Titania에 담지된 NiO의 촉매특성과 촉매성질에 관한 연구

배영일; 도임자; 손종락

Journal of the Korean Industrial and Engineering Chemistry, Vol.6, No.6, 1170-1180, December, 1995

Export Citation

Titania에 담지된 NiO의 촉매특성과 촉매성질에 관한 연구

Characterization and Catalytic Properties of Titania-Supported NiO Catalyst

배영일, 도임자, 손종락

초록

일련의 NiO-TiO2 촉매를 NiCl2와 TiCl4 혼합 용액을 공침전시켜 제조하였으며 이중에서 일부의 촉매는 H2SO4로 처리하여 촉매 표면을 개질하였다. 제조된 촉매의 특성을 FTIR, DSC-TGA, XRD 및 표면적 측정에 의하여 연구하였다. TiO2에 NiO를 첨가할수록 표면적 및 산의 양이 증가하였으며 NiO함량이 25 mol%에서 최대의 값을 나타내었다. 그리고 NiO의 함량이 25 mol%에서 propene의 부분산화반응과 1-butene의 이성화반응의 촉매활성도 최대를 보여 주었다. H2SO4로 개질된 NiO-TiO2/SO4(2-) 촉매는 미개질된 NiO-TiO2촉매에 비하여 1-butene의 이성화반응에서 월등히 향상된 촉매활성을 나타내었다. NiO 함량이 많을 수록 anatase가 rutile로 전이되는 온도가 NiO와 TiO2의 상호작용으로 높게 나타났으며 600 ℃ 이상의 소성온도에서 NiO와 TiO2가 결합하여 rhombohedral구조를 갖는 NiTiO3화합물이 생성되었다.

A series of NiO-TiO₂ catalysts were prepared by coprecipitation from the mixed solution of nickel chloride and titanium tetrachloride. Some of the samples were modified by treatment with H₂SO₄. The characterization of prepared catalysts was performed by using FTIR, DSC-TGA, and XRD, and by the measurment of surface area. The addition of NiO to TiO₂ caused the increase of surface area and acidity, showing a maximum at 25mo1% of NiO. Catalytic activities for prepene partial oxidation and 1-butene isomerization reactions also exhibited a maximum at 25mo1% of NiO. NiO-TiO₂/SO₄^2- modified whih H₂SO₄ exhibited remarkably enhanced catalytic activity for 1-butene isomerization compared with unmodified NiO-TiO₂. The addition of NiO to TiO₂ shifted the phase transition of TiO₂, from anatase to rutile towards higher temperatures due to the interaction between NiO and TiO₂. NiTiO₃ compound from NiO and TiO₂ was formed at calcination temperature above 600 ℃.

[References]

Wainwright MS, Foster NR, Catal. Rev.-Sci. Eng., 19, 211 (1979)
Dadyburjor DB, Jewur SS, Ruckenstein E, Catal. Rev.-Sci. Eng., 19, 293 (1979)
Lerchr JA, Noller H, J. Catal., 77, 152 (1982)
Tanabe K, Itoh M, Sato M, Chem. Commun., 676 (1973)
Hogan JP, Banks RL, Lanning WC, Clark A, Ind. Eng. Chem., 47, 752 (1955)
Uchida H, Imai H, Bull. Chem. Soc. Jpn., 38, 925 (1965)
Sohn JR, Ozaki A, J. Catal., 29, 303 (1979)
Sohn JR, Ozaki A, J. Catal., 61, 29 (1980)
WEndt G, Fritsch E, Schollner R, Siegel H, Z. Anorg. Allg. Chem., 467, 51 (1980)
Flinv RA, Larson OA, Beuther H, Ind. Eng. Chem., 52, 153 (1960)
Berndt GF, Thomson SJ, Webb GJ, J. Chem. Soc.-Faraday Trans., 79, 195 (1983)
Herwijnen TV, Doesburg HV, Jong DV, J. Catal., 28, 391 (1973)
Mills A, Proter G, J. Chem. Soc.-Faraday Trans., 78, 659 (1982)
Schrauzer GN, Guth TD, J. Am. Chem. Soc., 99, 7189 (1977)
Wainwright MS, Forster NR, Catal. Rev.-Sci. Eng., 19, 211 (1979)
Vannice MA, J. Catal., 74, 199 (1982)
Kataoka T, Dumesic JA, J. Catal., 112, 66 (1988)
Odenbrand CUI, Andersson SLT, Andersson LAH, Brandin JGM, Busca G, J. Catal., 125, 541 (1990)
Morrison C, Tanabe K, J. Catal., 35, 225 (1974)
Itoh M, Hattori H, Tanabe K, J. Catal., 35, 225 (1974)
Machej T, Dounmain B, Yasse B, Delmon B, J. Chem. Soc.-Faraday Trans., 84, 3905 (1988)
Okazaki S, Kurosaki A, Chem. Lett., 751 (1978)
Takahashi HO, Takagi M, Tanabe K, J. Catal., 68, 132 (1981)
Tanabe K, Hattori H, Chem. Lett., 625 (1976)
Takahashi O, Yamaguchi T, Sakuhara T, Hattori H, Tanabe K, Bull. Chem. Soc. Jpn., 53, 1807 (1980)
Sohn JR, Kim HJ, J. Catal., 101, 428 (1986)
Sohn JR, Kim HW, J. Mol. Catal., 52, 361 (1989)
Sohn JR, Ryu SG, Langmuir, 9, 126 (1993)
Morrow BA, McFarlane RA, Lian M, Lavalley JC, J. Catal., 107, 232 (1987)
Sohn JR, Park MY, Pae YI, Research Rev. of Kyungpook National Univ., 51, 87 (1991)
Sohn JR, Kim HW, Park MY, Park EH, Kim JT, Park SE, Appl. Catal. A: Gen., 128(1), 127 (1995)
Hammett LD, Deyrup AJ, J. Am. Chem. Soc., 54, 272 (1932)
Olah FGA, Prakash GKS, Sommer J, Science, 206, 13 (1979)
Parry EP, J. Catal., 2, 371 (1963)
Sohn JR, Ozaki A, J. Catal., 61, 29 (1980)
Ai M, Suzuki S, Bull. Chem. Soc. Jpn., 47, 3074 (1974)
Sohn JR, Pae YI, Park MY, Jo SG, React. Kinet. Catal. Lett., 55, 325 (1995)

[Referenced By]

[1] Wainwright MS, Foster NR, Catal. Rev.-Sci. Eng., 19, 211 (1979)

[2] Dadyburjor DB, Jewur SS, Ruckenstein E, Catal. Rev.-Sci. Eng., 19, 293 (1979)

[3] Lerchr JA, Noller H, J. Catal., 77, 152 (1982)

[4] Tanabe K, Itoh M, Sato M, Chem. Commun., 676 (1973)

[5] Hogan JP, Banks RL, Lanning WC, Clark A, Ind. Eng. Chem., 47, 752 (1955)

[6] Uchida H, Imai H, Bull. Chem. Soc. Jpn., 38, 925 (1965)

[7] Sohn JR, Ozaki A, J. Catal., 29, 303 (1979)

[8] Sohn JR, Ozaki A, J. Catal., 61, 29 (1980)

[9] WEndt G, Fritsch E, Schollner R, Siegel H, Z. Anorg. Allg. Chem., 467, 51 (1980)

[10] Flinv RA, Larson OA, Beuther H, Ind. Eng. Chem., 52, 153 (1960)

[11] Berndt GF, Thomson SJ, Webb GJ, J. Chem. Soc.-Faraday Trans., 79, 195 (1983)

[12] Herwijnen TV, Doesburg HV, Jong DV, J. Catal., 28, 391 (1973)

[13] Mills A, Proter G, J. Chem. Soc.-Faraday Trans., 78, 659 (1982)

[14] Schrauzer GN, Guth TD, J. Am. Chem. Soc., 99, 7189 (1977)

[15] Wainwright MS, Forster NR, Catal. Rev.-Sci. Eng., 19, 211 (1979)

[16] Vannice MA, J. Catal., 74, 199 (1982)

[17] Kataoka T, Dumesic JA, J. Catal., 112, 66 (1988)

[18] Odenbrand CUI, Andersson SLT, Andersson LAH, Brandin JGM, Busca G, J. Catal., 125, 541 (1990)

[19] Morrison C, Tanabe K, J. Catal., 35, 225 (1974)

[20] Itoh M, Hattori H, Tanabe K, J. Catal., 35, 225 (1974)

[21] Machej T, Dounmain B, Yasse B, Delmon B, J. Chem. Soc.-Faraday Trans., 84, 3905 (1988)

[22] Okazaki S, Kurosaki A, Chem. Lett., 751 (1978)

[23] Takahashi HO, Takagi M, Tanabe K, J. Catal., 68, 132 (1981)

[24] Tanabe K, Hattori H, Chem. Lett., 625 (1976)

[25] Takahashi O, Yamaguchi T, Sakuhara T, Hattori H, Tanabe K, Bull. Chem. Soc. Jpn., 53, 1807 (1980)

[26] Sohn JR, Kim HJ, J. Catal., 101, 428 (1986)

[27] Sohn JR, Kim HW, J. Mol. Catal., 52, 361 (1989)

[28] Sohn JR, Ryu SG, Langmuir, 9, 126 (1993)

[29] Morrow BA, McFarlane RA, Lian M, Lavalley JC, J. Catal., 107, 232 (1987)

[30] Sohn JR, Park MY, Pae YI, Research Rev. of Kyungpook National Univ., 51, 87 (1991)

[31] Sohn JR, Kim HW, Park MY, Park EH, Kim JT, Park SE, Appl. Catal. A: Gen., 128(1), 127 (1995)

[32] Hammett LD, Deyrup AJ, J. Am. Chem. Soc., 54, 272 (1932)

[33] Olah FGA, Prakash GKS, Sommer J, Science, 206, 13 (1979)

[34] Parry EP, J. Catal., 2, 371 (1963)

[35] Sohn JR, Ozaki A, J. Catal., 61, 29 (1980)

[36] Ai M, Suzuki S, Bull. Chem. Soc. Jpn., 47, 3074 (1974)

[37] Sohn JR, Pae YI, Park MY, Jo SG, React. Kinet. Catal. Lett., 55, 325 (1995)