TW201105429A - Method of treating incineration fly ash using microwave sintering technology - Google Patents

Abstract

The present invention is a kind of method of treating incineration fly ash using microwave sintering technology, which includes pressing incineration fly ash to form a pressed specimen; the pressed specimen carries out microwave sintering until a sintered body is obtained. Because the time of microwave sintering is longer than that of pressing specimen, pressing the incineration fly ash first can thus reduce the voids, increase the contact areas between the particles, and accelerate the reaction rate and shorten the reaction time, so that sintering time and energy source are saved, and manufacturing cost is reduced.

Description

201105429 六、發明說明： 【發明所屬之技術領域】 本發明係一種對於焚化飛灰的處理方法，尤其係一種 以微波燒結技術對於焚化飛灰的處理’以節省燒結時間以及 製造成本的方法。 【先前技術】 台灣地區目前有27座一般廢棄物（垃圾）焚化廠，每年 產生約1 6萬公噸的都市固體廢棄物焚化爐（Munic丨叫丨s〇丨丨d201105429 VI. Description of the Invention: [Technical Field] The present invention relates to a method for treating incineration fly ash, and more particularly to a method for treating incineration fly ash by microwave sintering technology to save sintering time and manufacturing cost. [Prior Art] There are currently 27 general waste (waste) incineration plants in Taiwan, producing about 166,000 metric tons of municipal solid waste incinerators per year (Munic 丨 丨s〇丨丨d)

Waste |ncine「at0「，簡稱MSW丨）飛灰。因Msw|飛灰含有 有害物質，如重金屬及戴奥辛等，所以被判定為有害廢棄 物。其組成相當複雜及不固定⑴，主要的成分有溶解性鹽 類（soluble saltsp】、氧化鈣（Ca〇)、二氧化矽（Sj〇2)、氧化 鋁（AI2〇3)、氧化鐵（Fe2〇3)、氧化鎂（Mg〇）、氧化鈉（Na2〇)、 氧化鉀（κ2ο)、五氧化二磷（p2〇5)、二氧化鈦（Tj〇2)、氧化 猛（MnO)、氧化銅（Cu〇)、氧化鋅（Zn〇)、氧化鉛（pb〇)、氧 化鉻（C「2〇3)、二氧化硫（s〇3)等；次要的成分有鋅（Zn)、鉛 (Pb)' 絡（c〇、鶴（Cd)、銅（Cu)、錫（Sn)、鋇（Ba)、綈（sb)、 錯（ΖΓ)、砷（As)、録（Co)' 銷（Mo)、热（Rb)、叙（Bi)、鈒（V)、 鈽（Ce)、鎵（Ga)、鑭（La)、敛（Nd)、鈮（Nb)、汞（Hg)等【2 3】。 MSWI *灰中重金屬以毒性特性溶出試驗（TcLp)所測得的 溶出濃度仍會高於法規標準。依環保署事業廢棄物管制中 心統計每年申報之有害事業廢棄物重金屬污泥高達3萬公 噸以上，且以含銅污泥產量為主，若未加處理而棄置將會 危害自然環境》 使用傳統熱處理技術（高溫熔融或燒結），則須耗費大量 201105429 的能源既不經濟亦不環保。最普遍的MSWI飛灰處理方法 是水泥固化法，但是，此法於長時間仍有重金屬溶出及固 化體繃解之虞，且在處理後會增加體積，而減少掩埋場的 使用壽命。因此，在掩埋處置前，必須將MSWI飛灰更進 一步處理’此為目前相關技術人員以及產業正積極研究的 目標。 雖》然微波加熱技術被應用已超過5 0年，但其被運用在 MSWI飛灰的處理則是新穎的技術。微波是一種兼具有電 _ 場及磁場的電磁能量形態，微波能量是一種頻率在300 MHz 〜300 GHz的非游離電磁輻射與其他傳統的熱處理技 術比較，微波技術具有偶極振動特性及介電損失效應提供 選擇性、均一及快速加熱等優點。在微波場中固態的介電 物質與電磁賴射間交互作用，介電物質產生極化現象，導 致被吸收的能量轉化為熱17]。 微波的應用在許多領域相當廣泛，包括陶变的燒結及 黏# 、化合物的合成[7]、受污染土壤的復 處理【9】、礦物的處理⑴]、結私技σ丄 r 輔助樣品消化程序[12, 16】、物皙的 乾燥或脫水、高分子 卞眾。物的加工及活性碳的再生【1〇]。 含重金屬污泥經微波轾 — 射文弋化的研究也受到關注，研究 ，结果顯不含銅污泥，夭Α _ + σ鐵粉或鋁粉經微波照射後，可有效 抑制金屬離子從污泥中 準…5匕先前之《^ 使污泥通過丁CLP溶出標 f 尤刖之研究鞋+杳： 有良好之安定效果，/=實廠飛灰經微波燒結處理程序後 【發明内容】 “疋對錯及鋅有明顯之安定趨勢[17]。 本發明人有鑑於既 开MSVV丨飛灰的處理方法會造成重 201105429 金屬溶出及固化體％解的問題’並且使體積增加，減少掩 埋場的筹命’另一方面還必須避免從銅污泥中有重金屬溶 出，因此經過不斷的研究以及試驗之後，終於發明出此以 微波燒結技術對於焚化飛灰的處理方法》 本發明之目的係在於提供一種以微波燒结技術對於焚 化飛灰的處理方法，以節省燒結時間以及製造成本的方法。 為達上述目的，本發明以微波燒結技術對於焚化飛灰的 處理方法，其係包括： 將焚化飛灰壓錠以形成壓錠試磕； 將該壓錠試體進行微波燒結，直到燒結完成以獲得一 燒結體。 其中’該焚化飛灰係單獨壓錠以形成該壓錠試體。 其中’該焚化飛灰係包含銅污泥，而焚化飛灰與銅污 /尼係以99 . 1〜1 : 1之比例混合後壓錠以形成該壓錠試體。 較佳的是，該焚化飛灰與銅污泥係以99 : 1〜2 : 1之 比例混合。 較佳的是，形成壓錠試體之後且在進行微波燒結之前， 尚匕括取十顆壓錠試體’將其係以一特定之擺設方式放置 於"石黑y 、 片上’該特定之擺放方式係以接觸於該石墨片的 第層以及放置於該第一層上方之第二層所組成，其中該 第層係以七顆壓錠試體所組成，其係由六顆壓錠試體對 稱圍％且緊靠於一壓錠試體（即中間一顆，周圍六顆），該第 層係由二顆壓錠試體所組成，該三顆壓錠試體係設置於 第一層的中央位置，且彼此緊靠。 -甘中，^ ’進行微波燒結之較佳的功率為600〜800瓦（W)， 201105429 而燒結時間為8分鐘以内；最佳的功率為7〇〇 w，而燒結 時間為3分鐘以内。 較佳的是，該燒結體之鉛溶出量係低於5 mg/L ;銅溶 出量係低於15 mg/L。 由於微波燒結之時間較壓錠樣品所需時間長，所以先 將飛灰和污泥進行壓錠，就能減少顆粒間的空隙，增加顆 粒間的接觸面積’並加快反應速率進而縮短反應時間，以 節省燒結的時間以及其耗費的能源，進而減少製程的成本。 【實施方式】 本發明以微波燒結技術對於焚化飛灰的處理方法，其 係包括： 將焚化飛灰單獨壓錠或將焚化飛灰與污泥以99 :彳： 1之比例混合後壓錠以形成一壓錠試體；Waste |ncine "at0", referred to as MSW丨) fly ash. Because Msw| fly ash contains harmful substances, such as heavy metals and dioxin, it is judged to be hazardous waste. Its composition is quite complicated and not fixed (1), the main ingredients are Dissolved salts (soluble salts), calcium oxide (Ca〇), cerium oxide (Sj〇2), alumina (AI2〇3), iron oxide (Fe2〇3), magnesium oxide (Mg〇), sodium oxide (Na2〇), potassium oxide (κ2ο), phosphorus pentoxide (p2〇5), titanium dioxide (Tj〇2), oxidized manganese (MnO), copper oxide (Cu〇), zinc oxide (Zn〇), lead oxide (pb〇), chromium oxide (C “2〇3), sulfur dioxide (s〇3), etc.; minor components are zinc (Zn), lead (Pb)' complex (c〇, crane (Cd), copper ( Cu), tin (Sn), barium (Ba), strontium (sb), erbium (As), arsenic (As), recorded (Co)' pin (Mo), heat (Rb), bis (Bi), 鈒 ( V), cerium (Ce), gallium (Ga), lanthanum (La), concentrating (Nd), cerium (Nb), mercury (Hg), etc. [2 3]. MSWI * Heavy metal in ash is tested for toxicity characteristics (TcLp The measured dissolution concentration will still be higher than the regulatory standards. The Waste Control Center of the industry counts up to 30,000 metric tons of heavy metal sludge that is declared annually, and it is mainly based on the production of copper-containing sludge. If it is disposed of, it will endanger the natural environment. Using traditional heat treatment technology (high temperature) Melting or sintering), it takes a lot of energy to use 201105429. It is neither economical nor environmentally friendly. The most common MSWI fly ash treatment method is cement curing method. However, this method still has heavy metal dissolution and solidified body disintegration for a long time. And after processing, it will increase the volume and reduce the service life of the landfill. Therefore, before the landfill disposal, the MSWI fly ash must be further processed. This is the current research goal of the relevant technical personnel and the industry. Microwave heating technology has been used for more than 50 years, but its application in MSWI fly ash is a novel technology. Microwave is a form of electromagnetic energy with both electric field and magnetic field. Microwave energy is a frequency of 300. Non-free electromagnetic radiation from MHz to 300 GHz compared to other conventional heat treatment techniques, microwave technology has dipole vibration characteristics and The electrical loss effect provides the advantages of selectivity, uniformity, and rapid heating. In the microwave field, the solid dielectric material interacts with the electromagnetic radiation, and the dielectric material generates polarization, which causes the absorbed energy to be converted into heat. The application of microwave is quite extensive in many fields, including the sintering and adhesion of ceramics, the synthesis of compounds [7], the reprocessing of contaminated soil [9], the treatment of minerals (1)], the technique of stagnation of σ丄r auxiliary samples. Procedure [12, 16], dry or dehydrated matter, and polymer. Processing of materials and regeneration of activated carbon [1〇]. The research on the heavy metal sludge by microwave 轾- 射 弋 也 也 也 也 , , , , , , , , , 轾 , 轾 轾 轾 也 也 也 也 也 也 _ _ _ _ _ _ + + + + + + + + + + + + The mud in the quasi-...5匕 previous "^ The sludge is passed through the D-CLP dissolution standard f. The research shoes +杳: have a good stability effect, /= the factory fly ash after the microwave sintering treatment program [invention content] There is a clear stability trend of 疋 right and wrong and zinc [17]. The inventors have considered that the treatment method of MSVV 丨 fly ash will cause the problem of heavy solution of metal dissolution and solidification in 201105429' and increase the volume and reduce the landfill. On the other hand, it is also necessary to avoid the dissolution of heavy metals from copper sludge. Therefore, after continuous research and experimentation, the treatment method of incineration fly ash by microwave sintering technology has finally been invented. Provided is a method for treating incineration fly ash by microwave sintering technology to save sintering time and manufacturing cost. To achieve the above object, the present invention uses microwave sintering technology for incineration The method for treating ash comprises: incinerating fly ash ingot to form a tablet test; microwave sintering the tablet body until sintering is completed to obtain a sintered body. wherein the incineration fly ash is separately pressed to form the same Ingot test body. The 'incineration fly ash system contains copper sludge, and the incineration fly ash and the copper stain/nitrite are mixed in a ratio of 99. 1 to 1:1, and then pressed to form the ingot test body. The incineration fly ash and the copper sludge are mixed in a ratio of 99:1 to 2:1. Preferably, after the ingot test body is formed and before the microwave sintering, ten ingot test bodies are prepared. It is placed in a specific arrangement on the "stone black y, on-chip". The specific placement is formed by contacting the first layer of the graphite sheet and the second layer placed above the first layer, wherein The first layer is composed of seven ingot test bodies, which are composed of six ingot test bodies symmetrically and close to one ingot test body (ie, one in the middle, six around), and the first layer is composed of two Compressed by a test piece, the three ingot test system is set The central position of one layer, and close to each other. - Ganzhong, ^ 'The preferred power for microwave sintering is 600~800 watts (W), 201105429 and the sintering time is within 8 minutes; the best power is 7〇〇 w, and the sintering time is within 3 minutes. Preferably, the sintered body has a lead elution amount of less than 5 mg/L; and the copper dissolution amount is less than 15 mg/L. It takes a long time, so the fly ash and the sludge are first pressed to reduce the gap between the particles, increase the contact area between the particles, and accelerate the reaction rate to shorten the reaction time, so as to save the sintering time and the energy it consumes. Further, the cost of the process is reduced. [Embodiment] The present invention relates to a method for treating incineration fly ash by microwave sintering technology, which comprises: separately incinerating fly ash or injecting fly ash with sludge to a ratio of 99:彳:1 After mixing, the ingot is pressed to form a tablet test body;

一取十顆壓鍵試體，將其係以一特定之擺設方式放置於 石墨片上，該特定之擺放方式係以接觸於該石墨片的第 -層以及放置於該第一層上方之第二層所組成，…第 一層係以七顆㈣試體所組成，其係由六顆錢試體對稱 圍繞且緊靠於一壓旋試體（即中間_顆，胃圍六顆），該第二 層係由三顆壓職體所組成，該三顆壓㈣體係設置於第 —層的中央位置，且彼此緊靠； 將上述以擺放完成之遷鍵試體以功率為600〜刚西的 條件進行微波燒結’直到熔融燒結完成的燒結時間為8分 鐘内’以獲得—燒結體’該堤結體之錯溶出量係、低於5 mg/L，鋼溶出量係低於1 5 mg/L。 201105429 實施例 本發明藉由以下實施例以示範本發明MSW|飛灰以微 波燒結處理的㈣，且試驗各種條件對於㈣燒結處理的 〜響而以下實;例僅為示範本發明，以讓於所屬領域中 具有通常知識者能夠更^ ^•此列文加了解本發明並可據以實施，因此 並非有意限制本發明之範脅。 以下所使用的感應耦合氬氣電漿原子發射光譜法（丨Cl AES)係法國J〇b丨n Yvon公司所生產之」γ24型感應耦合氬 氣電漿原子發射光譜儀（連續式），頻率4()湖Hz，使用氣 氣(A「)形成電襞(電毁氬氣流量(?”為12.丨〇，氬氣氣鞘 流量⑹）為〇_25 L/min，霧化室氬氣流量（nebu)為 0.3 L/min)。 本實細例所使用之飛灰係由台灣北部焚化廠取得，將 飛灰充分混合i天後以1Q5t供箱㈣3天保存備用。而 實施例所使用之污泥為甲級處理廠酸洗後不同&次之含鋼 污泥（TD10肖TD11)，污泥處理前先風乾並以球磨機研磨 至100-400 mesh(約〇·15_〇 〇63麵）大小，館存於⑽升 的大塑膠桶，實驗前再置於1〇5°c烘箱烘乾。 1-.,壓錠堆疊形妝的影響 方法： 先前進行之飛灰微波燒結實驗結果顯示（如第一圖），飛 灰加水混合調勻（未壓錠）進行微波程序處理，在30分鐘時 只有一半飛灰呈現燒結狀態，40及50分鐘時才完全繞: 並且重金屬TCLP分析結低於法規標準。 .201105429 焚化飛灰壓錠的微波燒結實驗中，將實廠飛灰或不同比 例混合飛灰與銅污泥，並壓錠為直徑約11 mm'高10 mm 之圓柱體’壓錠的製作流程及參數，壓錠是用鋼模（一圓柱 體中空直徑11mm、高約3公分）以人工方式（以橡皮槌手敲） 將飛灰壓成直徑11 mm高10mm左右之圓枉體。以1、2、 3、 4、6、7、8、10或11的圓柱體壓錠試體（pe丨丨ets)反覆 實驗驗證（如附件一）。 結果： 當10 pellets堆疊於石墨片後再置於坩堝上為最佳條 件（如附件二）。 不同微波時間與功率對微波燒結結果之影氅 方法： 以實廠飛灰進行本實施例最佳微波程序之確定，調整不同 微波功率（500、600、700及800 W)與不同微波時間〇、3、 4、 5、8、10、20、30、4〇與50分鐘）以進行比較，而獲 得最佳之微波條件。Ten ten-key test bodies are placed on the graphite sheet in a specific manner, which is placed in contact with the first layer of the graphite sheet and placed above the first layer. The second layer consists of... The first layer consists of seven (four) specimens, which are symmetrically surrounded by six money specimens and are close to a compression test (ie, the middle _, the stomach circumference six). The second layer is composed of three pressing bodies, and the three pressure (four) systems are disposed at the central position of the first layer, and are close to each other; the power of the migrating test body with the above-mentioned placement is 600~ The condition of the west is subjected to microwave sintering 'until the sintering time of the completion of the melt sintering is 8 minutes. 'Actaining the sintered body', the amount of the dissolved body of the bank is less than 5 mg/L, and the amount of steel dissolution is less than 1 5 mg/L. 201105429 EXAMPLES The present invention is exemplified by the following examples to demonstrate the MSW|fly ash of the present invention treated by microwave sintering (4), and various conditions are tested for the (4) sintering treatment; the examples are merely exemplary inventions, Those of ordinary skill in the art are able to understand the invention and can implement it, and thus are not intended to limit the scope of the invention. The inductively coupled argon plasma atomic emission spectrometry (丨Cl AES) used in the following is a γ24 type inductively coupled argon plasma atomic emission spectrometer (continuous) produced by J〇b丨n Yvon, France, frequency 4 () Lake Hz, using gas (A ") to form electricity (electrical argon flow rate (?" is 12. 丨〇, argon gas sheath flow (6)) is 〇 _25 L / min, atomization chamber argon The flow rate (nebu) is 0.3 L/min). The fly ash used in this practical example was obtained from the incineration plant in northern Taiwan. The fly ash was thoroughly mixed for 1 day and then stored in the box for 1Q5t (4) for 3 days. The sludge used in the example is the different & second steel-containing sludge (TD10 Xiao TD11) after pickling in the Grade A treatment plant. The sludge is air-dried and ground to 100-400 mesh by a ball mill before treatment. 15_〇〇63 face) size, the museum is stored in a large plastic bucket of (10) liters, and then placed in an oven at 1〇5°c before drying. 1-. The effect of the ingot stacking makeup: The results of the previously performed fly ash microwave sintering experiment (as shown in the first figure), the fly ash and water mixed and mix thoroughly (unpressed) for microwave processing, only half of the fly in 30 minutes The ash is in a sintered state and is completely wound at 40 and 50 minutes: and the heavy metal TCLP analysis is below the regulatory standards. .201105429 In the microwave sintering experiment of incineration fly ash ingot, the fly ash or copper sludge in the factory fly ash or different proportions, and the ingot is the production process and parameters of the cylinder 'pressing ingot with a diameter of about 11 mm' and a height of 10 mm. The ingot is a steel mold (a cylinder with a hollow diameter of 11 mm and a height of about 3 cm). The fly ash is pressed into a round body having a diameter of 11 mm and a height of about 10 mm by a manual method. Cylindrical ingot test bodies (pe丨丨ets) of 1, 2, 3, 4, 6, 7, 8, 10 or 11 were verified by experiments (see Annex 1). RESULTS: When 10 pellets were stacked on a graphite sheet and placed on a crucible, it was the best condition (see Annex 2). Different microwave time and power influence on microwave sintering results: The actual microwave program of this example is determined by the actual fly ash, and different microwave powers (500, 600, 700 and 800 W) and different microwave times are adjusted. 3, 4, 5, 8, 10, 20, 30, 4 and 50 minutes) for comparison to obtain the best microwave conditions.

經微波照射之飛灰或不同比例混合之飛灰與銅污泥壓錠 樣品以毒性特性溶出程序（t〇xicjty characteristjc bach丨叩 P瞭dUre，TCLP，R.1311, US EPA)來評估燒結後之安定效 果，所得之濾液以丨CP分析其重金屬濃度。進行毒性特性溶出 程序時，直接使用萃取溶液B (pH為2.88 ± 0·05之〇」M 醋酸溶液）。由於經微波燒結後之燒結體以瑪瑙研缽研磨並 混和均勻’取1.00 ± 〇.〇1 g之研磨顆粒置於5〇机之Μ 瓶内，加入20 mL之萃取溶液Β。之後將咤瓶置入萃取 201105429 容器内，再將萃取容器架在旋轉萃取裝置上，以轉速3〇 土 2 「pm連續翻轉18 ± 2小時。完成毒性特性溶出程序後之萃 取溶液先量測其pH值並記錄之，並以〇·45 μ m之玻璃纖 維濾紙過濾，濾液再以濃硝酸酸化至pH值小於2.0，並於 一星期内以ICP-AES分析其重金屬濃度。 結果：Microwave-irradiated fly ash or fly ash and copper sludge ingot samples mixed in different proportions were evaluated by toxic characteristic dissolution procedure (t〇xicjty characteristjc bach丨叩P dUre, TCLP, R.1311, US EPA) The effect of the stability was determined, and the obtained filtrate was analyzed for its heavy metal concentration by 丨CP. For the toxicity characteristic dissolution procedure, use extraction solution B (pH 2.88 ± 0·05 〇) M acetic acid solution). Since the sintered body after microwave sintering was ground in an agate mortar and mixed uniformly, the abrasive particles of 1.00 ± 〇. 〇 1 g were placed in a 5 〇 machine bottle, and 20 mL of the extraction solution was added. After that, the bottle is placed in the extraction container 201105429, and the extraction container is placed on the rotary extraction device, and the mixture is continuously inverted for 18 ± 2 hours at a speed of 3 Torr 2 pm. The extraction solution after the completion of the toxic characteristic dissolution procedure is first measured. The pH was recorded and filtered through a glass fiber filter paper of 〇·45 μm. The filtrate was acidified to a pH of less than 2.0 with concentrated nitric acid and analyzed for heavy metal concentration by ICP-AES within one week.

由附件二的實驗結果顯示實薇焚化飛灰之壓鍵微波燒 結體隨功率增加而縮短燒結時間’當功率為500W時8分 鐘有燒結現象’但當功率為600W時4分鐘即有燒結現象， 且至8分鐘即已完全燒結’而功率為7〇〇vv時提前至3分 鐘即可燒結，700 W及800 W至4分鐘即完全燒結，且所 有壓錠之圓柱體燒結熔融在一起。由附件三亦可看出，此 一堆置方式可使樣品吸收微波轉化為熱之後較不易因熱輻 射至爐壁散失，而使樣品較易形成許多熱點（h〇t sp〇ts)， 使樣品整體溫度可持續上升，當溫度升至臨界溫度（Tc)以 上牯即產生熱變形（thermal runaway)現象，樣品因溫度提 尚愈來愈會吸收微波，並在中間之圓柱體產生熱池（h〇t p〇〇丨) 現象而使所有之圓柱體逐漸熔融燒結在一起。 由第一圖的實驗結果顯示，飛灰之燒結體經試 驗分析結果顯示鉛之溶出量低於法規標準。先前進行之飛 灰微波燒結實驗結果顯示(如第一圖），飛灰加水混合調勻進 行微波程序處理，纟40 & 5〇分鐘時可達到相同的效果， 惟微波燒結之時繼錠樣品所需時間長，故由實驗社果 顯示㈣可減少顆粒間的空隙:，增加顆粒間的接觸面積， 並加快反應速率進而縮短反應時間。 201105429 3.微波燒結技術共同處理焚化飛灰與銅污泥 方法 由實廠飛灰微波燒結所得最佳微波程序結果，再進一步探 討飛灰與銅污泥（FATD10或FATD11) ’銅污泥FATD10及 FATD11為實廠不同批次之污泥，飛灰及銅污泥之成分詳 見表1，銅污泥除高濃度之銅外（FATD10為11，231 mg/kg 及FATD11為6,084mg/kg)，還有高濃度之鉛（FATD10為 91,228mg/kg 及 FATD11 為 35,186mg/kg)，FATD10 或 籲 FATD11之銅污泥在不同比例混合（99:1 ~0:1)之重金屬溶出 情形，此實施例中以功率600 W及微波時間50分鐘之微波 條件（雖然實廠飛灰在600 W時8分鐘即可完全燒結，為求微 波燒結反應完全仍採微波時間50分鐘），進行飛灰與銅污泥 之微波燒結程序。 表1飛灰及銅污泥之成分The experimental results in Annex II show that the pressed sintered microwave sintered body of Shiwei incineration fly ash shortens the sintering time with the increase of power. 'The sintering phenomenon occurs when the power is 500W for 8 minutes' but the sintering phenomenon occurs when the power is 600W for 4 minutes. And it is completely sintered to 8 minutes, and the sintering is advanced to 3 minutes when the power is 7 〇〇vv, and completely sintered at 700 W and 800 W to 4 minutes, and the cylinders of all the ingots are sintered and fused together. It can also be seen from Annex III that this stacking method can make the sample absorb microwaves into heat and is less likely to be lost to the furnace wall due to heat radiation, so that the sample is more likely to form many hot spots (h〇t sp〇ts). The overall temperature of the sample can continue to rise. When the temperature rises above the critical temperature (Tc), the thermal runaway phenomenon occurs. The sample absorbs the microwave more and more due to the temperature rise, and generates a hot pool in the middle cylinder. H〇tp〇〇丨) The phenomenon causes all the cylinders to gradually melt and sinter together. The experimental results in the first figure show that the results of the test analysis of the sintered body of fly ash show that the amount of lead dissolved is lower than the regulatory standards. The results of the previously performed fly ash microwave sintering experiment (as shown in the first figure), the fly ash and water mixed and homogenized for microwave processing, 纟40 & 5 〇 minutes can achieve the same effect, but the microwave sintering time of the ingot sample It takes a long time, so it is shown by the experimental results (4) that the voids between the particles can be reduced: the contact area between the particles is increased, and the reaction rate is accelerated to shorten the reaction time. 201105429 3. Microwave sintering technology co-processing incineration fly ash and copper sludge method The best microwave program results obtained from the actual fly ash microwave sintering, and further explore fly ash and copper sludge (FATD10 or FATD11) 'copper sludge FATD10 and FATD11 is the sludge of different batches of the factory. The composition of fly ash and copper sludge is shown in Table 1. Copper sludge except for high concentration of copper (11,231 mg/kg for FATD10 and 6,084 mg/kg for FATD11) There is also a high concentration of lead (FATD10 is 91,228mg/kg and FATD11 is 35,186mg/kg), FATD10 or FATD11 copper sludge is mixed in different proportions (99:1 ~0:1) heavy metal dissolution, this In the embodiment, the microwave condition of 600 W and microwave time is 50 minutes (although the fly ash of the factory can be completely sintered in 8 minutes at 600 W, and the microwave sintering time is still 50 minutes for the microwave sintering reaction), the fly ash and the fly ash are carried out. Microwave sintering procedure for copper sludge. Table 1 Composition of fly ash and copper sludge

Component FA* TD10* TD11* Major oxides (%) CaO 42.5 10.51 18.69 AI2〇3 4.4 2.02 2.69 Si02 7.12 16.15 17.42 Na20 10.46 1.08 2.19 K20 4.53 1.43 0.5 Mi门or elements (mg/kg) Zn 10,103 854 4,002 201105429Component FA* TD10* TD11* Major oxides (%) CaO 42.5 10.51 18.69 AI2〇3 4.4 2.02 2.69 Si02 7.12 16.15 17.42 Na20 10.46 1.08 2.19 K20 4.53 1.43 0.5 Mi door or elements (mg/kg) Zn 10,103 854 4,002 201105429

Cr 349 145 4,659 Pb 1,990 91,228 35,186 Cd 147 N.D. N.D. Fe 1,253 1,227 1,794 Mg 7,838 2,263 5,703 Cu 453 11,231 6,084 *N.D表示金屬離子濃度低於偵測極限(偵測極限為〇 i mg，L) * FA*:焚化飛灰，TD10*:銅污泥 FATD10，TD11*:鋼污泥 FATD11 結果： 由附件四顯示’飛灰與銅污泥混合比例在99:1-2:1皆 可形成有強度之燒結體，而在混合比例在1:1所形成燒结 體強度較差，混合比例〇:1(即銅污泥TD1〇)僅有灼燒之現 象；混合比例在99:1〜24:1所形成之燒結體幾乎熔融在一 起，無法辨識原本之圓柱體外觀；隨著銅污泥添加比例的 增加，混合比例在19:1〜1:1所形成之燒結體雖有熔融在一 起之現象，但仍可辨識其圓柱體外觀。由實驗結果顯示飛 灰與銅污泥共同處理是可行的，混合比例在99··1〜2:1皆可 形成有強度之燒結體’並有資材化之可行性。 由第三圖的實驗結果顯示’ FATD10樣品微波前，鉛 之毒性特性溶出濃度隨著銅污泥添加比例的増加（99:彳~6:1) 而增加，且遠高於法規標準（5 mg/L)e樣品微波後，只要 形成燒結體，不論4或10 pellets的樣品，其鉛毒性特性 溶出濃度均低於法規標準。而4 pe丨丨ets樣品添加比例98 2、 、24:1、14:1因未形成燒結體，故鉛毒性特性溶出濃 11 201105429 度仍运尚於法規標準β 10 pe丨丨ets的樣品所形成之燒結體有 較佳的安定效果》 由第四圖的實驗結果顯示，FATD11樣品微波前，錯 之毒性特性溶出濃度隨著銅污泥添加比例的増加（99:15:” 而增加，且遠高於法規標準。樣品微波後，4 pe丨丨ets樣品 混合比例97:1、44:1、6:1形成燒結體，其鉛毒性特性溶 出》辰度均低於法規標準。其餘添加比例因未形成燒結體， 故鉛毒性特性溶出濃度仍遠高於法規標準。 ® 由第五圖的實驗結果顯示，FATD1 0樣品不論微波前 後’銅之毒性特性溶出濃度均低於法規標準（1 5 mg/L);僅 銅污泥FATD1 0微波前之毒性特性溶出濃度高於8〇 mg/L， 且遠高於法規標準，惟經微波程序後即低於法規標準。由 第五圖實驗結果顯示’ FATD11或FATD11樣品不論微波 前後’銅之毒性特性溶出濃度均低於法規標準（15 mg/L)， 且微波後銅之毒性特性溶出濃度均低於微波前的濃度。 經由上述實施例的試驗後，可知本發明主要有下列優 鲁點： 1. 將飛灰經壓錠成形後可大幅縮短微波燒結時間，將 飛灰和銅污泥混合經壓錠後，亦有相同結果；當微波功率 適當地增加亦可縮短燒結時間，並可節省能源之使用。 2. 飛灰與污泥壓錠試體之燒結體經TCLP試驗分析後 顯示鉛之溶出低於法規標準（5 mg/L)。 3. 本發明之微波程序、壓錠圓柱體及恰當之堆置方 式，能讓壓錠試體易於燒結。 4. 飛灰與銅污泥共同處理為一可行之方式，其混合比 12 .201105429 例在99:1〜1:1可形成燒結體後，其錯與銅之溶出均低於法 規標準（5肖15 mg /L);飛灰與鋼污泥比例在99卜…所 形成之燒結體有較高之強度。 5·研究結果顯示’無論係、以顯的方式可縮短微波時 間，若再提高功率則能進-步縮短微波時間，故可大幅縮 短燒結的時間、能源與成本。 【圖式簡單說明】 • 第一圖係先前（飛灰加水混合調勻）進行之飛灰微波燒 結後’錯等重金屬的毒性特性溶出濃度比較圖。 第二圖係本發明實施例中的樣品在不同微波時間與微 波功率燒結後鉛的毒性特性溶出濃度圖。 第三圖係本發明焚化飛灰與銅污泥（FATD10)共同處 理於微波别後鉛的毒性特性溶出濃度比較圓。 第四圖係本發明焚化飛灰與銅污泥（FATD1彳）共同處 理於微波則後鉛的毒性特性溶出濃度比較圖。 # 第五圖係本發明焚化飛灰與銅污泥（FATD10)共同處 理，於微波前後銅的毒性特性溶出濃度比較圖。 第六圖係本發明焚化飛灰與銅污泥（FATD11)共同處 理，於微波前後銅的毒性特性溶出濃度比較圖。 【附件簡單說明】 附件一係顯示本發明之壓錠試體最佳的擺放方式之試 驗過程。 附件二係顯示本發明之壓錠試體最佳的擺放方式。 附件二係本發明實施例中以不同微波功率燒結的 形。 13 201105429 附件四係本發明實施例中飛灰與銅污泥以不同比例混 合之壓錠試體經微波燒結的情形。 【主要元件符號說明】 無 【參考文獻】 [1] C. C. Wiles, Municipal solid waste combustion ash: state-of-the-knowledge, J. Hazard. Mater, 47 (1996), 325-344.Cr 349 145 4,659 Pb 1,990 91,228 35,186 Cd 147 NDND Fe 1,253 1,227 1,794 Mg 7,838 2,263 5,703 Cu 453 11,231 6,084 *ND indicates that the metal ion concentration is below the detection limit (detection limit is 〇i mg, L) * FA*: Incineration Fly ash, TD10*: copper sludge FATD10, TD11*: steel sludge FATD11 Result: As shown in Annex IV, the mixing ratio of fly ash and copper sludge can form a sintered body with strength at 99:1-2:1. However, the sintered body formed at a mixing ratio of 1:1 is inferior in strength, and the mixing ratio 〇:1 (ie, copper sludge TD1〇) has only a burning phenomenon; the sintering ratio is formed at 99:1 to 24:1. The body is almost fused together, and the appearance of the original cylinder cannot be recognized. With the increase of the proportion of copper sludge added, the sintered body formed by the mixing ratio of 19:1 to 1:1 may be melted together, but still Identify the appearance of its cylinder. The experimental results show that the co-processing of fly ash and copper sludge is feasible, and the mixing ratio of 99··1 to 2:1 can form a sintered body with strength and the feasibility of materialization. The experimental results in the third figure show that before the FATD10 sample microwave, the toxic characteristic dissolution concentration of lead increases with the addition ratio of copper sludge (99: 彳~6:1), and is much higher than the regulatory standards (5 mg). /L) After the sample is microwaved, as long as the sintered body is formed, the lead toxicity characteristic dissolution concentration of the sample of 4 or 10 pellets is lower than the regulatory standards. And 4 pe丨丨ets sample addition ratio 98 2, 24:1, 14:1 because no sintered body is formed, so the lead toxicity characteristics are dissolved 11 201105429 degrees still in the sample of the legal standard β 10 pe丨丨ets The sintered body formed has a better stability effect. The experimental results in the fourth figure show that before the microwave of the FATD11 sample, the dissolved toxicity characteristic concentration increases with the increase of the copper sludge addition ratio (99:15:), and It is much higher than the regulatory standards. After the sample microwave, the mixing ratio of the 4 pe丨丨ets sample is 97:1, 44:1, 6:1, and the lead toxicity characteristics are lower than the regulatory standards. Since the sintered body is not formed, the lead toxicity characteristic dissolution concentration is still much higher than the regulatory standards. ® The experimental results in the fifth graph show that the FATD1 0 sample has a lower toxic characteristic dissolution concentration than the microwave before and after the microwave (1 5 Mg/L); only copper sludge FATD1 0 before the microwave toxicity characteristics dissolution concentration is higher than 8〇mg / L, and far higher than the regulatory standards, but after the microwave program is lower than the regulatory standards. Display 'FATD11 or FATD11 samples regardless of microwave Before and after the 'copper toxic characteristic dissolution concentration is lower than the regulatory standards (15 mg / L), and the toxic characteristic dissolution concentration of copper after microwave is lower than the concentration before microwave. After the test of the above examples, it is known that the present invention mainly has The following Ulu points: 1. The fly ash can be greatly shortened after the ingot is formed. The fly ash and copper sludge are mixed and pressed, and the same result is obtained. When the microwave power is properly increased, the sintering time can be shortened. It can save energy. 2. The sintered body of fly ash and sludge ingot test body shows that the dissolution of lead is lower than the regulatory standard (5 mg/L) after TCLP test. 3. Microwave program and ingot cylinder of the present invention And the appropriate stacking method can make the ingot test body easy to be sintered. 4. The fly ash and copper sludge are treated together as a feasible way, and the mixing ratio is 12.201105429. The sintered body can be formed at 99:1~1:1. After that, the dissolution and the dissolution of copper are lower than the regulatory standards (5 Xiao 15 mg / L); the ratio of fly ash to steel sludge is 99... The sintered body formed has a higher strength. 5. The research results show ' Microwaves can be shortened regardless of the way If you increase the power, you can shorten the microwave time step by step, so you can greatly shorten the sintering time, energy and cost. [Simplified illustration] • The first picture is the fly ash from the previous (flying ash plus water mixing) Comparison of the toxic characteristic dissolution concentration of the wrong heavy metal after microwave sintering. The second figure is the toxic characteristic dissolution concentration of lead in the sample of the present invention after sintering at different microwave times and microwave power. The third figure is the incineration of the present invention. Fly ash and copper sludge (FATD10) are treated together in the microwave. The toxic characteristics of the lead are compared. The fourth figure is the toxicity of lead in the treatment of the incineration fly ash and copper sludge (FATD1彳) in the microwave. Characteristic dissolution concentration comparison chart. # The fifth figure is a comparison chart of the toxic characteristic dissolution concentration of copper in the incineration fly ash and the copper sludge (FATD10) of the present invention. The sixth figure is a comparison chart of the toxic characteristic dissolution concentration of copper in the incineration fly ash and the copper sludge (FATD11) of the present invention. [A Brief Description of the Attachment] Attachment 1 shows the test procedure for the best placement method of the ingot test body of the present invention. The second part shows the best placement method of the ingot test body of the present invention. The second embodiment is a shape which is sintered at different microwave powers in the embodiment of the present invention. 13 201105429 Annex IV is a case in which the ingot test body in which the fly ash and the copper sludge are mixed in different ratios is subjected to microwave sintering in the embodiment of the present invention. [Explanation of main component symbols] None [References] [1] C. C. Wiles, Municipal solid waste combustion ash: state-of-the-knowledge, J. Hazard. Mater, 47 (1996), 325-344.

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Claims (1)

201105429 七、申清專利範圍： 1· 一種以微波燒結技術對於焚化飛灰的處理方立 係包括： ” 將焚化飛灰壓錠以形成壓錠試體； 將該壓錠6式體進行微波燒結’直到燒結完成以獲得一 燒結體》 /如申請專利錢第彳項所述之方法，其中該焚化飛 灰係單獨壓錠以形成該壓錠試體。 ^ 3.如申請專利範圍第1項所述之方法，其中該焚化飛 灰係包含鋼污泥，而焚化飛灰與銅污泥係以99 : ^〜1 之比例混合後壓錠以形成該壓錠試體。 4‘如申請專利範圍第3項所述之方法，其中該焚化 飛灰與銅污泥以99 : 1〜2 : 1之比例混合。 5_如申請專利範圍第1至4項中任一項所述之方法， 其中該壓錠試體為圓柱體。 鲁 6’如申a青專利範圍第5項所述之方法，其中該圓柱 體直控為11毫米（mm)、高為10 mm。 7·如申請專利範圍第5項所述之方法，其中形成壓 鍵試體之後且在進行微波燒結之前，尚包括取十顆壓錠試 體’將其係以一特定之擺設方式放置於一石墨片上，該特 定之擺放方式係以接觸於該石墨片的第一層以及放置於該 第 層上方之第二層所組成，其中該第一層係以七顆壓旋 試體所組成，其係由六顆壓錠試體對稱圍繞且緊靠於一壓 鍵試體’該第二層係由三顆壓錠試體所組成，該三顆壓錠 試體係設置於第一層的中央位置，且彼此緊靠。 17 •201105429 8·如申請專利範圍第6項所述之方法，其中形成壓 鍵試體之後且在進行微波燒結之前’尚包括取十顆壓鍵試 體，將其係以一特定之擺設方式放置於一石墨片上，該特 定之擺放方式係以接觸於該石墨片的第一層以及放置於該 第一層上方之第二層所組成，其中該第一層係以七顆壓錢 試體所組成’其係由六顆壓鍵試體對稱圍繞且緊靠於一塵 錠試體’該第二層係由三顆壓錠試體所組成，該三顆壓錠 試體係設置於第一層的中央位置，且彼此緊靠。 Θ.如申請專利範圍第1至4項中任一項所述之方法， 其中進行微波燒結之功率為600~800瓦（W)，而燒結時間 為8分鐘以内。 10·如申請專利範圍第7項所述之方法，其中進行微 波燒結之功率為600〜800瓦（W)，而燒結時間為8分鐘以 内0 1 1.如申請專利範圍第8項所述之方法，其中進行微 波燒結之功率為600〜800瓦（VV)，而燒結時間為8分鐘以 内0 12.如申請專利範圍第1至4項中任—項所述之方 法’其中進行微波燒結之功率為700 W，而燒結時間為3 分鐘以内。 13_如申請專利範圍第7項所述之方法，其中進行微 波燒結之功率為700 W，而燒結時間為3分鐘以内。 14.如申請專利範圍第8項所述之方法，其中進行微 波燒結之功率為700 W，而燒結時間為3分鐘以内。 1 5.如申請專利範圍第2項所述之方法，其中該燒結 18 201105429 體之鉛溶出量係低於5 mg/L。 16.如申請專利範圍第3項所述之方法，其中該燒結 體之鉛溶出量係低於5 mg/L ;銅溶出量係低於1 5 mg/L。 八、圖式：（如次頁）201105429 VII. Shenqing patent scope: 1. A microwave sintering technology for the treatment of incineration fly ash includes: ” Incineration fly ash ingot to form a tablet test body; microwave sintering of the tablet 6 body until sintering The method of claim 1, wherein the incineration fly ash is separately pressed to form the tablet body. ^ 3. The method of claim 1, Wherein the incineration fly ash system comprises steel sludge, and the incineration fly ash and the copper sludge are mixed at a ratio of 99: ^~1 and then pressed to form the ingot test body. 4' as described in claim 3 The method, wherein the incineration fly ash is mixed with the copper sludge in a ratio of 99:1 to 2:1. The method according to any one of claims 1 to 4, wherein the ingot test body is a cylinder The method of claim 5, wherein the cylinder has a direct control of 11 mm (mm) and a height of 10 mm. 7. The method of claim 5 , after forming a pressed key test body and performing microwave burning Before the knot, it is also included that ten ingot test bodies are placed on a graphite sheet in a specific manner, which is placed in contact with the first layer of the graphite sheet and placed on the first layer. The second layer is composed of the upper layer, wherein the first layer is composed of seven compression test pieces, which are symmetrically surrounded by six ingot test bodies and abutting against a pressed key test body. The three ingot test bodies are arranged in the central position of the first layer and are in close proximity to each other. 17 • 201105429 8 · The method described in claim 6 of the patent application, wherein the press bond test is formed After the body and before the microwave sintering, the ten test pieces are taken, and placed on a graphite piece in a specific arrangement, the specific arrangement is to contact the first piece of the graphite piece. a layer consisting of a second layer placed above the first layer, wherein the first layer is composed of seven pressure-molding samples, which are symmetrically surrounded by six pressure-bonded test bodies and abutted against a dust ingot The test piece 'this second layer is made up of three ingot test bodies The method of any one of the first to fourth aspects of the present invention, wherein the power of the microwave sintering is 600. ~800 watts (W), and the sintering time is within 8 minutes. 10. The method of claim 7, wherein the microwave sintering power is 600 to 800 watts (W), and the sintering time is 8 minutes. 1. The method according to claim 8, wherein the microwave sintering power is 600 to 800 watts (VV), and the sintering time is within 8 minutes. 12. The patent application ranges from 1 to 4. The method of any of the items wherein the microwave sintering power is 700 W and the sintering time is within 3 minutes. 13_ The method of claim 7, wherein the power for microwave sintering is 700 W, and the sintering time is within 3 minutes. 14. The method of claim 8, wherein the microwave sintering power is 700 W and the sintering time is within 3 minutes. 1 5. The method of claim 2, wherein the sintered 18 201105429 body has a lead dissolution of less than 5 mg/L. 16. The method of claim 3, wherein the sintered body has a lead elution amount of less than 5 mg/L; and a copper dissolution amount of less than 15 mg/L. Eight, schema: (such as the next page) 1919