, the shape-controlled palladium nano-particle-supporting catalyst may include 0.1-20 wt% of the palladium nanoparticles, and preferably 0.5-5 wt%. If the palladium nanoparticles contain less than 0.1% by weight, the yield of hydrogen peroxide may be low, while conversely, if it exceeds 20% by weight, the hydrogen peroxide selectivity may be low.
본 발명의 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노입자를 포함하는 촉매의 제조방법은 하기와 같을 수 있다.A method for preparing a catalyst comprising palladium nanoparticles of any one or more of octahedron and lomobic dodecahedron of the present invention may be as follows.
제조된 팔라듐 나노입자를 용매에 재분산시킨 후, 담지체에 담지하여 제조할 수 있고, 상기 용매는 물 및 에탄올 중 선택되는 어느 하나 이상을 포함할 수 있다.The palladium nanoparticles thus prepared may be redispersed in a solvent and then supported on a support. The solvent may include at least one selected from water and ethanol.
한편, 본 발명의 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노입자를 포함하는 형상 제어된 팔라듐 나노 입자 담지 촉매는 팔라듐 나노입자의 형상의 변화 없이 담지체 상에 포함되어있다.On the other hand, the shape-controlled palladium nano-particle-supporting catalyst comprising palladium nanoparticles of any one or more selected from the octahedron and the lomobic dodecahedron of the present invention is contained on the carrier without changing the shape of the palladium nano- .
따라서, 본 발명에서 제공하는 형상 제어된 팔라듐 나노입자 담지 촉매의 팔라듐 나노입자는 과산화수소 생성시 동반하는 부반응을 억제해 과산화수소 선택도를 향상시켜, 생산성이 우수한 과산화수소 직접 생산이 가능하게 한다. Therefore, the palladium nanoparticles of the shape-controlled palladium nano-particle-supporting catalyst provided in the present invention can suppress the side reaction accompanying the generation of hydrogen peroxide, thereby improving the selectivity of hydrogen peroxide and enabling the direct production of hydrogen peroxide having excellent productivity.
결론적으로 본 발명에서 제공하는 형상 제어된 옥타헤드론 및 롬빅 도데카헤드론 중 선택되는 어느 하나 이상의 형태인 팔라듐 나노입자를 포함하는 형상 제어된 팔라듐 나노입자 담지 촉매를 사용하는 과산화수소 직접 생산방법은 생산성이 우수한 과산화수소 직접 생산이 가능할 수 있다.
In conclusion, the direct hydrogen peroxide production method using a shape-controlled palladium nano-particle-supported catalyst comprising palladium nanoparticles, which is one or more of the shape-controlled octahedron and lombic dodecaheadolone provided by the present invention, This excellent direct hydrogen peroxide production may be possible.
이하 본 발명을 실시예에 기초하여 더욱 상세하게 설명하지만, 하기에 개시되는 본 발명의 실시 형태는 어디까지 예시로써, 본 발명의 범위는 이들의 실시 형태에 한정되지 않는다. 본 발명의 범위는 특허청구범위에 표시되었고, 더욱이 특허 청구범위 기록과 균등한 의미 및 범위 내에서의 모든 변경을 함유하고 있다. 또한, 이하의 실시예, 비교예에서 함유량을 나타내는 "%" 및 "부"는 특별히 언급하지 않는 한 중량 기준이다.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.
실시예Example : : 옥타헤드론Octahedron 형태인 팔라듐 담지 촉매 제조방법 Method for preparing palladium-supported catalyst
아스코르빅산(Ascorbic acid) 0.680 mmol, PVP 0.189 mmol, 브롬칼륨(KBr) 5 mmol를 3차 초순수물에 녹여 16mL를 준비한 후 80℃에서 5분간 마그네틱 막대를 이용해서 교반한다. 디소듐 테트라클로로팔라데이트(Disodium tetrachloropalladate, Na2PdCl4) 용액(63.8 mM) 6 mL를 넣고 같은 온도에서 3시간 동안 마그네틱 막대로 교반하여 반응을 진행시킨다. 반응 후 반응용액과 아세톤을 1: 10의 비율로 혼합하여 넣고 원심분리기(3500rpm, 10분)를 통해 생성된 나노 입자를 회수한 후 3차 초순수물을 이용하여 수차례 세척과정을 진행하여 팔라듐 큐브 입자를 제조하였다. 0.680 mmol of ascorbic acid, 0.189 mmol of PVP, and 5 mmol of potassium bromide (KBr) are dissolved in tertiary ultrapure water to prepare 16 mL of the solution, followed by stirring at 80 ° C. for 5 minutes using a magnetic rod. Add 6 mL of disodium tetrachloropalladate (Na 2 PdCl 4 ) solution (63.8 mM) and stir at the same temperature for 3 hours with a magnetic stir bar. After 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 several times with tertiary ultrapure water, and palladium cube Particles were prepared.
그리고 큐브 입자(39.6mg)을 3차 초순수물(22mL)에 재분산시켜 시드(seed) 용액 1.8 mg/mL를 준비하였고, 포름알데히드(Formaldehyde, 200μL, 37 wt% in H2O), PVP 0.189 mmol 를 3차 초순수물에 녹여 16mL의 용액을 제조한 후, 상기 제조한 시드(seed)용액 1.2 mL를 혼합하여 30분간 교반하였다. 그리고 60℃에서 5분간 마그네틱 막대를 이용해서 교반하였다.The cube particles (39.6 mg) were re-dispersed in tertiary ultrapure water (22 mL) to prepare a seed solution of 1.8 mg / mL. Formaldehyde (200 μL, 37 wt% in H 2 O) mmol were dissolved in tertiary ultrapure water to prepare 16 mL of a solution, and 1.2 mL of the seed solution prepared above was mixed and stirred for 30 minutes. The mixture was stirred at 60 ° C for 5 minutes using a magnetic rod.
그리고 디소듐 테트라클로로팔라데이트(Disodium tetrachloropalladate, Na2PdCl4, 33 mM)용액 6 mL를 넣고 같은 온도에서 3시간 동안 60℃에서 마그네틱 막대로 교반하여 반응을 진행시켰다. 반응 후 아세톤을 넣고 원심분리기를 통해 생성된 나노 입자를 회수한 후 3차 초순수물을 이용하여 수차례 세척과정을 진행하였다. 이렇게 준비된 팔라듐 나노입자를 3차 초순수물(4mL)에 재분산시킨 후 실리카 담체(4 g, 비표면적(specific surface area) = 291 m2/g, 기공부피(pore volume) = 1.105 cm3/g, 제조사; Sigma-Aldrich)에 담지한 후 진공 오븐(60℃, 24시간)에서 건조시켜서, 옥타헤드론 형태인 팔라듐 담지 촉매를 제조하였다.
Then, 6 mL of disodium tetrachloropalladate (Na 2 PdCl 4 , 33 mM) solution was added thereto, and the mixture was stirred at the same temperature for 3 hours at 60 ° C. with a magnetic rod. After the reaction, acetone was added and the nanoparticles produced by the centrifugal separator were recovered and then washed several times using tertiary ultrapure water. The prepared palladium nanoparticles were redispersed in tertiary ultrapure water (4 mL), and then the silica carrier (4 g, specific surface area = 291 m 2 / g, pore volume = 1.105 cm 3 / g , Manufactured by Sigma-Aldrich), and dried in a vacuum oven (60 ° C, 24 hours) to prepare a palladium-supported catalyst in the form of an octahedron.
비교예Comparative Example
아스코르빅산(Ascorbic acid) 0.680 mmol, PVP 0.189 mmol, 브롬칼륨(KBr) 5 mmol를 3차 초순수물에 녹여 16mL의 수용액을 제조한 후, 80℃에서 10분간 마그네틱 막대를 이용해서 교반한다. 디소듐 테트라클로로팔라데이트(Disodium tetrachloropalladate, Na2PdCl4) 용액(63.8 mM) 6 mL를 넣고 같은 온도에서 3시간 동안 마그네틱 막대로 교반하여 반응을 진행시킨다. 반응 후 반응용액과 아세톤을 1: 10의 비율로 혼합하여 넣고 원심분리기(3500rpm, 10분)를 통해 생성된 나노 입자를 회수한 후 3차 초순수물을 이용하여 수차례 세척과정을 진행한다. 제조된 팔라듐 나노입자를 3차 초순수물(4mL)에 재분산시킨 후 무정형의 (4 g, 비표면적(specific surface area) = 291 m2/g, 기공부피(pore volume) = 1.105 cm3/g, 제조사; Sigma-Aldrich)에 담지한 후 진공 오븐(60℃, 24시간)에서 건조시켜서, 9 nm 큐브형태의 팔라듐 담지 촉매를 제조하였다.
0.680 mmol of ascorbic acid, 0.189 mmol of PVP, and 5 mmol of potassium bromide (KBr) were dissolved in tertiary ultrapure water to prepare 16 mL of an aqueous solution, followed by stirring at 80 ° C. for 10 minutes using a magnetic rod. Add 6 mL of disodium tetrachloropalladate (Na 2 PdCl 4 ) solution (63.8 mM) and stir at the same temperature for 3 hours with a magnetic stir bar. After the reaction, the reaction solution and acetone are mixed at a ratio of 1:10, the nanoparticles produced through a centrifuge (3500 rpm, 10 minutes) are recovered, and washed several times with tertiary ultrapure water. The prepared palladium nanoparticles were redispersed in tertiary ultrapure water (4 mL), and then the amorphous (4 g, specific surface area = 291 m 2 / g, pore volume = 1.105 cm 3 / g , Manufactured by Sigma-Aldrich), and dried in a vacuum oven (60 DEG C, 24 hours) to prepare a palladium-supported catalyst in the form of a 9 nm cube.
수소와 산소로부터 과산화수소 직접생산Direct production of hydrogen peroxide from hydrogen and oxygen
제조예Manufacturing example
이중 자켓 반응기에 반응용매 (초순수물, 120 mL; 에탄올(ethanol) 30 mL; 및 인산(H3PO4) 0.03 M)와 실시예의 촉매를 200 mg을 넣고 3시간 동안 반응을 진행하였다. 반응 온도는 20℃, 압력은 1 atm으로 유지하였고, 반응가스 (H2/O2 =1/10)는 분당 22 mL을 일정하게 흘려주었다. 그리고 반응 후 생성된 과산화수소를 수거하였다.The reaction was carried out for 3 hours by adding a reaction solvent (ultrapure water, 120 mL; ethanol; 30 mL; and phosphoric acid (H 3 PO 4 ) 0.03 M) and 200 mg of the catalyst of the example to the double jacket reactor. 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. The hydrogen peroxide produced after the reaction was collected.
비교제조예Comparative Manufacturing Example
실시예의 촉매를 사용하지 않고, 비교예의 촉매를 사용한 것을 제외하고는 상기 제조예와 동일하게 과산화수소를 수거하였다.
Hydrogen peroxide was collected in the same manner as in the above production example except that the catalyst of the example was not used and the catalyst of the comparative example was used.
실험예Experimental Example 1 One
투과 전자현미경을 통하여 실시예 및 비교예를 관찰하였다.The examples and comparative examples were observed through a transmission electron microscope.
결과적으로, 도 1 및 2는 실시예에서 제조된 옥타헤드론형태의 팔라듐 담지 촉매를, 도 3 및 4에서는 비교예에서 제조된 팔라듐 담지 촉매를 확인할 수 있다.As a result, FIGS. 1 and 2 show the palladium-supported catalysts of the octahedron type prepared in the examples, and FIGS. 3 and 4 show the palladium-supported catalysts prepared in the comparative examples.
구체적으로 설명하면, 먼저 도 1에서는 생성된 나노입자가 옥타헤드론 형태를 가지고 있음을 확인할 수 있고, 입자의 평균 크기는 23 nm를 갖는다. 또한 옥타헤드론 입자의 면간 거리 (0.227 nm)와 FFT 패턴을 통해 옥타헤드론은 fcc 팔라듐 {111}면으로 둘러 쌓여 있음을 확인할 수 있다. Specifically, in FIG. 1, it can be seen that the nanoparticles produced have an octahedron form, and the average size of the particles is 23 nm. In addition, it can be confirmed that the octahedron is surrounded by {111} faces of fcc palladium by the interplanar distance (0.227 nm) of the octahedron particles and the FFT pattern.
도 2에서는 생성된 팔라듐 옥타헤드론 나노 입자가 크기 및 형상의 변화 없이 실리카위에 담지된 걸 확인할 수 있다.In FIG. 2, it can be confirmed that the produced palladium octahedron nanoparticles are supported on the silica without change in size and shape.
그리고 도 3에서는 균일한 크기 (9 nm)를 갖는 큐브형태의 팔라듐 나노입자가 생성됨을 확인할 수 있고, 또한 면간 거리 (0.195 nm)와 FFT 패턴을 통해 큐브가 fcc 팔라듐 {100}면으로 둘러 쌓여있음을 확인할 수 있으며, 도 4를 통해서는 생성된 큐브형태의 팔라듐 나노 입자가 크기 및 형상의 변화 없이 실리카위에 잘 분산되어 있음을 확인할 수 있다.In Fig. 3, it can be seen that cube-shaped palladium nanoparticles having a uniform size (9 nm) are produced. Also, the cube is enclosed by {100} faces of fcc through the interplanar distance (0.195 nm) and the FFT pattern And FIG. 4 shows that the generated cube-shaped palladium nanoparticles are well dispersed on silica without change in size and shape.
실험예Experimental Example 2 2
(1)제조예에서 수거한 과산화수소의 농도를 요오드 적정법을 이용해서 [수학식 1]로 측정하여, 하기 과산화수소 선택도 및 생산성(Productivity)계산에 사용하였다.(1) The concentration of hydrogen peroxide collected in the production example was measured by the iodometric titration method using the formula (1), and the hydrogen peroxide selectivity and the productivity were calculated.
(2)제조예에서 반응 전과 후의 수소의 기체의 변화량을 기체크로마토그래피를 이용하여 측정하고, 하기 [수학식 2]를 이용해 수소의 전환율을 계산하여, 도 5 에 나타내었다.(2) The change amount of hydrogen gas before and after the reaction in the production example was measured by gas chromatography, and the conversion rate of hydrogen was calculated using the following formula (2), and it is shown in FIG.
(3)제조예의 과산화수소의 선택도는 하기 [수학식 3]으로 계산하여, 도 5 에 나타내었다.(3) The selectivity of hydrogen peroxide in the production example is calculated by the following formula (3) and is shown in Fig.
(4)제조예의 과산화수소의 생산성을 하기 [수학식 4]로 계산하여, 도 6에 나타내었다.(4) The productivity of hydrogen peroxide in the production example is calculated by the following formula (4), and is shown in Fig.
[수학식 1][Equation 1]
[수학식 2]&Quot; (2) "
[수학식 3]&Quot; (3) "
[수학식 4]&Quot; (4) "
도 5 및 6에서 실시예 및 비교예를 사용하여 수소와 산소로부터 생산된 과산화수소의 결과를 알 수 있다.The results of hydrogen peroxide produced from hydrogen and oxygen can be seen in Figures 5 and 6 using the examples and comparative examples.
구체적으로 도 5에서 알 수 있듯이, 수소 전환율은 약 10%로 제조예 및 비교제조예가 비슷한 값을 가지나, 과산화수소 선택도는 실시예의 촉매(Pd octahedron/SiO2, 41%)를 사용한 제조예가 비교예의 촉매(Pd cube/SiO2, 30%)를 사용한 비교제조예보다 11% 높은 값을 갖는다는 것을 확인할 수 있다. Specifically, as can be seen from FIG. 5, the hydrogen conversion was about 10%, and the production example and the comparative preparation example had similar values, while the hydrogen peroxide selectivity was comparable to the production example using the catalyst of the example (Pd octahedron / SiO 2 , 41% And 11% higher than the comparative example using the catalyst (Pd cube / SiO 2 , 30%).
그리고 도 6은 실시예 및 비교예의 촉매 성능에 따른 생산성(productivity)을 비교한 결과를 나타내며, 실시예의 촉매(Pd octahedron/SiO2, 106 mmol of H2O2·g-1Pd·h-1)를 사용한 제조예가 비교예의 촉매(Pd cube/SiO2, 86 mmol of H2O2·g-1Pd·h-1)를 사용한 비교제조예보다 높은 생산성(productivity)을 보인다. 6 shows the results of comparing the productivity according to the catalyst performance of the examples and the comparative examples. The catalyst of the example (Pd octahedron / SiO 2 , 106 mmol of H 2 O 2揃 g -1 Pd 揃 h -1 (Pd cube / SiO 2 , 86 mmol of H 2 O 2揃 g -1 Pd 揃 h -1 ) exhibited higher productivity than the comparative example using the catalyst of the comparative example (Pd cube / SiO 2 , 86 mmol of H 2 O 2揃 g -1 Pd 揃 h -1 ).
따라서, 실시예의 촉매가 과산화수소 직접 생산에 과산화수소의 선택도와 생산성(productivity)측면에서 우수하다. Therefore, the catalyst of the example is excellent in the selectivity and productivity of hydrogen peroxide in the direct production of hydrogen peroxide.
즉, 팔라듐 옥타헤드론 입자를 둘러싸고 있는 팔라듐{111} 결정면이 팔라듐 큐브 입자를 둘러싸고 있는 팔라듐{100} 결정면보다 수소와 산소로부터 과산화수소를 과산화수소 합성하는데 적합한 팔라듐의 결정면이라고 볼 수 있다.That is, the palladium {111} crystal plane surrounding the palladium octahedron particles is a crystal plane of palladium suitable for synthesizing hydrogen peroxide from hydrogen and oxygen than the palladium {100} crystal plane surrounding the palladium cube particles.
Claims (11)
옥타헤드론 형태인 팔라듐 나노 입자를 포함하는 형상 제어된 팔라듐 나노 입자 담지 촉매를 사용하고,
상기 형상 제어된 팔라듐 나노입자 담지 촉매는 팔라듐 나노 입자가 담지체에 담지된 것이며,
상기 팔라듐 나노 입자의 크기는 5 nm 내지 30 nm 이고,
상기 형상 제어된 팔라듐 나노 입자 담지 촉매는 상기 팔라듐 나노입자를 0.1 내지 20 중량% 포함하며,
할로겐 화합물을 사용하지 않고 과산화수소를 생산하는 것을 특징으로 하는 과산화수소 직접 생산 방법. In a method for directly producing hydrogen peroxide using hydrogen and oxygen,
Controlled palladium nano-particle-supported catalyst containing palladium nanoparticles in the form of octahedron,
The shape-controlled palladium nano-particle-supporting catalyst is one in which palladium nano-particles are supported on a support,
The size of the palladium nanoparticles is 5 nm to 30 nm,
The shape-controlled palladium nano-particle-supporting catalyst comprises 0.1 to 20% by weight of the palladium nanoparticles,
Wherein hydrogen peroxide is produced without using a halogen compound.
상기 담지체는 금속 산화물계; 및 탄소계 중 선택되는 어느 하나 이상을 포함하고,
상기 금속산화물계는 실리카, 알루미나, 타이타니아 및 지르코니아 중 선택되는 어느 하나 이상을 포함하며,
상기 탄소계는 탄소나노튜브, 그래핀 및 메조포러스 탄소 중 선택되는 어느 하나 이상을 포함하는 것을 특징으로 하는 과산화수소 직접 생산 방법.The method according to claim 1,
The support may be a metal oxide system; And a carbon-based material,
The metal oxide system includes at least one selected from silica, alumina, titania, and zirconia,
Wherein the carbon-based system comprises at least one selected from carbon nanotubes, graphene, and mesoporous carbon.
상기 형상 제어된 팔라듐 나노 입자 담지 촉매 및 알코올 용매를 포함하는 반응기에서 반응물인 수소 및 산소를 공급하여 반응시키는 것을 특징으로 하는 과산화수소 직접 생산방법.The method according to claim 1,
Wherein the reaction is carried out by supplying hydrogen and oxygen as reactants in a reactor including the shape-controlled palladium nano-particle-supporting catalyst and an alcohol solvent.
반응기에 질소를 추가로 공급하여 반응시키는 것을 특징으로 하는 과산화수소 직접 생산방법.6. The method of claim 5,
And further adding nitrogen to the reactor to effect the reaction.
상기 알코올 용매는 산을 더 포함하는 것을 특징으로 하는 과산화수소 직접 생산방법. 6. The method of claim 5,
Wherein the alcohol solvent further comprises an acid.
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