크롬 산화물 촉매를 이용한 Vinyl Chloride의 산화 분해반응

이해완; 김영채; 문세기

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.1, 58-66, February, 1999

Export Citation

크롬 산화물 촉매를 이용한 Vinyl Chloride의 산화 분해반응

Catalytic Oxidation of Vinyl Chloride on Chromium Oxide Catalysts

이해완, 김영채, 문세기

초록

알루미나에 담지한 CrO_x 촉매를 이용하여 200∼400℃의 온도 구간에서 공기 중 vinyl chloride의 산화반응을 조사하였다. 탄소를 포함하는 주생성물은 CO 및 CO₂로, 온도의 증가에 따라 CO₂의 선택도는 증가하고 CO는 감소하였다. 이로부터 CrO_x 촉매상에서 vinyl chloride는 먼저 CO로 일차산화 후 다시 CO₂로 완전산화됨을 알 수 있었다. 반응물에 HCl을 첨가하였을 때 vinyl chloride의 전환율은 변화가 없었으나 CO₂의 선택도는 감소하였는데 이는 주반응생성물인 HCl이 vinyl chloride의 CO₂로 완전산화를 방해함을 의미한다. 반응물에 물이 없는 조건하에서 vinyl chloride를 산화시킬 때 상당량의 Cl₂가 생성되었으나 물을 첨가 시 Cl₂는 검출되지 않았다. Vinyl chloride 분해활성은 1% Pt 담지촉매를 제외한 다른 촉매에 비해 높았으며, 275℃에서 12% CrO_x/Al₂O₃의 반응속도를 기준으로 각 촉매의 활성을 비교시 1% Pt/Al₂O₃ 보다 1.2배정도 활성이 떨어지나 다른 촉매에 비하여 각각 3배에서 8배 가량 높은 활성을 나타내었다.

The catalytic oxidation of vinyl chloride was investigated over CrO_x impregnated on Al₂O₃ at temperature between 200 and 400℃. The major carbonaceous products were CO and CO₂, and the selectivity of CO₂ was gradually increased with increasing reaction temperature, while that of CO was dropped consequently. This suggests that CO is the first product which is further oxidized to CO₂ in the oxidation of vinyl chloride over CrO_x/Al₂O₃. The addition of HCl in the feed didn't affect the conversion of vinyl chloride, but the selectivity of CO₂ decreased by adding HCl. It implies that HCl inhibits, the complete oxidation of vinyl chloride to CO₂. When oxidizing vinyl chloride in dry air, significant amounts of Cl₂ were observed, while no Cl₂ was detected in the humid condition. The activities of several catalysts including various precious metals and other transition metal oxides were measured, it was found that the catalytic activity of 12% CrO_x/Al₂O₃ was 1.2 times lower than that of 1% Pt/alumina, but it was 3 to 8 times more active than other catalysts for vinyl chloride oxidation at 275℃.

Keywords:Catalytic Oxidation;Vinyl Chloride;Light-off Curve;Chromium Oxide

[References]

Shirley WA, Chem. Eng. Prog., 90(7), 26 (1994)
Bradstreet JW, "Hazardous air Pollutants: Assessment, Liabilities and Regulatory Compliance," Noyes Publications (1995)
Mycock JC, McKenna JD, Theodore L, "Handbook of Air Pollution Control Engineering and Technology," Lewis Publishers (1995)
Moretti EC, Mukhopadhyay N, Chem. Eng. Prog., 20 (1993)
Ruddy EN, Carroll LA, Chem. Eng. Prog., 28 (1993)
Chu W, Windawi H, Chem. Eng. Prog., 92(3), 37 (1996)
Spivey JJ, Ind. Eng. Chem. Res., 26, 2165 (1987)
Windawi H, Wyatt M, Platinum Mater. Rev., 37(4), 186 (1993)
Bond GC, Sadeghi N, J. Appl. Chem. Biotechnol., 25, 241 (1975)
Rossin JA, Farris MM, Ind. Eng. Chem. Res., 32, 1024 (1993)
Chen BS, Bai CS, Cook R, Wright J, Wang C, Catal. Today, 30(1-3), 15 (1996)
Mendyka B, Piotrowska AM, Syczewska K, Catal. Today, 11, 597 (1992)
Papenmeier DM, Rossin JA, Ind. Eng. Chem. Res., 33(12), 3094 (1994)
Spivey JJ, Butt JB, Catal. Today, 11, 465 (1992)
Windawi H, Zhang ZC, Catal. Today, 30(1-3), 99 (1996)
Weldon J, Senkan SM, Combust. Sci. Technol., 47, 229 (1986)
Musick JK, Williams FW, Ind. Eng. Chem. Prod. Res. Dev., 13(3), 175 (1974)
Petrosius SC, Drago RS, Young V, Grunewald GC, J. Am. Chem. Soc., 115, 6131 (1993)
Manning MP, Hazardous Waste, 1(1), 41 (1984)
Lago RM, Green ML, Tsang SC, Odlyha M, Appl. Catal. B: Environ., 8(1), 107 (1996)
Subbanna P, Greene H, Desal F, Environ. Sci. Technol., 22, 557 (1988)
Ramanathan K, Spivey JJ, Combust. Sci. Technol., 63, 247 (1989)
Immamura S, Tarumoto H, Ishida S, Ind. Eng. Chem. Res., 28, 1449 (1989)
Imamura S, Imakubo KI, Furuyoshi S, Ind. Eng. Chem. Res., 30, 2355 (1991)
Greene HL, Prakash DS, Athota KV, Appl. Catal. B: Environ., 7(3-4), 213 (1996)
Jiang XZ, Zhang LQ, Wu XH, Zheng L, Appl. Catal. B: Environ., 9(1-4), 229 (1996)
Konya Z, Hannus I, Kiricsi I, Appl. Catal. B: Environ., 8(4), 391 (1996)
Chatterjee S, Greene HL, Appl. Catal. A: Gen., 98, 139 (1993)
Ramachandran B, Greene HL, Chatterjee S, Appl. Catal. B: Environ., 8(2), 157 (1996)
Stenger HG, Buzan GE, Appl. Catal. B: Environ., 2, 117 (1993)
Lee HW, Kim YC, Moon SK, J. Korean Ind. Eng. Chem., 9(4), 497 (1998)
Groenveld C, Wittgen PPM, J. Catal., 59, 153 (1979)
Vigneron S, Deprelle P, Hermia J, Catal. Today, 27(1-2), 229 (1996)
Larsson PO, Andersson A, Wallenberg LR, Svensson B, J. Catal., 163(2), 279 (1996)
Michalowicz R, M.S. Thesis, MIT, Cambridge, MA (1982)

[1] Shirley WA, Chem. Eng. Prog., 90(7), 26 (1994)

[2] Bradstreet JW, "Hazardous air Pollutants: Assessment, Liabilities and Regulatory Compliance," Noyes Publications (1995)

[3] Mycock JC, McKenna JD, Theodore L, "Handbook of Air Pollution Control Engineering and Technology," Lewis Publishers (1995)

[4] Moretti EC, Mukhopadhyay N, Chem. Eng. Prog., 20 (1993)

[5] Ruddy EN, Carroll LA, Chem. Eng. Prog., 28 (1993)

[6] Chu W, Windawi H, Chem. Eng. Prog., 92(3), 37 (1996)

[7] Spivey JJ, Ind. Eng. Chem. Res., 26, 2165 (1987)

[8] Windawi H, Wyatt M, Platinum Mater. Rev., 37(4), 186 (1993)

[9] Bond GC, Sadeghi N, J. Appl. Chem. Biotechnol., 25, 241 (1975)

[10] Rossin JA, Farris MM, Ind. Eng. Chem. Res., 32, 1024 (1993)

[11] Chen BS, Bai CS, Cook R, Wright J, Wang C, Catal. Today, 30(1-3), 15 (1996)

[12] Mendyka B, Piotrowska AM, Syczewska K, Catal. Today, 11, 597 (1992)

[13] Papenmeier DM, Rossin JA, Ind. Eng. Chem. Res., 33(12), 3094 (1994)

[14] Spivey JJ, Butt JB, Catal. Today, 11, 465 (1992)

[15] Windawi H, Zhang ZC, Catal. Today, 30(1-3), 99 (1996)

[16] Weldon J, Senkan SM, Combust. Sci. Technol., 47, 229 (1986)

[17] Musick JK, Williams FW, Ind. Eng. Chem. Prod. Res. Dev., 13(3), 175 (1974)

[18] Petrosius SC, Drago RS, Young V, Grunewald GC, J. Am. Chem. Soc., 115, 6131 (1993)

[19] Manning MP, Hazardous Waste, 1(1), 41 (1984)

[20] Lago RM, Green ML, Tsang SC, Odlyha M, Appl. Catal. B: Environ., 8(1), 107 (1996)

[21] Subbanna P, Greene H, Desal F, Environ. Sci. Technol., 22, 557 (1988)

[22] Ramanathan K, Spivey JJ, Combust. Sci. Technol., 63, 247 (1989)

[23] Immamura S, Tarumoto H, Ishida S, Ind. Eng. Chem. Res., 28, 1449 (1989)

[24] Imamura S, Imakubo KI, Furuyoshi S, Ind. Eng. Chem. Res., 30, 2355 (1991)

[25] Greene HL, Prakash DS, Athota KV, Appl. Catal. B: Environ., 7(3-4), 213 (1996)

[26] Jiang XZ, Zhang LQ, Wu XH, Zheng L, Appl. Catal. B: Environ., 9(1-4), 229 (1996)

[27] Konya Z, Hannus I, Kiricsi I, Appl. Catal. B: Environ., 8(4), 391 (1996)

[28] Chatterjee S, Greene HL, Appl. Catal. A: Gen., 98, 139 (1993)

[29] Ramachandran B, Greene HL, Chatterjee S, Appl. Catal. B: Environ., 8(2), 157 (1996)

[30] Stenger HG, Buzan GE, Appl. Catal. B: Environ., 2, 117 (1993)

[31] Lee HW, Kim YC, Moon SK, J. Korean Ind. Eng. Chem., 9(4), 497 (1998)

[32] Groenveld C, Wittgen PPM, J. Catal., 59, 153 (1979)

[33] Vigneron S, Deprelle P, Hermia J, Catal. Today, 27(1-2), 229 (1996)

[34] Larsson PO, Andersson A, Wallenberg LR, Svensson B, J. Catal., 163(2), 279 (1996)

[35] Michalowicz R, M.S. Thesis, MIT, Cambridge, MA (1982)