- 學位論文
電子業廢溶劑作為水泥窯輔助燃料戴奧辛排放特性之研究
A Study on Characteristics of Dioxin Emission from Cement Kiln with Burning Waste Solvent Discharged from Electronic Industries
摘要
台灣工業迅速發展，廢溶劑被廣泛使用在各產業製程中，如半導體製造業(2710)、光電材料及元件製造業(2792)及石化業(1712)等產業；因水泥製造為高耗能之產業，而廢溶劑熱值高（3,000~7,000 kcal/kg）之特性可作為替代燃料使用，且利用水泥窯所具有之良好3T燃燒條件，可破壞廢棄物中之有害成分，但因廢溶劑成分複雜，水泥窯中混燒處理存在之戴奧辛有危害人體健康物質之可能性；因此為探討水泥窯中戴奧辛之特性變化，本研究係選定國內兩家大型水泥廠，蒐集其93~95年水泥窯混燃廢溶劑之戴奧辛煙道排放濃度，以探討戴奧辛排放濃度、毒性當量濃度、17種異構物與PCDDs與PCDFs之分布情形；以及蒐集水泥窯之各項操作條件與戴奧辛排放濃度及特性進行評析，為更客觀評估以廢溶劑作為輔助燃料之可行性，本研究另蒐集無混燃廢溶劑時之戴奧辛煙道檢測資料以期了解之間差異，最後亦提供相關廢溶劑產源及水泥廠之環境管理措施供相關單位參酌。 由戴奧辛17種主要異構物分布情況之研究結果顯示：（1）水泥窯煙道戴奧辛17種異構物之總量濃度分佈高低依序為2,3,7,8-TeCDF（36%）、2,3,4,7,8-PeCDF（9%）、1,2,3,7,8-PeCDF（8%）、1,2,3,4,6,7,8-HpCDF（8%）分，四者總實測濃度為0.927 ng/Nm3，佔整體貢獻量之61 %；（2）戴奧辛17種異構物毒性當量濃度中，以2,3,4,7,8-PeCDF貢獻度為最高34.76 %；其次依序是2,3,7,8-TeCDF為27.82%；2,3,7,8-TeCDD 11.29%；1,2,3,7,8-PeCDD 8.32%；（3）煙道廢氣戴奧辛中PCDFs對總濃度之貢獻度，最高為92％，顯見PCDFs所佔比例最高，如此可直接證明廢溶劑中的確含有來自於工業上之絕緣油、熱媒、潤滑劑、可塑劑等含多氯聯苯較多之廢液。 另本研究發現，有混燃較無混燃廢溶劑的17種戴奧辛異構物中僅有2,3,7,8-TeCDD、2,3,7,8-TeCDF及1,2,3,7,8-PeCDF三項總貢獻度增加，其中以2,3,7,8-TeCDF增量318.23%最多，其次依序是2,3,7,8-TeCDD、1,2,3,7,8-PeCDF；不管有無混燃廢溶劑其廢氣煙道戴奧辛中主要毒性之來源皆為PCDFs，而非在戴奧辛濃度中所佔比例較高之PCDDs，惟廢溶劑的添加似乎對於PCDFs有增量之效果（69%增量至77%） 在探討水泥窯操作條件方面，發現以戴奧辛指標性物種2,3,4,7,8-PeCDF毒性當量濃度與廢氣處理量、廢溶劑與總燃料比、生料與熟料（水泥）等進行回歸分析，皆無法看出明顯相關性，僅生料及熟料與2,3,4,7,8-PeCDF毒性當量濃度稍呈低度正相關，其餘皆呈現低度負相關。
並列摘要
By decades, because of high industrial growth in Taiwan, waste solvent has been continuously produced from several industrial industries, like semi-conductor industries, optoelectronic industriesand petrochemical industries etc. It is a creative idea that recycling and reusing these high heating value (3,000 ~ 7,000 kcal/kg) of waste solvents from above industries as aidded fuel of cement industry, one of extremly high power consuming industries, and the waste solvent can alse take the advantage of good 3T(time, temperature, turbulence) combustion condition in cement kiln for destruction to the harmful factors to the environment. Unfurtunely, the composition of the waste solvent is too complex to handle it without a perfect control method in combustion process. The most serious porblem is the porduction of dioxins during combustion process in cement industry. There are three purposes of the research; the first of all is analyzing the emitting dioxins characteristics produced of combustion tunnel of cement industry by gathering the concentration data from two famous cement factories in Taiwan between 2004 to 2006. The secondary is discussing the distribution of dioxins emitting concentration, the concentration of the toxicity equivalent quantity and the concentration distribution of 17 PCDDs/PCDFs of dioxins. The third is evaluing feasibility of burning waste solvent as aidded fued of cement kiln by gathering operation conditions of cement kiln and analyizing characteristics and concentration of dixions emission. For figuring out differences and the relationships of dioxins emission from cement kiln with and without using waste solvent as aidded fuel, the study also gathered dioxins emission data from cement kiln where was purely burning petrochmical fuel. The more is all the information about source of waste solvent and enviromental managenent methods of cement factory will be provided as references for any unit which care about this theme. The results of analyizing the distribution of 17 PCDDs/PCDFs of dioxins are:1.) The total concentration distribution of 17 PCDDs/PCDFs of dioxins in order from high to low are 2,3,7,8-TeCDF（36%）, 2,3,4,7,8-PeCDF（9%）, 1,2,3,7,8-PeCDF（8%）, and 1,2,3,4,6,7,8-HpCDF（8%）, and the sum of these four measured concentration is 0.927 ng/Nm3, 61% of whole contributed concentration.2.) The concentration of the toxicity equivalent quantity in these 17 PCDDs/PCDFs of dioxins, the highest contribution is 2,3,4,7,8-PeCDF (34.76%), the senondary positon is 2,3,7,8-TeCDF (27.82%), the third is 2,3,7,8-TeCDD (11.29%) and the last one is 1,2,3,7,8-PeCDD (8.32%).3.) PCDFs is the majority of dioxins (92%) in waste gas tunnel of cement kiln. It is the most powerful evidence of proofing that the composition of waste solvent included Polychlorinated bipheyls (PCB) materials. In addition, by comparing toxicity equivalent quantity of 17 PCDDs/PCDFs of dioxins from cement kiln burned with and without waste solvent, three contributed concentration of the toxicity equivalent quantity clearly raised, there are 2,3,7,8-TeCDF (raising about 318.23%), 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDF in order. The major toxic production is from PCDFs, not PCDDs which is higher propertion concentration of dioxins in both with or without aidded fuel cement kiln but it is interesting that waste solvent will raise the quantity of PCDFs from 69% to 77%. Regarding the operating conditions of cement kiln, there is no distinct relationship between the toxicity equivalent quantity of 2,3,4,7,8-PeCDF, the key point of dioxins, and waste gas processing quantity, ratio of waste solvent and all fuel weight, or clinker aw materials of cement by regression analysis methods. Only slightly positive relation between clinker aw materials of cement and 2,3,4,7,8-PeCDF and the others are slightly negative relation with 2,3,4,7,8-PeCDF.