1360572 六、發明說明： 【發明所屬之技術領域】 本發明涉及一 域，尤其是關於一 料及其製造方法。 種替代燃料及廢棄物資源化領 種以油泥為主成分之新賴固態燃1360572 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a field, and more particularly to a material and a method of manufacturing the same. Alternative fuels and waste resources, the new solid-state fuel with sludge as the main component
【先前技術】 油泥的來源與組成非常的複雜，從石油（含各 種油品）的儲存、石化製程中各操作單元，甚至廢 水處理流程均有油泥的產生。就石油煉製廠而言， 油泥主要來源可歸納為⑴石油煉製廠製程單元，（2) 廢水處理廠，（3)儲油槽的清洗’（4)停爐間的維護； 其中以定期清洗石油儲存槽的槽底殘渣和廢水處理 廠的油污泥為最大宗。而槽底所積存的油泥為固體 或半固體之物質或沈積物，成分包含（1)油中物質分 解或分離而成之碳氫化合物，（2)油槽外進入之非碳 氫化合物，（3)固體物或砂（伴隨原油）、水、鐵銹或 渣及重質碳氫化合物等’也因此油泥的成份主要有 三大類：（1)水份’（2)無機性固體物，（3)碳氫化合物， 其比例依不同來源而有不同，大致為水分含 10〜60% ’碳氫化合物30〜80%，無機性固體物質 10〜40%。其中，碳氫化合物的發熱值約 10,300〜10,700kcal/kg。 因油泥含高量碳氫化合物，值得從油泥中回收 4 1360572 較高級的能源成分，一方面增加油品產量，另一方 面減少待處理的固體廢棄物（如發明專利號 CN98113781.4從廢油泥中提取原油的工藝方法）；若 將油泥視為廢棄物處理處置，歸納一般處理油泥先 前技術可分為（1)從污染源頭直接減少待處理量，（2) 資源回收再利用’（3)燃燒/焚化，（4)穩定化後掩埋處 理。由此可知’以燃燒/焚化方式處理油泥可達到減 量與資源回收的雙重目的。 雖然將油泥燃燒/焚化可達到減量與回收熱能， 但油泥具黏稠狀及惡臭之惟質，在清除、運輸、貯 存及使用上均極為不方便，同時未經適當前處之油 泥，其燃燒效率不高，使得廢氣中含有大量的煙塵、 SOx NOx專空氣污染物，易引起嚴重之空氣污染問 題，致使國内多數油泥無法充分的回收再利用，從 97年廢油及油泥工業廢棄物申報再利用數量僅 公606公噸（如表一）’可以得到印證，依此推估大 量未被回收再利用之油泥可能均進入掩埋場處理。 類別 申報再利用數 量（公嘲） 合計（公噸） 資料來源： 委託許可再利用機 農 8,160.92 委託公民營廢棄物處 (清)理機;^ 13,445.56 21,606.48 2·業[Prior Art] The source and composition of sludge are very complicated. From the storage of petroleum (including various oils), the operation units in the petrochemical process, and even the waste water treatment process, there is sludge production. In the case of petroleum refineries, the main sources of sludge can be summarized as (1) petroleum refinery process units, (2) wastewater treatment plants, and (3) oil storage tank cleaning' (4) maintenance of the shutdown room; The bottom of the oil storage tank and the oil sludge of the wastewater treatment plant are the largest. The sludge accumulated at the bottom of the tank is a solid or semi-solid substance or sediment containing (1) hydrocarbons decomposed or separated from the oil, and (2) non-hydrocarbons entering outside the oil tank, (3) Solid matter or sand (with crude oil), water, rust or slag and heavy hydrocarbons, etc. 'There are mainly three major categories of sludge: (1) water '(2) inorganic solids, (3) carbon Hydrogen compounds, the ratio varies depending on the source, and the water content is approximately 10 to 60% 'hydrocarbon 30 to 80%, and the inorganic solid material is 10 to 40%. Among them, the calorific value of hydrocarbons is about 10,300 to 10,700 kcal/kg. Because the sludge contains high amounts of hydrocarbons, it is worthwhile to recover 4 1360572 higher-grade energy components from the sludge, on the one hand to increase oil production, on the other hand to reduce solid waste to be treated (such as invention patent number CN98113781.4 from waste sludge In the process of extracting crude oil, if the sludge is treated as waste, the prior art of general treatment of sludge can be divided into (1) directly reducing the amount of treatment from the source of pollution, and (2) recycling and recycling of resources [(3) Combustion/incineration, (4) Stabilization and post-burial treatment. It can be seen that the treatment of sludge by combustion/incineration can achieve the dual purposes of reduction and resource recovery. Although the burning/incineration of sludge can achieve the reduction and recovery of heat energy, the sludge has the viscosity and the odor, which is extremely inconvenient in the removal, transportation, storage and use, and the combustion efficiency of the sludge without proper frontage. Not high, so that the exhaust gas contains a lot of soot, SOx NOx special air pollutants, easy to cause serious air pollution problems, resulting in most domestic sludge can not be fully recycled and reused, from the 1997 waste oil and sludge industrial waste declaration The use of only 606 metric tons (as shown in Table 1) can be confirmed, and it is estimated that a large number of unrecycled sludge may enter the landfill. Category Declared Recycling Quantity (Male Memo) Total (metric tons) Source: Entrusted Recycling Machine Agriculture 8,160.92 Entrusted Citizens' Camp Waste Office (Clean) Machine; ^ 13,445.56 21,606.48 2·
5 1360572 然以土地掩埋方式處理油泥，仍有極大的污染 風險存在，萬一穩定化不良，可能會有污染地下水 源，ia·成健康危害之慮。且在廢油泥的有機成份中 有多種芳香烴化合物及多環芳香烴化合物 (polyaromatic hydrocarbons，PAHs )等致癌物質的存 在（如benzene，ethylbenzene，naphthalene t〇luene， xylene等）；在無機成份方面亦含有相當量的重金 屬，如鎳、鈒、鋅、猛等；其毒性視其中苯紛所佔 比例而疋’故國内急待有新的油泥處理技術問世， 解決掩埋場土地不足之窘境’同時降低環境污染的 風險。 在混合油泥燃料組合物之先前技術中，發明專 利公告號TW489123揭露一種直接將油泥潑灑在石 油焦之方法，讓油泥被石油焦吸附，因該含油泥燃 料以石油焦為主要燃料成分，雖然解決部分油泥廢 棄物問，但油泥之惡臭味使得石油焦變得更具異 味，使得石油焦銷售受到阻力；又當噴灑之油泥所 含有害物質（如重金屬等），其石油焦之毒性溶出試 驗檢測結果仍有可能高於有害事業廢棄物認定標 準。 發明專利公開號CN101368118揭露一種含油泥 型煤，其由20〜50%的原煤、2〜35%的油泥、10〜4〇〇/〇 的煤泥及3〜8%的固硫消煙劑所組成，但未說明製造 6 方法’無法據以實施；又因該含油泥型煤係以原煤 為主要燃料成分，所含油泥最多僅可容許35%，無法 大量處理油泥廢棄物問題；該組合物添加油泥會增 加產品異味問題外’當使用之油泥所含有害物質（如 重金屬等），其含油泥型煤之毒性溶出試驗檢測結果 仍有可能高於有害事業廢棄物認定標準。 發明專利公開號CN101215487揭露一種生物質 油泥型煤的製造方法，其將重量比8〇%的煙煤、15 %的油泥、4〜5%的生物質混合後，在有機改性澱粉 類黏結劑作用下，於成型設備壓製而成。因該含油 泥型煤係以煙煤為主要燃料成分，最多僅可容許b %油泥及4〜5%生物質，無法大量處理油泥及生物質 廢棄物問題；又該組合物結合方式乃利用少量之澱 粉類黏結劑（重量比〇 4〜〇 75%)，其添加組成之中 間穩疋化及固定化結構不強，無法有效抑制異味及 將有σ物貝成分固疋在燃料中，故添加油泥會增加 產品異味問題外，當使用之油泥所含有害物質（如 重金屬等）’其生物質油泥型煤之毒性溶出試驗檢測 結果仍有可能高於有害事業廢棄物認定標準。 次廢棄物資源化的處理方式是為了延長非再生性 貝源的有效循環利用，達到永續發展目標最重要的 方法。因此’發明人為解決前述油泥直接燃燒/焚化、 及掩理處理所遭遇問題’以及改善發明專利公告號5 1360572 Although the sludge is treated by land burial, there is still a great risk of pollution. In case of poor stability, there may be pollution of groundwater sources, and ia. And in the organic components of waste sludge, there are a variety of aromatic hydrocarbon compounds and polycyclic hydrocarbons (PAHs) and other carcinogens (such as benzene, ethylbenzene, naphthalene t〇luene, xylene, etc.); Contains a considerable amount of heavy metals, such as nickel, antimony, zinc, and so on; its toxicity depends on the proportion of benzene in it; so the country is in urgent need of new sludge treatment technology, to solve the problem of land shortage in the landfill' while reducing The risk of environmental pollution. In the prior art of the mixed sludge fuel composition, the invention patent publication No. TW489123 discloses a method of directly spraying oil sludge on petroleum coke to allow the sludge to be adsorbed by petroleum coke, since the oil-containing fuel is mainly composed of petroleum coke, although Part of the sludge waste is asked, but the foul smell of the sludge makes the petroleum coke more odor, which makes the sales of petroleum coke suffer resistance; and when the sprayed sludge contains harmful substances (such as heavy metals), the toxic dissolution test of petroleum coke The test results may still be higher than the hazardous business waste certification standards. The invention patent publication No. CN101368118 discloses a clay-containing coal which is composed of 20 to 50% of raw coal, 2 to 35% of sludge, 10 to 4 〇〇/〇 of coal slime and 3 to 8% of sulfur-fixing smoke suppressant. Composition, but does not state that the manufacturing method 6 cannot be implemented; and because the sludge-containing coal is based on raw coal, the sludge can only be allowed to be up to 35%, and the problem of sludge disposal cannot be handled in large quantities; Adding sludge will increase the odor of the product. 'When the used sludge contains harmful substances (such as heavy metals, etc.), the test results of the toxic dissolution test of the sludge containing coal may still be higher than the standard of hazardous industrial waste. The invention patent publication No. CN101215487 discloses a method for manufacturing a biomass sludge coal which combines 8% by weight of bituminous coal, 15% of sludge and 4 to 5% of biomass, and then acts on an organically modified starch-based binder. Next, it is pressed into a molding machine. Because the oil-containing coal type uses bituminous coal as the main fuel component, it can only allow b% sludge and 4~5% biomass, and can not deal with the problem of sludge and biomass waste in large quantities; Starch-based cement (weight ratio 〇4~〇75%), the intermediate composition of the added composition is not stable, the immobilization structure is not strong, the odor is not effectively suppressed, and the stagnation component is solidified in the fuel, so the sludge is added. In addition to the problem of odor of the product, when the used sludge contains harmful substances (such as heavy metals, etc.), the test results of the toxic dissolution test of the biomass sludge coal may still be higher than the standard of hazardous business waste. The treatment of secondary waste recycling is to promote the effective recycling of non-renewable shellfish and the most important method to achieve sustainable development goals. Therefore, the inventors have solved the problems encountered in the direct combustion/incineration of the sludge and the treatment of the sludge, and improved the invention patent announcement number.