KR20060003933A - Titanium silicalite zeolite and the manufacturing method thereof - Google Patents
Titanium silicalite zeolite and the manufacturing method thereof Download PDFInfo
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- KR20060003933A KR20060003933A KR1020040051846A KR20040051846A KR20060003933A KR 20060003933 A KR20060003933 A KR 20060003933A KR 1020040051846 A KR1020040051846 A KR 1020040051846A KR 20040051846 A KR20040051846 A KR 20040051846A KR 20060003933 A KR20060003933 A KR 20060003933A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 57
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 238000007865 diluting Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 4
- XUGVQALCOCWLET-UHFFFAOYSA-F [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].[Ti+4] Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Ti+4].[Ti+4] XUGVQALCOCWLET-UHFFFAOYSA-F 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- VBLQNYINPWASGP-UHFFFAOYSA-M oxygen(2-) titanium(3+) chloride Chemical compound [O-2].[Ti+3].[Cl-] VBLQNYINPWASGP-UHFFFAOYSA-M 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- -1 TEOT Chemical compound 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000000796 flavoring agent Substances 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
본 발명에서는 실리카라이트의 실리콘과 치환될 수 있는 고용량 이상으로 티타늄을 과잉첨가하여 우수한 유기물 분해기능과 광촉매 기능을 동시에 수행 가능한 나노 입자크기의 티타늄 실리카라이트계 제올라이트 분말을 제조하였다.In the present invention, by adding an excessive amount of titanium at a high capacity that can be substituted with silicon of silica light, titanium silicalite zeolite powder having a nano particle size capable of simultaneously performing excellent organic decomposition and photocatalytic functions was prepared.
본 발명에서는 먼저 실리콘 원을 에탄올로 희석한 후, 상기 희석용액에 TiO2/(SiO2＋TiO2)의 몰비가 0.01 내지 0.2가 되도록 티타늄 원을 적하하여 교반한다. 그리고, 여기에 형취제로서 테트라 프로필 암모늄 히드록사이드(TPAOH)를 교반 및 혼합하고, 여기에 증류수를 가하여 가수분해시킨 다음, 이를 가열하여 티타늄 실리카라이트계 제올라이트 분말을 제조한 후, 동결 건조하고 하소하여 최종 티타늄 실리카라이트계 제올라이트 분말을 제조한다. 이 때, TPAOH의 농도는 SiO2의 농도를 24몰 기준으로 하여 TPAOH/SiO2＝0.36으로 되도록 하고, 증류수의 농도는 H2O/SiO2＝16으로 되도록 한다.In the present invention, the silicon source is first diluted with ethanol, and then the titanium source is added dropwise to the diluting solution so that the molar ratio of TiO 2 / (SiO 2 + TiO 2 ) is 0.01 to 0.2. Then, tetrapropyl ammonium hydroxide (TPAOH) is stirred and mixed as a flavourant, and distilled water is added thereto to hydrolyze it, which is then heated to prepare a titanium silicalite zeolite powder, followed by freeze drying and calcining. To prepare a final titanium silicalite zeolite powder. At this time, the concentration of TPAOH is such that the concentration of, and distilled water to the TPAOH / SiO 2 = 0.36 and the concentration of SiO 2 in 24 mol based on the H 2 O / SiO 2 = 16 .
제올라이트, 실리콘, 티타늄, 실리카라이트, 테트라 에틸 오르토실레인, 테트라 에틸 오르토 티타네이트, 테트라 프로필 암모늄 히드록사이드, TEOS, TEOT, TPAOHZeolite, Silicon, Titanium, Silicalite, Tetraethyl Orthosilane, Tetraethyl Ortho Titanate, Tetrapropyl Ammonium Hydroxide, TEOS, TEOT, TPAOH
Description
도 1은 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 전자 현미경 사진. 1 is an electron micrograph of TS-1 zeolite powder prepared according to the present embodiment.
도 2는 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 입도분포도.2 is a particle size distribution diagram of TS-1 zeolite powder prepared according to the present embodiment.
도 3은 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 X선 회절분석도.3 is an X-ray diffraction diagram of the TS-1 zeolite powder prepared according to the present embodiment.
본 발명은 티타늄 실리카라이트계 제올라이트 및 그 제조방법에 관한 것으로, 특히 실리카라이트의 실리콘을 치환하여 고용될 수 있는 양 이상으로 티타늄이 과잉첨가되어 우수한 유기물 분해기능과 광촉매 기능을 동시에 수행할 수 있는 티타늄 실리카라이트계 제올라이트 및 그 제조방법에 관한 것이다.The present invention relates to a titanium silicalite zeolite and a method for manufacturing the same. In particular, titanium is excessively added in an amount more than that which can be dissolved by substituting silicon of silicalite, and thus titanium can perform excellent organic decomposition and photocatalytic functions simultaneously. It relates to a silicalite zeolite and a method of manufacturing the same.
천연 또는 인공적으로 합성되는 제올라이트(Zeolite)는 다양한 조성과 구조를 가지고 있으며, 세제, 촉매, 흡착제, 흡습제 등의 여러 분야에서 사용되는 물질이다. Natural or artificially synthesized zeolite (Zeolite) has a variety of compositions and structures, and is a material used in various fields such as detergents, catalysts, adsorbents, absorbents.
특히, 제올라이트에 관한 합성방법의 다양화로 여러 형태가 개발되었는데, 최근에는 제올라이트의 구조에 천이금속 이온을 고용하는 방법으로 촉매특성이 더욱 향상되어져, 초분자 촉매, 광화학, 나노화학, 전기화학분야에까지 그 응용분야가 넓어지고 있다.In particular, various forms have been developed due to the diversification of the synthesis method for zeolites. In recent years, the catalyst properties have been further improved by employing transition metal ions in the structure of the zeolite, and have been applied to the field of supramolecular catalysts, photochemistry, nanochemistry, and electrochemistry. Applications are expanding.
그 중에서도 티타늄 실리카라이트계(이른바, TS-1) 제올라이트는 1983년 Taramasso 등에 의하여 최초로 개발된 것으로서(미국특허 제4,410,501호), 일부 Si+4를 Ti+4가 치환하는 구조를 가진다. 이렇게 치환한 Ti+4는 유기물의 산화를 선택적으로 활성화시키는 기능을 하는 것으로 보고되어 많은 연구자들의 관심의 대상이 되었으며, 이에 대한 연구가 활발히 이루어져왔다.Among them, titanium silicalite-based (so-called, TS-1) the zeolite has a structure such as a by Taramasso 1983 nyeon first developed (U.S. Patent No. 4,410,501), a part of Si Ti +4 +4 substituted. Such substituted Ti +4 has been reported to have a function of selectively activating the oxidation of organic matter has been of interest to many researchers, the research has been actively studied.
즉, TS-1 제올라이트는 불포화 탄화수소의 에폭시화 반응, 방향족 탄화수소의 수산화 반응 및 포화 탄화수소와 알콜의 산화반응, 벤젠, 페놀, 알칸 등의 수화반응 등에서 효과적인 촉매로서 기능을 한다. 특히, 과산화수소(H2O2)를 산화제로 하는 수용액 내에서 TS-1 제올라이트는 H2O2를 분해하지 않고 유기물만을 선택적으로 산화시키는 촉매로서 아주 효과적인 기능을 수행한다. That is, TS-1 zeolite functions as an effective catalyst in epoxidation of unsaturated hydrocarbons, hydroxylation of aromatic hydrocarbons and oxidation of saturated hydrocarbons and alcohols, and hydration reactions of benzene, phenol, and alkane. In particular, TS-1 zeolite in an aqueous solution containing hydrogen peroxide (H 2 O 2 ) as an oxidant performs a very effective function as a catalyst for selectively oxidizing only organic matter without decomposing H 2 O 2 .
그러나, TS-1 제올라이트 합성분말 중의 일부 Ti+4가 Si+4의 사이트에 고용되지 못하고 TiO2가 생성되는 경우에는 생성된 TiO2가 광촉매로서 작용하여 오히려 H2O2를 분해하게 된다. 이는 결국 유기물을 선택적으로 산화시키는 촉매특성을 저하시키는 것이므로, 통상적인 TS-1 제올라이트의 합성공정에 있어서는 TiO2가 생성되지 않도록 공정조건을 조절하고 있는 실정이다.However, when some Ti +4 in the TS-1 zeolite synthetic powder is not dissolved in the site of Si +4 and TiO 2 is produced, the produced TiO 2 acts as a photocatalyst to decompose H 2 O 2 . As a result, since the catalytic properties for selectively oxidizing organic matters are lowered, the process conditions are controlled so that TiO 2 is not generated in the conventional synthesis process of TS-1 zeolite.
본 발명의 목적은 상기와 같은 문제점을 이용하여, 나노 크기의 TS-1 제올라이트를 합성하면서 과잉 Ti를 첨가하여 적당량의 TiO2가 TS-1 제올라이트 전체에 균질하게 분산되도록 분포시킴으로써 유기물 분해기능의 촉매특성을 크게 저하하지 않는 범위에서 광촉매 특성을 부여하는 티타늄 실리카라이트계 제올라이트 및 그 제조방법을 제공하는데 있다.An object of the present invention is to utilize the above problems, while synthesizing the nano-size TS-1 zeolite, by adding excess Ti to distribute the appropriate amount of TiO 2 to homogeneously dispersed throughout the TS-1 zeolite catalyst of organic decomposition function It is to provide a titanium silicalite zeolite that provides a photocatalytic property in a range that does not significantly degrade the property and a method of manufacturing the same.
이와 같은 목적을 달성하기 위한 본 발명의 특징으로서, 본 발명에 의한 티타늄 실리카라이트계 제올라이트는 실리콘 산화물과 티타늄 산화물로 구성되며, 상기 티타늄 산화물은 실리콘을 치환하여 고용될 수 있는 양 이상으로 포함됨을 특징으로 한다.As a feature of the present invention for achieving the above object, the titanium silicalite zeolite according to the present invention is composed of silicon oxide and titanium oxide, the titanium oxide is characterized in that it contains more than the amount that can be dissolved by substituting silicon It is done.
또한, 본 발명의 다른 특징으로서, 본 발명에 의한 티타늄 실리카라이트계 제올라이트는 TiO2/(SiO2＋TiO2)의 몰비가 0.01 내지 0.2가 되도록 실리콘 산화물과 티타늄 산화물로 구성되는 것을 특징으로 한다.In addition, as another feature of the present invention, the titanium silicalite zeolite according to the present invention is characterized by being composed of silicon oxide and titanium oxide such that the molar ratio of TiO 2 / (SiO 2 + TiO 2 ) is 0.01 to 0.2.
또한, 본 발명의 다른 특징으로서, 상기 티타늄 실리카라이트계 제올라이트는 50 내지 200nm의 입자크기를 갖는 것을 특징으로 한다.In addition, as another feature of the present invention, the titanium silicalite zeolite is characterized in that it has a particle size of 50 to 200nm.
또한, 본 발명의 다른 특징으로서, 본 발명에 의한 티타늄 실리카라이트계 제올라이트의 제조방법은 먼저 실리콘 원을 에탄올로 희석한 후, 상기 희석용액에 TiO2/(SiO2＋TiO2)의 몰비가 0.01 내지 0.2가 되도록 티타늄 원을 적하하여 교반하 는 제 1단계와, 제 1단계에서 얻어진 혼합용액에 형취제로서 테트라 프로필 암모늄 히드록사이드(TPAOH)를 교반 및 혼합하는 제 2단계와, 제 2단계에서 얻어진 혼합물을 증류수를 가하여 가수분해하는 제 3단계와, 제 3단계에서 얻어진 가수분해물을 가열하여 티타늄 실리카라이트계 제올라이트 분말을 제조하는 제 4단계와, 제 4단계에서 제조된 상기 티타늄 실리카라이트계 제올라이트 분말을 동결 건조하고, 이를 하소하는 제 5단계로 이루어지는 것을 특징으로 한다.In addition, as another feature of the present invention, the method for producing a titanium silicalite zeolite according to the present invention first dilutes the silicon source with ethanol, and then the molar ratio of TiO 2 / (SiO 2 + TiO 2 ) to the dilution solution is 0.01 to In the first step of dropping and stirring the titanium source to be 0.2, the second step of stirring and mixing tetrapropyl ammonium hydroxide (TPAOH) as a odorant to the mixed solution obtained in the first step, and in the second step A fourth step of hydrolyzing the obtained mixture by adding distilled water, a fourth step of heating the hydrolyzate obtained in the third step to prepare titanium silicalite zeolite powder, and the titanium silicalite zeolite prepared in the fourth step The powder is lyophilized and characterized in that it comprises a fifth step of calcining it.
또한, 본 발명의 다른 특징으로서, SiO2의 농도를 24몰 기준으로 하여 상기 제 2단계의 상기 TPAOH의 농도는 TPAOH/SiO2＝0.36으로 되도록 하고, 상기 제 3단계의 상기 증류수의 농도는 H2O/SiO2＝16으로 되도록 하는 것을 특징으로 한다. Further, as another feature of the invention, the concentration of the distilled water in the concentration of the TPAOH in the second step by the concentration in the 24-mole basis, and such that the TPAOH / SiO 2 = 0.36 in the first stage 3 SiO 2 is H characterized in that that the 2 O / SiO 2 = 16.
또한, 본 발명의 다른 특징으로서, 상기 제 4단계는 상기 혼합물질을 80 내지 120℃에서 24시간 내지 144시간동안 가열하는 것을 특징으로 한다.In another aspect of the present invention, the fourth step is characterized in that the mixture is heated at 80 to 120 ℃ for 24 to 144 hours.
또한, 본 발명의 다른 특징으로서, 상기 제 5단계의 상기 하소온도는 500 내지 600℃로 되는 것을 특징으로 한다.In addition, as another feature of the present invention, the calcining temperature of the fifth step is characterized in that 500 to 600 ℃.
또한, 본 발명의 다른 특징으로서, 상기 실리콘 원은 테트라 에틸 오르토실레인(TEOS), 테트라 에틸 오르토실리케이트, 실리카 졸, 테트라 메틸 오르토실리케이트, 테트라 메틸 오르 실로사인, 테트라 프로필 오르토실리케이트 중의 적어도 어느 하나를 사용하는 것을 특징으로 한다.In another aspect of the present invention, the silicon source may include at least one of tetraethyl orthosilane (TEOS), tetraethyl orthosilicate, silica sol, tetramethyl orthosilicate, tetramethyl orsilosine, and tetrapropyl orthosilicate. It is characterized by using.
또한, 본 발명의 다른 특징으로서, 상기 티타늄 원은 테트라 에틸 오르토티타네이트(TEOT), 티타늄 부톡사이드, 티타늄 에톡사이드, 티타늄 이소프로톡사이드, 티타튬 테트라클로라이드, 티타늄옥사이드 클로라이드 중의 적어도 어느 하나를 사용하는 것을 특징으로 한다.In addition, as another feature of the present invention, the titanium source is at least one of tetra ethyl ortho titanate (TEOT), titanium butoxide, titanium ethoxide, titanium isoprooxide, titanium titanium chloride, titanium oxide chloride It is characterized by using.
또한, 본 발명의 다른 특징으로서, 본 발명에 의한 티타늄 실리카라이트계 제올라이트는 티타늄이 과잉첨가되어 유기물 분해제 및 광 촉매제로서 사용되는 것을 특징으로 한다.In addition, as another feature of the present invention, the titanium silicalite zeolite according to the present invention is characterized in that titanium is excessively added and used as an organic substance decomposition agent and a photocatalyst.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서의 티타늄 실리카라이트계 제올라이트는 대략 다음과 같은 단계로 제조되어진다.The titanium silicalite zeolite in the present invention is prepared in approximately the following steps.
(가) 먼저, 각각 실리콘 알콕시드 및 티타늄 알콕시드로부터 실리콘 옥사이드 원(source) 및 티타늄 옥사이드 원을 준비한다. 이 때, 실리콘 원 및 티타늄 원은 통상적으로 사용되는 것이면 사용 가능하다. (A) First, a silicon oxide source and a titanium oxide source are prepared from silicon alkoxide and titanium alkoxide, respectively. At this time, a silicon source and a titanium source can be used if it is what is normally used.
즉, 실리콘 원으로서는 테트라 에틸 오르토실레인(TEOS), 테트라 에틸 오르토실리케이트, 실리카 졸, 테트라 메틸 오르토실리케이트, 테트라 메틸 오르 실로사인, 테트라 프로필 오르토실리케이트 등 중 어느 하나 이상 사용 가능하며, 바람직하게는 테트라 에틸 오르토실레인(TEOS)이 가장 양호하다. That is, as the silicon source, any one or more of tetraethyl orthosilane (TEOS), tetra ethyl orthosilicate, silica sol, tetra methyl orthosilicate, tetra methyl orsilosine, tetrapropyl orthosilicate and the like can be used, preferably tetra Ethyl orthosilane (TEOS) is the best.
또한, 티타늄 원으로서는 가수분해가 가능한 티타늄 화합물을 사용하며, 테트라 에틸 오르토티타네이트(TEOT), 티타늄 부톡사이드, 티타늄 에톡사이드, 티타늄 이소프로톡사이드, 티타튬 테트라클로라이드, 티타늄옥사이드 클로라이드 등이 사용가능하며, 바람직하게는 테트라 에틸 오르토티타네이트(TEOT)가 가장 양호하다.In addition, a titanium compound capable of hydrolysis is used as the titanium source, and tetra ethyl ortho titanate (TEOT), titanium butoxide, titanium ethoxide, titanium isoprooxide, titanium titanium chloride, titanium oxide chloride, and the like are used. Possible, preferably tetra ethyl ortho titanate (TEOT).
(나) 별도의 용기에 에탄올을 넣고 이에 상기 실리콘 옥사이드를 적하하여 희석한 후, 이에 상기 티타늄 옥사이드 원을 적하하며 교반하고 혼합한다. 이 때, 반응물 TiO2/(SiO2＋TiO2)의 몰비는 0.01 내지 0.2가 되도록 한다. (B) Add ethanol to a separate container and dilute the silicon oxide dropwise therein, and then stir and mix the titanium oxide source dropwise thereto. At this time, the molar ratio of the reactant TiO 2 / (SiO 2 + TiO 2 ) is set to 0.01 to 0.2.
(다) 상기 혼합물에 제올라이트 결정을 형성하는 형취제(template)를 적하하며 교반하여 혼합물을 형성한다.(C) A template for forming zeolite crystals is added dropwise to the mixture, followed by stirring to form a mixture.
상기 형취제로서는 테트라 프로필 암모늄 히드록사이드(TPAOH), 테트라 에틸 암모늄 히드록사이드, 테트라 부틸 암모늄 히드록사이드, 테트라 프로필 암모늄 브로마이드, 피롤리딘, 프로필아민, 디프로필아민, 트리 프로필아민 등이 사용가능하며, 바람직하기로는 상기 TPAOH가 가장 양호하다.Tetrapropyl ammonium hydroxide (TPAOH), tetra ethyl ammonium hydroxide, tetra butyl ammonium hydroxide, tetra propyl ammonium bromide, pyrrolidine, propylamine, dipropylamine, tripropylamine, etc. are used as the odorant. Possible, preferably the TPAOH is the best.
(라) 상기 혼합물에 증류수를 적하하여 가수분해 반응을 일으킨다. 이 때, 증류수의 몰비는 SiO2의 농도인 25몰을 기준으로 하여 H2O/SiO2＝16이 되도록 한다.(D) Distilled water is added dropwise to the mixture to cause a hydrolysis reaction. At this time, the molar ratio of the distilled water is such that on the basis of a concentration of 25 mol SiO 2 H 2 O / SiO 2 = 16.
(마) 상기 혼합물을 80 내지 120℃에서 24시간 내지 144시간동안 가열하여 나노 크기의 TS-1 제올라이트 분말을 제조한 후, 10,000 내지 20,000rpm으로 원심분리하고 수세, 동결 및 건조한다.(E) The mixture is heated at 80 to 120 ° C. for 24 to 144 hours to prepare nano-sized TS-1 zeolite powder, followed by centrifugation at 10,000 to 20,000 rpm, followed by washing with water, freezing and drying.
(바) 상기 건조된 분말을 500 내지 600℃ 범위에서 수시간동안 하소하여 유기 유도체를 제거하고 최종 TS-1 제올라이트 분말을 제조한다.(F) The dried powder is calcined in the range of 500 to 600 ° C. for several hours to remove the organic derivative and to prepare the final TS-1 zeolite powder.
이하, 본 발명의 바람직한 실시예를 첨부한 도면을 참조하여 더욱 상세히 설명한다. 다만, 본 발명이 하술하는 실시예는 본 발명의 전반적인 이해를 돕기 위하여 제공되는 것이며, 본 발명은 하기 실시예로만 한정되는 것은 아니다.Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in more detail. However, the examples described below are provided to help the overall understanding of the present invention, and the present invention is not limited only to the following examples.
[실시예]EXAMPLE
본 실시예에서는 실리콘 원으로서는 테트라 에틸 오르토실레인(TEOS)을, 티타늄 원으로서는 테트라 에틸 오르토티타네이트(TEOT)를, 형취제로서는 테트라 프로필 암모늄 히드록사이드(TPAOH)를 선택하였고, 용매로서는 에탄올을, 가수분해를 위한 물은 증류수를 사용하였다.In this embodiment, tetraethyl orthosilane (TEOS) is selected as the silicon source, tetraethyl ortho titanate (TEOT) is selected as the titanium source, and tetrapropyl ammonium hydroxide (TPAOH) is used as the odorant, and ethanol is used as the solvent. As the water for hydrolysis, distilled water was used.
먼저, TEOS 및 TEOT를 아르곤 가스분위기의 글러브 박스 안에서 평량하였다. 별도의 용기에 에탄올을 넣고 이에 TEOS를 적하하여 희석한 후, 이 희석용액에 TEOT를 천천히 적하하면서 30분간 교반 및 혼합하였다. 그리고, 이에 TPAOH를 천천히 적하하며 교반하여 혼합한 다음, 증류수를 가하였다. 이상에서와 같이 첨가된 반응혼합물에 있어 주 성분의 몰비는 다음과 같다.First, TEOS and TEOT were weighed in a glove box in an argon gas atmosphere. Ethanol was placed in a separate container and TEOS was added dropwise thereto, followed by dilution. The solution was stirred and mixed for 30 minutes while slowly dropping TEOT. Then, TPAOH was slowly added dropwise and stirred, mixed, and distilled water was added thereto. The molar ratio of the main components in the reaction mixture added as above is as follows.
[TiO2/(SiO2＋TiO2)]＝0.05[TiO 2 / (SiO 2 + TiO 2 )] = 0.05
TPAOH/SiO2＝0.36(SiO2의 농도는 25몰 기준)TPAOH / SiO 2 = 0.36 (SiO 2 concentration is based on 25 mol)
H2O/SiO2＝16(SiO2의 농도는 25몰 기준)H 2 O / SiO 2 = 16 (SiO 2 concentration is based on 25 mol)
상기의 혼합물을 80℃에서 24시간 동안 리플럭싱(refluxing)한 후, 이를 테프론 용기에 넣어 오토클레이브(autoclave) 안에서 100℃로 24시간 동안 열처리하여 TS-1 제올라이트 분말을 합성하였다. 합성된 상기 TS-1 제올라이트 분말은 증류수로 희석한 후, 5℃에서 15,000rpm으로 10분간 원심분리 및 세척하고, 동결 건조기에서 건조하였다. 그리고, 550℃에서 6시간 동안 하소하여 유기 유도체를 제거하여 최종 분말을 제조하였다.After the mixture was refluxed at 80 ° C. for 24 hours, it was placed in a Teflon container and heat-treated at 100 ° C. for 24 hours in an autoclave to synthesize TS-1 zeolite powder. The synthesized TS-1 zeolite powder was diluted with distilled water, centrifuged and washed for 10 minutes at 15,000 rpm at 5 ° C, and dried in a freeze dryer. Then, calcining at 550 ℃ for 6 hours to remove the organic derivative to prepare a final powder.
도 1은 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 전자 현미경 사진이며, 도 2는 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 입도분포도이다.1 is an electron micrograph of the TS-1 zeolite powder prepared according to the present embodiment, and FIG. 2 is a particle size distribution diagram of the TS-1 zeolite powder prepared according to the present embodiment.
이와 같이 제조된 TS-1 제올라이트 분말은 균질한 구형의 형상을 하고 있으며, 입자크기는 50 ~ 200nm, 평균입경은 55nm, 입도범위는 45 ~ 80nm로 측정되었다.TS-1 zeolite powder thus prepared has a homogeneous spherical shape, the particle size of 50 ~ 200nm, the average particle diameter was 55nm, the particle size range was measured to 45 ~ 80nm.
도 3은 본 실시예에 의하여 제조된 TS-1 제올라이트 분말의 X선 회절분석도를 나타내며, 회절패턴이 TS-1 제올라이트 상의 피크를 나타내어 TS-1 제올라이트가 합성되었음을 확인할 수 있다.Figure 3 shows the X-ray diffraction analysis of the TS-1 zeolite powder prepared according to the present embodiment, the diffraction pattern shows a peak on the TS-1 zeolite can be confirmed that the TS-1 zeolite was synthesized.
본 실시예에 의하여 제조된 TS-1 제올라이트의 산화반응 정도를 측정하기 위하여 기타 촉매들과 함께 2-부탄올에 촉매로 사용하여 그 정도를 비교하였다. 반응조건으로는 2-부탄올 10ml, 산화제 H2O2 10ml에 촉매제 1g을 넣고 70℃에서 1시간 30분간 반응시켰다.In order to measure the degree of oxidation of the TS-1 zeolite prepared according to the present example, the catalyst was used as a catalyst in 2-butanol along with other catalysts to compare the degree. As reaction conditions, 1 g of a catalyst was added to 10 ml of 2-butanol and 10 ml of an oxidizing agent H 2 O 2 , and reacted at 70 ° C. for 1 hour and 30 minutes.
2-부탄올의 전환(Conversion) 정도를 측정하여 이를 표 1에 정리하였는데, 기타 촉매제와 비교할 때 본 실시예에 의하여 제조된 TS-1 제올라이트의 전환율은 22.2%로서 매우 우수한 값을 보임을 알 수 있다. 이 때, 전환율은 아래의 식 1과 같이 정의되며, 면적은 성분측정 결과그래프 상에서 각 성분영역의 면적을 가리킨다.The conversion degree of 2-butanol was measured and summarized in Table 1. However, when compared with other catalysts, the conversion rate of TS-1 zeolite prepared by the present example was 22.2%, which is very excellent. . At this time, the conversion rate is defined as in Equation 1 below, and the area indicates the area of each component region on the component measurement result graph.
(표 1)Table 1
전환율(%)＝2-부타논의 면적/(2-부타논＋2-부탄올)의 면적 (식 1)% Conversion = area of 2-butanone / (2-butanone + 2-butanol) (Equation 1)
다음으로는, 본 실시예에 의하여 제조된 TS-1 제올라이트를 사용할 때 선택적 촉매환원과정을 통하여 대기 중에 배출되는 대기오염물질인 질소 산화물(NOx)을 제거하는 정도를 알아보기 위하여 NO의 제거율을 조사하여 이를 표 2에 나타내었는데, NO 제거율이 비교적 우수한 값을 보여 우수한 질소 산화물 제거능력을 가지고 있음을 알 수 있다.Next, when using the TS-1 zeolite prepared according to the present embodiment, the removal rate of NO was examined to determine the degree of removal of nitrogen oxide (NO x ), which is an air pollutant discharged to the atmosphere through a selective catalytic reduction process. The results of the investigation are shown in Table 2, which shows that the NO removal rate is relatively excellent, indicating that the NO removal ability is excellent.
(표 2)Table 2
이상에서 설명한 바와 같이, 본 발명에 의하면 실리카라이트의 Si와 치환하여 고용될 수 있는 Ti의 정량 이상을 과잉첨가함으로써 TiO2가 균질하게 분산된 나노 입자크기의 TS-1 제올라이트 분말을 제조할 수 있었으며, 본 발명에 의한 TS-1 제올라이트 분말은 우수한 유기물 분해기능과 광촉매 기능을 동시에 수행할 수 있어 그 응용범위를 더욱 넓힐 수 있게 된다.As described above, according to the present invention, by over-adding more than the quantitative amount of Ti that can be dissolved by replacing Si of silicalite, TS-1 zeolite powder having a uniformly dispersed TiO 2 size can be prepared. , TS-1 zeolite powder according to the present invention can perform an excellent organic material decomposition function and photocatalyst function at the same time to further extend the application range.
아울러 본 발명의 바람직한 실시 예는 예시의 목적을 위해 개시된 것이며, 당업자라면 누구나 본 발명의 사상과 범위 안에서 다양한 수정, 변경, 부가 등이 가능할 것이고, 이러한 수정, 변경 등은 특허청구범위에 속하는 것으로 보아야 한다.In addition, a preferred embodiment of the present invention is disclosed for the purpose of illustration, those skilled in the art will be able to various modifications, changes, additions, etc. within the spirit and scope of the present invention, these modifications, changes, etc. should be seen as belonging to the claims. do.
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