臺灣博碩士論文加值系統

儲存柴油所用容器多為金屬材質，可能與生質柴油反應使其成分變化而導致酸價升高、黏度增加、與不溶物形成。此外，含水分亦會影響微生物生長。本研究目的為探討儲油槽材質在柴油與油污泥中的腐蝕速率及相關影響因子。本研究以我國市售柴油(包括B2、B5、ULSD及LSD)為測試油品，調整其酸價、硫含量、與含水分等性質，針對地下油槽常採用之材質試片(SS304、SS430、碳鋼、鍍鋅鋼、FRP與Epoxy)，參考ASTM G31-72方法進行加熱浸泡試驗，以檢討腐蝕效應。針對不同硫含量與含分離水相油品中的試片腐蝕速率，進行成對t檢定，結果所得之p值皆大於0.05。在95%信心水準下，不同硫含量與含分離水相油品對應測試材質造成腐蝕速率並無顯著差異。以浸泡於不同酸價油品中的碳鋼與鍍鋅鋼試片腐蝕速率，進行成對t檢定，結果所得之p值小於0.05，故在95%信心水準下，不同油品酸價對應的碳鋼與鍍鋅鋼材質腐蝕速率有顯著差異。在另一部分油泥確實會對油品的性質造成影響，當油品含高酸價與高含水分的油泥時，油品酸價與含水分皆隨所添加油泥比例增加而增加，而氧化穩定性隨所添加油泥比例增加而下降。而油泥對B2與B5生質柴油油品酸價與含水分的影響大於超低硫石化柴油與低硫石化柴油。浸泡於含50 vol.%油泥油品中的試片腐蝕速率之成對t檢定結果，除SS430外其他測試材質p值皆小於0.05，故在95%信心水準下，含油泥油品對碳鋼、FRP與Epoxy有顯著腐蝕速率差異，對SS430並未造成顯著的腐蝕速率差異。

Most of the containers of diesel were made of metals, which may react with the stored biodiesel. The increases of acid value and viscosity as well as the formation of the insoluble matters resulted from the degradation of biodiesel. In addition, the water content of biodiesel was related to the microbial contamination. In this study, the effects of diesels with/without oil sludge on materials of storage tanks were investigated. Diesel samples with different acid values, sulfur contents, and water contents were tested to quantify their effects on the corrosion rates of tested materials. ASTM G31-72, the heating immersion test method, was adopted to simulate the corrosion of these materials. The paired t-test showed that there were no significant difference at the 95% confidence level among corrision rates of all tested materials immersed in oil samples with different sulfur content with separated water phase. For carbon steel and galvanized steel, there were significant difference between diesel samples with different acid values at the 95% confidence level. The existance of oil sludge in diesel was found effective on diesel’s properties. The acid value and water content of diesel increased with the addition of the oil sludge, the oxidation stability decreased in contrast. The effects of oil sludge addition ot the B2 and B5 biodiesel on water content and acid value were higher than the ultra-low sulfur diesel and low-sulfur diesel. The paired t-test showed that there were significant difference at the 95% confidence level among corrision rates of all tested materials immersed in oils with oil sludge except for SS430.

目錄
摘要 i
Abstract ii
圖目錄 v
表目錄 vii
第一章 緒論 1
1.1 研究緣起 1
1.2 研究目標 3
第二章 文獻回顧 5
2.1 生質柴油使用現況 5
2.2 國內儲油槽與油箱材質 7
2.3 生質柴油腐蝕機制 9
2.4 生質柴油腐蝕相關研究 10
2.5 油槽腐蝕與產生油污泥 13
2.6 腐蝕量試方法比較 16
第三章 方法與材料 20
3.1 研究流程 20
3.2 實驗器材與腐蝕速率測試方法 21
3.3 本研究使用材料 24
3.4 油品性質分析方法 26
3.4.1 酸價 26
3.4.2 含水分 26
3.4.3 氧化穩定性 27
3.5 腐蝕速率實驗參數 28
3.5.1 不同成份油品對儲槽材質腐蝕速率 29
3.5.2 油污泥對柴油性質與儲槽腐蝕影響 30
第四章 實驗結果與討論 32
4.1 不同成份油品對儲槽材質腐蝕速率研究 32
4.1.1 硫含量對油品腐蝕速率之影響 34
4.1.2 酸價與含水分對油品腐蝕速率之影響 38
4.2 油污泥對柴油性質與儲槽腐蝕影響 44
4.2.1室溫下油污泥對油品性質影響 44
4.2.1.1 室溫下含油污泥對油品酸價影響分析 44
4.2.1.2 室溫下含油污泥對油品含水分影響分析 50
4.2.1.3 室溫下含油污泥對油品氧化穩定性影響分析 58
4.2.2室溫下油槽材質於含油泥油品中之腐蝕探討速率 61
第五章 結論與建議 64
5.1 結論 64
5.2 建議 65
參考文獻 66

[1]National renewable energy laboratory, “Biodiesel handling and use guide”, Fourth edition, 2009, pp.19.
[2]Gallant., “The effects of ultra low sulfur diesel on generator set engines in data center emergency system applications”, 2008.
[3]Knothe, G., and Steidley, R.K., “Fatty acid alkyl esters as solvents: evaluation of the kauri-butanol value comparison to hydrocarbons, dimethyl diesters, and other Oxygenates”, Industrial and engineering chemistry research, 2011.
[4]中華民國立法院議案關係文書, “生質柴油政策評估報告”, 2015.
[5]中國石油學會, 財團法人工業技術研究院, “加油站地下儲油槽防止腐蝕技術規範手冊”, 2013.
[6]International energy agency, “Overview on advanced biofuels developments”, 2015, pp.10-13.
[7]Fangrui, M., Milford A.H., “Biodiesel production: a review”, Bioresource technology,1999.
[8]Gerpen, J.V., Shanks, B., Pruszko, R., Clements, D., Knothe, G., “Biodiesel Analytical Methods”, National renewable energy laboratory, 2004.
[9]Bockey, D., “Report on the current situation and prospects -abstract from the UFOP Annual report”, 2013, pp.7.
[10]Jim L., “Biofuels mandates around the world: 2015”, biofuelsdigest.com, 2014.
[11]USDA Foreign agricultural Service, Biofuels Annual, 2014, http://www.fas.usda.gov/commodities/biofuels.
[12]中華民國經濟部標準檢驗局, “CNS 1219 石油產品銅片腐蝕性試驗法”, 1990.
[13]American society of the international association., “Corrosiveness to copper from petroleum products by copper strip test D130”, 2012.
[14]張騰, 孫春志, 王珉, 和金盼盼, “生質柴油腐蝕性試驗研究”, 廣州化工, 第40卷, 12期, 2012.
[15]陳飛, 吳楨芬, 蘇有勇, 和王華, “生質柴油對銅的腐蝕特性及動力研究”, 中國油脂, 第39卷, 第2期, 2014.
[16]Haseeb, A.S.M.A., Fazal, M.A., Jahirul, H.H., and Masjuki, H.H., “Compatibility of automotive materials in biodiesel: A review”, Fuel, 2011, pp.922-931.
[17]Kenneth, P., Barnitt, R., Hayes, R.R., Ratcliff, M., McCormick, R.L, and Lou H.,
“100,000-mile evaluation of transit buses operated on biodiesel blends (B20)”
SAE Technical Paper, 2006.
[18]Mazzoleni, C., Kuhns, H.D, Moosmüller, H., Witt J., Nussbaum N.J., and Chang M., “A case study of real-world tailpipe emissions for school buses using a 20% biodiesel blend”, Sci Total Environ, 2007.
[19]Rashid, U., “Anwar, F., Bryan R.M, and Knothe, G., Moringa oleifera oil: a possible source of biodiesel”. Bioresour Technol, 2008.
[20]Rashid, U., Anwar, F., and Knothe, G., “Evaluation of biodiesel obtained from cottonseed oil”, Fuel Process Technol, 2009.
[21]Terry, B., “Impact of biodiesel on fuel system component durability”, FTC, 2005.
[22]Dinkov, R., Hristov, G., Stratiev, D., and Aldayri, V.B., “Effect of commercially available antioxidants over biodiesel/diesel blends stability”, Fuel, 2009.
[23]Clark, S.J, Wagner, L., Schrock, M.D., and Piennaar, P.G., “Methyl and ethyl soybean esters as renewable fuels for diesel engines”, JAOCS, 1984.
[24]Fazal, M.A., Haseeb, A.S.M.A., and Masjuki, H.H., “Comparative corrosive characteristics of petroleum diesel and palm biodiesel for automotive materials., Fuel Processing Technology”, 2010, pp.1308-1315.
[25]Fazal, M.A., Haseeb, A.S.M.A., and Masjuki, H.H., “Effect of temperature on the corrosion behavior of mild steel upon exposure to palm biodiesel”, Energy, 2011, pp.3328-3334.
[26]Kamisnki, J., and Kurzydlowski, K.J. “Use of impedance spectroscopy on testing corrosion behaviour of mild steel upon exposure to palm biodiesel”, Energy, 2008, pp.3328-3334.
[27]Kaul, S., Saxena, R.C, and Kumar, A., “Corrosion behavior of biodiesel from seed oils of Indian origin on diesel engine parts”, Fuel process technol, 2007, pp.303-307.
[28]Pinheiro, B.C.A., and Holanda, J.N.F., “Obtainment of porcelain floor tiles added with petroleum oily sludge, Ceramics International”, 2013, pp.39-57.
[29]張偉民, “原油槽油泥控制與原油均質化”, 石油季刊, 第38卷, 第二期, 2001, pp.63-81.
[30]Moltó, J., Barneto, A.G., Ariza, J., and Conesa, J.A., “Gas production during the pyrolysis and gasification of biological and physico chemical sludges from oil refinery”, Journal of Analytical and Applied Pyrolysis, 2012, pp.103-167.
[31]Bücker, F., Barbosa, C.S., Quadros, P.D., Bueno, M.K., Fiori, P., Huang, C., Frazzon, P.G., Ferrao, M.F., Bento, C.F.A.O., and Fatima, M., “Fuel biodegradation and molecular characterization of microbial biofilms in stored diesel/biodiesel blend B10 and the effect of biocide”, International Biodeterioration & Biodegradation 95, 2014, pp.346-355.
[32]Passman, F.J., “Microbial contamination and its control in fuels and fuel systems since 1980 review”, International Biodeterioration & Biodegradation 81, 2013, pp.88-104.
[33]Steel Tank Institute, “Keeping water out of your storage system”, 2006.
[34]Lima, C.S., Lima, R.O., Silva, E.F., Castro, K.K.V., Filho, O.C., Soares, A., Sandra, A., and Antônio, S., “Analysis of petroleum oily sludge produced from water-Oil separator”, Virtual Quim, Vol 6, No. 5, 2014, pp.1160-1171.
[35]Chang, C.Y., Shie, J., Lin, L., Wu, J.P., Lee, C.H., Jong, D., and Chan, C. F., “Major products obtained from the pyrolysis of oil sludge”, Energy & Fuels, 2000, pp.1176-1183.
[36]Bücker, F., Santestevan, N. A., Roesch, L. F., Jacques, R.J.S., Peralba, M.C.R., Bento, C.F.A.O., and Menezes, F., “Impact of biodiesel on biodeterioration of stored Brazilian diesel oil”, International Biodeterioration & Biodegradation 65, 2011, pp.172-178.
[37]Silva, T.R., Verde, L.C.L., Oliveira, V.M. and Santos, E.V., “Diversity analyses of microbial communities in petroleum samples from Brazilian oil fields”, International Biodeterioration & Biodegradation 81, 2013, pp.57-70.
[38]American Society of the International Association., “Laboratory Immersion Corrosion Testing of Metals G31”, 2012.
[39]Jakab, M.A., Westbrook, S.R., and Hutzler, S.A., “Testing for compatibility of steel with biodiesel”, Steel tank institute, 2008.
[40]Aoki, I.V., Hernandez, R.P.B., Chicoma, D.L., Pinto, H.P.F., and Aquino, I.P., “Influence of light temperature and metallic ions on biodiesel degradation and corrosiveness to copper and brass”, Fuel 102, 2012, pp.795-807.
[41]Bhatnagar, A.K., Saxena, R.C., Kumar, A., Negi, M.S., and Kaul, S., “Corrosion behavior of biodiesel from seed oils of Indian origin on diesel engine parts”, Fuel Processing Technology 88, 2007, pp.303-307.
[42]Cursaru, D.L., Ramadan, G.B.I., and Florin, M., “Degradation of automotive materials upon exposure to sunflower biodiesel”, Industrial Crops and Products 54, 2014, pp.149-158.
[43]Enzhu, H., Yufu, X., Xianguo, H., Lijun, P., and Shaotong, J., “Corrosion behaviors of metals in biodiesel from rapeseed oil and methanol”, Renewable Energy 37, 2012, pp.371-378.
[44]Geller, D.P., Adams, T.T., Goodrum, J.W., and Pendergrass, J., “Storage stability of poultry fat and diesel fuel mixtures: Specific gravity and viscosity”, Fuel 87, 2008, pp.92-102.
[45]Haseeb, A.S.M.A., Fazal, M.A., and Masjuki, H.H., “Effect of temperature on the corrosion behavior of mild steel upon exposure to palm biodiesel”, Energy 36, 2011, pp.3328-3334.
[46]Haseeb, A.S.M.A., Fazal, M.A., and Masjuki, H.H., “Comparative corrosive characteristics of petroleum diesel and palm biodiesel for automotive materials”, Fuel Processing Technology 91, 2010, pp.1308-1315.
[47]Munoz R.A.A., Montes R.H.O., Almeida E.S., Nascimento A.N., Oliveira P.V., Richter E.M., and Fernandes, D.M., “Storage stability and corrosive character of stabilised biodiesel exposed to carbon and galvanised steels”, Fuel 107, 2013, pp.609-614.
[48]Sukkasi, S., Sukjamsri, C., Ukrit, S., Sawalee, S., and Yuttanant, B., “Investigation of electrodeposited Ni-based coatings for biodiesel storage”, Applied Energy 88, 2011, pp.909-913.
[49]中華民國行政院環境保護署, “廢棄物對鋼之腐蝕速率檢測方法”, 2005.
http://www.niea.gov.tw/niea/REFUSE/R20902C.htm.
[50]中華民國經濟部標準檢驗局, “CNS14906石油產品酸價試驗法(電位滴定法)”, 2005.
[51]Chongkhong, S., Tongurai, C., Chetpattananondh, P., and Bunyakan, C., “Biodiesel production by esterification of palm fatty acid distillate”, Biomass and Bioenergy, vol. 31, no. 8, 2007, pp.563-568.
[52]中華民國經濟部標準檢驗局, “CNS15096油脂衍生物(脂肪酸甲酯)—氧化
穩定性測定法(加速氧化法)”, 2007.
[53]Park, J.Y.D., Kim, K., Lee, J.P., Park, S.C., Kim, Y.J., and Lee, J.S., “Blending effects of biodiesels on oxidation stability and low temperature flow properties”, Bioresource technology, vol. 99, no. 5, 2008, pp.1196-1203.
[54]Leung, D.Y.C., Koo, B.C.P., and Guo, Y., “Degradation of biodiesel under different storage conditions”, Bioresource Technology, vol. 97, no. 2, 2006, pp. 250-256.
[55]Moser, B.R., “Biodiesel production, properties and feedstocks”, In Vitro Cellular & Developmental Biology-Plant, vol. 45, 2009, pp.229-266.
[56]Atadashi, I.M.M., Aroua K., Abdul, A.A.R., and Sulaiman, N.M.N., “Production of biodiesel using high free fatty acid feedstocks”, Renewable and Sustainable Energy Reviews, vol. 16, no. 5, 2012, pp.3275-3285.
[57]任長春, “電力金具熱浸鍍鋅標面白銹的產生與預防”, 電力金具, 第二期, 2006.
[58]Frankel, E.N., “Volatile lipid oxidation products”, Prog Lipid Res, 1983, pp.1-33.
[59]Shinichi, G., “Benchmarking of Biodiesel Fuel Standardization in East Asia Working Group”, 2010.
[60]Smart, N.G. and Bockeris, J.O., “Effect of water activity on corrosion”, Corrosion 92, vol.48, 1992.
[61]Anderko, A. and Young, R.D. “Simulation of CO2/H2S corrosion using thermodynamic and electrochemical models”, Report of OLI System Inc., 2004.
[62]Branen, A.L., Davidson, P.M., Salminen, S., and Thorngate III, J.H., “A.Food Additives”, Marcel Dekker, 1990, pp.141-143.
[63]Sakae, F., and Mizuno, D., Corrosion science, 2007, pp.211-219.
[64]Sazzad, B.S., Fazal, M.A., Haseeb, A.S.M.A., and Masjuki, H.H., “Retardation of oxidation and material degradation in biodiesel: A review”, RSC Advances, 2016.
[65]Guthrie, Jeffrey, Battat, Bridgitte, Grethlein and Chris, AMPTIAC Quarterly, 2002, pp.11-15.
[66]Jin, D., Xuehua, Z., Wu, P., Jiang, L.G., and Hongliang, Renewable Energy, 2015, pp.457-463.