201245103 六、發明說明： 【發明所屬之技術領域】 本發明係與水泥材料有關，更詳而言之是指一種 利用垃圾焚化混合灰與化學機械研磨污泥等有害事業 廢棄物為材料之再生水泥材料及其再生方法者。 【先前技術】 台灣地區之都市垃圾大部份以垃圾焚化爐焚化處 理，惟因焚化廠所產生之飛灰與洗滌灰均含有多種毒 害健康之重金屬，為有害事業廢棄物，一般均立即以 水泥與螯合劑固化處理，以免污染環境而造成危害。 台灣目前有24座垃圾焚化廠運轉，於2〇〇9年環保署 之公告其產出之飛灰與洗滌灰多達27萬公噸，一般均 將飛灰與洗滌灰以水泥固化處理，再委由包商棄運至 事業廢棄物掩埋場掩埋，但掩埋處理除了仍可能會有 毒害重金屬溶出之風險[1]，鑑於台灣地狹人稠，且民 意對環境保護亦有高度要求，致使掩埋場之設置愈行 困難，因此飛灰與洗滌灰之資源化再利用，成為亟待 解決的環境保護與永續發展問題。 又’ σ灣之半導體產業居世界領先地位，半導體 產業晶圓製造加工過程中之化學機械研磨與濕式酸 洗會產生化學機械研磨液污泥（chemical mechanical polishing sludge; CMP污泥）與氫氟酸污泥（HF污 泥），兩者混合而成之污泥簡稱為CMps污泥亦為有 201245103 害事業廢棄物；其再處理或再利用的研究或發明，迄 目刖為止並未能見。因該污泥含有多種之氧化劑、添 加劑、分散劑、研磨緩衝之有機與無機化合物等，其 中更含有奈米級之Si〇2、ΑΙΑ;等微粒子[2,3]，尤以 si〇2顆粒粒徑更小，約介於2〇〜3〇〇 nm間若不妥 慎處理，極易造成生態環境危害之虞，更可能對人體 健康構成威脅，亟待妥善處理。惟目前科學園區半導 體產業晶圓製造加工場’都將該CMps混合污泥委由 棄運廠商處理，若任意掩埋其潛藏之危機則不容忽視。 醤界般均5忍為奈米粒子可能會隨呼吸之吸入而 傷及肺部’亦可能穿人皮膚進人身體、肺部和消化系 統而造成細胞之傷害。又，人體普遍對新物質缺乏免 疫力，因此對奈米粒子之毒性可能毫無抵抗力。Y & c 〇匕i etal. [4]以20〜12〇nm*同種類之奈米微粒對老鼠肺 泡表皮細胞屏障性能之影響進行實驗，結果顯示：因 暴露於不同奈米粒子而造成肺泡表皮細胞屏障功能不 同程度之損傷。根據Linetal· [5]之研究，以15、46nm 、.、2粒子對人工培養的肺支氣管上皮癌細胞進; °式笞°式驗顯示造成依劑量而定之細胞毒性。根: =1^11[6]之研九，以4〇〜5〇〇〇1^直徑標記有螢光之 米Sl〇2粒子，進行對人工培養之人體上皮細胞實驗 結果顯不：40〜7〇 nm之營光Si〇2奈米粒子可於 胞核内引起異形蛋白質聚集體的形成，抑制複製、 201245103 =、田月l %殖。Moor [7]闡述人造奈米粒子釋出於水 生%^兄’經由細胞攝入等途徑，可能會傷害水生動物 之細胞與組織，進而指 , 疋叫捐及其健康，甚或造成生態與人 類食物鏈之危機，因此呼韻對每一新的奈米材料，需 要有防範性的處置方式，用來評估其對環境健康造成 的危害。 有關垃圾焚化廠底灰資源化再利用之研究與應 用，目前已有成效，除了可應用於道路路基底層材料、 燒製紅磚、透水磚，亦可燒製成建築物所用之磁磚， 惟垃圾焚化廠飛灰之資源化再利用則仍處於積極開發 研究階段，J. Pera，等人[8]以焚化底灰經篩選4 mm〜 20 mm間顆粒尺寸者用以取代粗骨材，其混凝土之28 天強度可達25 Mpa，即使以50%之大量取代率仍不影 响耐久性。Luca Bertolini, et al.[9]將飛灰用水洗滌以 減低其氯含量’並將底灰加水研磨與底灰乾磨之方 式’分別取代30%水泥製作成水泥砂漿試體，進行研 究比對，呈現濕磨底灰抗壓強度高於標準試體，並顯 現優良卜作風反應。201245103 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a cement material, and more particularly to a recycled cement using waste industrial waste such as waste incineration mixed ash and chemical mechanical polishing sludge. Materials and their methods of regeneration. [Prior Art] Most of the urban waste in Taiwan is incinerated by waste incinerators. However, the fly ash and washing ash generated by the incineration plant contain a variety of heavy metals that are harmful to health, and are hazardous industrial wastes. Curing with chelating agents to avoid harm to the environment. At present, there are 24 garbage incineration plants operating in Taiwan. In 1989, the Environmental Protection Agency announced that the output of fly ash and washing ash is as high as 270,000 metric tons. Generally, fly ash and washing ash are solidified by cement. It is abandoned by the contractor to the commercial waste landfill, but the buried treatment may still have the risk of poisoning heavy metal dissolution [1]. In view of the fact that Taiwan is densely populated and the public opinion also has high requirements for environmental protection, the landfill is caused. It is increasingly difficult to set up, so the recycling of fly ash and washing ash has become an urgent issue for environmental protection and sustainable development. Also, the semiconductor industry of Sigma Bay is the world leader. Chemical mechanical polishing and wet pickling in the wafer manufacturing process of the semiconductor industry will produce chemical mechanical polishing sludge (CMP sludge) and hydrogen fluoride. Acid sludge (HF sludge), a mixture of the two is referred to as CMps sludge, which is also 201245103 hazardous waste; its research or invention of reprocessing or reuse has not been seen until recently. Because the sludge contains a variety of oxidants, additives, dispersants, grinding buffered organic and inorganic compounds, etc., which also contain nano-sized Si〇2, ΑΙΑ; and other micro-particles [2,3], especially si〇2 particles The particle size is smaller, and if it is not properly handled between 2〇~3〇〇nm, it is easy to cause damage to the ecological environment, and it is more likely to pose a threat to human health and needs to be properly handled. However, the current semiconductor park semiconductor manufacturing wafer processing and processing site has disposed of the CMps mixed sludge by the abandonment manufacturer. If any hidden crisis is buried, it cannot be ignored. The average age of 5 is that nano particles may injure the lungs with the inhalation of breathing. It may also cause damage to cells by wearing human skin into the body, lungs and digestive system. Moreover, the human body is generally immune to the lack of immunity to new substances and therefore may be unreactive to the toxicity of nanoparticles. Y & c 〇匕i et al. [4] experimented with the effect of 20~12〇nm* nanoparticles of the same type on the barrier properties of mouse alveolar epidermal cells, and the results showed that alveolar cells were caused by exposure to different nanoparticles. Epidermal cell barrier function varies to varying degrees. According to the study of Linetal·[5], artificially cultured lung bronchial epithelial cancer cells were treated with 15, 46 nm, . , and 2 particles; the ° 笞 ° test showed a dose-dependent cytotoxicity. Root: =1^11[6] of the research nine, with 4〇~5〇〇〇1^ diameter marked with fluorescent rice S1〇2 particles, the results of artificial culture of human epithelial cells are not: 40~ The 7〇nm camp light Si〇2 nanoparticle can cause the formation of heterogeneous protein aggregates in the nucleus, inhibiting replication, 201245103 =, Tianyue l% colonization. Moor [7] states that artificial nanoparticles are released from the aquatic %^ brother's path through cell intake, which may harm the cells and tissues of aquatic animals, and thus, screaming for donation and its health, or even causing ecological and human food chains. The crisis, therefore, for every new nanomaterial, Hu Yun needs a preventive treatment to assess its environmental health hazards. The research and application of the recycling of bottom ash in waste incineration plants has been effective. It can be applied to the road base material, fired red bricks and permeable bricks, and can also be used to burn tiles used in buildings. The resource recycling of waste incineration plant fly ash is still in the active development research stage. J. Pera, et al. [8] used the incineration bottom ash to screen the grain size between 4 mm and 20 mm to replace the coarse aggregate. The 28-day strength of concrete can reach 25 Mpa, even without a large replacement rate of 50%. Luca Bertolini, et al. [9] washed the fly ash with water to reduce its chlorine content and added 30% cement to the cement mortar sample by adding water ash and bottom ash dry grinding, respectively. The compressive strength of the wet-ground ash is higher than that of the standard test body, and the excellent wind-like reaction is exhibited.
Amer Ali-Rawas等人[1 〇]以垃圾焚化飛灰取代部分 水泥與取代部份砂進行水泥砂漿試體之研究，其取代 砂者坍度會變小，取代水泥者坍度會增加，且其28天 強度則相近或稍高。Lin等人[11]將都市垃圾焚化飛灰 熔融處理之熔渣粉末，分別以0%、1 〇%與20%之水泥 201245103 取代率灌鑄成2·54 cm x 2.54 cm x 2.54 cm水泥漿試 體，試驗結果顯示：試體28天抗壓強度為未取代者強 度之84%〜96%，試體9〇天抗壓強度為未取代者強度 之95%〜π〇%。其後，Lin等人[1213]再針對都市 垃圾焚化飛灰經熔融處理研磨成粉末，於取代部份水 泥製成水泥漿試體後，進行其水化作用之觀察與八丨2〇3 於水合活性之分析研究，均獲良好之成果，但其28天 以前之強度仍低於純水泥漿試體。Lin [14]將MSWi 飛灰熔渣粉末依10〜40 %比例，分別取代！型、〖丨型 之波特蘭水泥與Belite水泥，製成2.54 cm χ 2 M cm χ 2.54 cm水泥聚試體，其抗壓強度之成長與標準試體相 較其早期強度之增長較低，但晚期強度之增長則較 多。Lee等人[15，16]將飛灰熔渣粉末依1〇%〜4〇%比 例，取代I型波特蘭水泥製成5 cm x 5 cm χ 5 cm水泥 砂漿試體，其抗壓強度之成卩與標準試體相較，其Μ 天強度約為75〜89%，90天強度則為％〜1〇4%，確 與前述水泥漿試體之試驗結果相仿。其後，La等人 [1 7-20]再以添加玻璃粉或水玻璃集塵灰與Ms%〗混合 灰共融處理，其試驗成果似顯現垃圾焚化混合灰熔^ 用以取代部份水泥資源再㈣之可能性。惟其早期強 度（14天以前）不足之問題仍待克服；否則因灌之θ 凝土結構構件無法依一般營建工程之時間拆模，’對施 工之管理與安全將構成威脅，亦使1期增長而增加成 201245103Amer Ali-Rawas et al. [1 〇] replaced some cement with waste incineration fly ash and replaced some sand for the study of cement mortar samples. The degree of replacement of sand will be smaller, and the degree of replacement of cement will increase. Its 28-day intensity is similar or slightly higher. Lin et al. [11] poured the slag powder from the municipal waste incineration fly ash into a slurry of 2·54 cm x 2.54 cm x 2.54 cm with a substitution rate of 0%, 1% and 20% cement 201245103, respectively. The test results showed that the compressive strength of the test body was 84% to 96% of the strength of the unsubstituted person, and the compressive strength of the test body was 95% to π% of the strength of the unsubstituted person. Later, Lin et al. [1213] further processed the municipal waste incineration fly ash into a powder by melt treatment, and after replacing the part of the cement into a cement slurry test, the hydration observation and the gossip were carried out. The analysis of hydration activity has achieved good results, but its strength before 28 days is still lower than that of pure cement slurry. Lin [14] replaced MSWi fly ash slag powder with 10~40% ratio! Type, 丨 type Portland cement and Belite cement, made of 2.54 cm χ 2 M cm χ 2.54 cm cement poly-test body, the growth of compressive strength is lower than that of the standard test body. However, the increase in late intensity is more. Lee et al. [15,16] replaced the type I Portland cement with a 5 cm x 5 cm χ 5 cm cement mortar sample at a ratio of 1% to 4% by weight of fly ash slag powder, and its compressive strength. Compared with the standard test body, the enthalpy is about 75~89%, and the 90-day strength is %~1〇4%, which is similar to the test results of the cement slurry. Later, La et al. [1 7-20] added the glass powder or water glass dust ash and Ms% mixed ash co-fusion treatment, and the test results seemed to show that the garbage incineration mixed ash fusion was used to replace part of the cement. The possibility of resources (4). However, the problem of insufficient early strength (14 days ago) still needs to be overcome; otherwise, due to the fact that the θ concrete structural members cannot be demolished according to the time of the general construction project, 'the management and safety of the construction will pose a threat, and the first phase will also grow. And increase to 201245103
本，且不易管控而較無實用性，本發明之MSWI-CMPS 熔渣混凝土則不受影響，可依一般營建工程之時間拆 模使用，而無安全之顧慮。 參考資料： 1. V. Herck, P. B.Van der Bruggen, G. Vogel, and C. Vandecasteele，"Application of computer modeling to predict the leaching behaviour of heavy metals from MSWI fly ash and comparison with a sequential extraction method 〃，Waste Management Vol. 20, pp. 203〜210 (2000). 2. Lai CL, Lin SH. Treatment of chemical mechanical polishing wastewater by electrocoagulation: system performances and sludge settling characteristics. Chemosphere 2004; 54: 235-242. 3. Den W, Huang C. Electrocoagulation for removal of silica nano-particles from chemical -mechanical-planarization wastewater. Colloids Surf A 2005; 254: 81-89. 4. Nazanin R. Yacobi, Harish C. Phuleria, Lucas Demaio, Chi H. Liang, Ching-An Peng, Edward D. Crandall, “Nanoparticle effects on rat alveolar epithelial cell monolayer barrier properties”，Toxicology in Vitro, 21, PP. 1373-1381 (2007). 5. Weisheng Lin, Yue-wern Hung, Xiao-Dong Zhou, Yinfa Ma, uIn vitro toxicity of silica nanoparticles in human lung cancer cells’’，Toxicology and Applied pharmacology， 217, PP. 252-259 (2006). 8 201245103 6. Min Chen, Anna von Mikecz, “Formation of nucleoplasmic protein aggregates impairs nuclear function in response to Si〇2 nanoparticles’’ Experimental Cell Research, 305, PP.51- 62 (2005). 7. Μ. N. Moor, “Do nanoparticles present ecotoxicological risks for the health of the aquatic environment”, Environment International, 32, PP. 967-976 (2006). 8. J. Pera, L. coutaz, J. Ambroise，M. Chababbet，“Use of incinerator bottom ash in concrete”，Cement and Concrete Research, Vol. 27, No. 1，pp. 1~5 (1997). 9. Luca Bertolini, Maddalena Carsana, Davide Cassago, Alessandro Quadrio Cuzio, Carsana, Mario collepardi, “MSWI ashes as mineral additions in concrete”，Cement and Concrete Research, Vol. 34, pp. 1899-1906 (2004). 10. Amer Ali al-rawas, Abdel Wahid Hago, Ramzi Taha, Khalid Al-Kharousi, “Use of incinerator ash as replacement for cement and sand in cement mortars”, Building and Environment, Vol. 40, pp. 1261-1266 (2005). ll.K. L. Lin，K. S. Wang, B. Y. Tzeng，C. Y. Lin, “The reuse of municipal solid waste incinerator fly ash slag as a cement substitute”， Resources, Conservation and Recycling, Vol. 39, pp. 315〜324 (2003). 12.K. L. Lin，et al，“ Effect of AI2O3 on the hydration activity of municipal solid waste incinerator fly ash slag55, Cement and Concrete Research, Vol. 30, pp. 587〜592 (2004). 201245103 13. K. L. Lin, K. S. Wang and C. H. Lin，“The hydration properties of pastes containing municipal solid waste incinerator fly ash slag55, Journal of Hazardous Materials, B109, pp. 173 〜181 (2004). 14. Kae-Log Lin, “The influence of municipal Solid waste incinerator fly ash slag blended in cement pastes’’，Cement and concrete Research，Vol.35, pp. 979〜953 (2005). 15. 李增欽，王偉哲，吳逸翔，「添加垃圾焚化飛灰熔渣粉 末水泥砂漿試體抗壓強度之探討」，聯合大學學報，第 二期，pp. 20〜30 (2005)。 16. Tzen-Chin Lee, Wei-Jer Wang, Ping-Yu Shih, K.L. Lin, “Enhancement in early strengths of slag-cement mortars by adjusting basicity of the slag prepared from fly-ash of MSWP5, Cement and Concrete Research, Vol. 39, pp. 651-658 (2009). 17. Tzen-Chin Lee, Wei-Jer Wang, Ping-Yu Shih, “Slag-cement mortar made with cement and slag vitrified from MSWI fly-ash/scrubber-ash and glass frit”，Constr. Build. Mater. 22, 1914-1921 (2008). 18. Tzen-Chin Lee, Μ. K. Rao, “Recycling municipal incinerator fly- and scrubber-ash into fused slag for the substantial replacement of cement in cement-mortars, Waste Management 29, 1952-1959 (2009). 19. Tzen-Chin Lee，Z. S. Li, “Conditioned MSWI ash-slag-mix as a replacement for cement in cement mortar”，Construction and Building Materials, 24, pp. 201245103 970-979 (2010). 20.Tzen-Chin Lee, Chieh-Jen, Ming-Kang Rao, Xun-Wei Su, “Modified MSWI ash-mix slag for use in cement concrete”，Construction and Building Materials, 25, pp. 1513-1520 (2011). 【發明内容】 本發明之主要目的即在提供一種利用有害事業廢 棄物為材料之再生水泥材料及其再生方法，其以垃圾 焚化混合灰與化學機械研磨污泥等有害事業廢棄物取 代部分水泥，卜作嵐反應對其抗壓強度之成長效果非 常優越，而可直接使用於營建混凝土工程之用，且， 其重金屬溶出量遠低於法規規定值，使用安全無虞， 甚具減廢、資源再利用之環境保護效益者。 緣是，為達成前述之目的，本發明係提供一種 利用有害事業廢棄物為材料之再生水泥材料，係以垃 圾焚化混合灰與半導體製程化學機械研磨產生之污泥 乾粉，依所需鹽基度調配混合，經熔融、研磨處理後 而獲得。 此外，本發明更提供一種前述再生水泥材料之再 生方法，係將垃圾焚化爐飛灰、洗滌灰依比例混合成 混合灰，再添加不同重量比例之半導體化學機械研磨 污泥乾粉，予以混合後進行熔融處理，再經研磨處理 後獲得可取代部分水泥之再生水泥材料。 【實施方式】 201245103 以下’兹舉本發明二較佳實施例，並配合圖式做 進一步之詳細說明如後： 本發明-較佳實施例之利用有害事業廢棄物為材 料之再生水泥材料，係以垃圾焚tMSWI混合灰與半 導體製程化學機械研磨產生之。则污泥乾粉，依所 需鹽基度S (S=Ca0/Si02)調配混合，、經、溶融、研磨處 理後而獲得，詳言之： 該垃圾焚化混合灰係由通過#1〇〇篩之垃圾焚化飛 灰（淡灰黃色，比重2.91)與洗務灰（接近白色而略 帶灰色，比重2.62 )以重量比！ ： 3均勻混合而成，比 重為2.69，該半導體製程化學機械研磨產生之污泥乾 粉係取自半導體晶圓製造廠之CMPS污泥餅，將其烘 乾後以洛杉磯試驗儀滾磨成粉末狀，取通過#1〇〇篩 者，稱為CMPS污泥粉，色乳白，比重為2·4〇，比表 面積為 10640 cm2/g。 垃圾焚化（MSWI)混合灰與CMPS污泥係依預定重 里比（1 · 0 · 5、1 . 〇. 7 5與1. 〇 : 1. 〇 )均勻混合，以氧 化鋁坩堝盛裝再置於電熱高溫爐中，依程式設定逐漸 升溫至1350°C ’並於持溫半小時後予以氣冷（或水 淬），而得調質混合灰熔渣（MS WI-CMPS熔渣），為一 淡黃棕色之玻璃質固化物，再經球磨機研磨至可通過 # 400號篩之粉末’象牙白色，比重為2.71，比表面 積為 6657 cm2/g。 12 201245103 前揭MS WI混合灰與CMPS污泥炫融處理前之混 合比例以鹽基度S(S=CaO/Si〇2)介於0.54.8之間為 較佳。 月1j揭相關成伤之内谷如表一所示，其中，水泥係 國產波特蘭第一型水泥，比重3. 15，細度為3520 cm2/g。 表1水泥、垃圾飛灰、飛灰熔渣與CMP污泥化學成份分析表 水泥 混合灰 CMP污泥 炫渣 (】：〇·5) 溶渔 (1 ： 0.75) 炫逢 (1:1) Al203(wt%) 5.29 5.85 14.95 9.16 14.18 16.48 Si〇2(wt%) 21.21 3.09 50.56 24.33 38.58 49.16 S〇3 (wt%) — 4.49 1.78 1.60 1.72 1.78 Cr(wt%) — 27.63 一 一 — _ K20(wt°/〇) 一 3.55 一 0.84 0.85 1.07 CaO(wt%) 63.71 40.49 28.37 45.18 32.73 23.30 Ti02(wt%) — 0.76 — 0.91 一 一 FeO(wt%) 3.36 1.46 — 0.92 1.52 1.41 ZnO(wt%) — 4.04 一 —— — — Br〗(wt%) 一 1.17 _ — 一 — MgO(wt%) 2.79 0.78 一 0.74 1.47 0.99 PbO(wt%) — 2.77 一 一 ~~—--- — 藉此，本發明該再生水泥材料可供取代部分水泥材 料之用，取代水泥之數量為一般水泥用量的5%到30% (重量百分比）之間’前揭MSWI混合灰與CMPS污泥 之較佳重量比為1:〇.5至1: 0.75之間’最佳者為1:0.5, MS WI混合灰與CMPS污泥熔融處理前之混合比例鹽基 度較佳者為0.8-1.8之間’水泥取代量較佳者為1〇%與 20%之間。 由上可知，本發明亦提供該再生水泥材料之再生 13 201245103 方法’係將垃圾焚化爐飛灰、洗滌灰依比例混合成混 合灰’再添加不同重量比例之半導體化學機械研磨污 泥乾粉’予以混合後進行熔融處理，再經研磨處理後 獲得可取代部分水泥之再生水泥材料。 以下’係以本發明該再生水泥材料分別取代〇、5、 10、20與30 wt.%之波特蘭I型水泥，灌鑄成5x5x5-cm3 之炼渣水泥砂漿試體，並參照有關水泥砂漿之astm 規範進行流度、凝結與抗壓強度等試驗，試驗結果顯 示其流度與抗壓強度均比純水泥砂漿優越，該再生水 泥材料確能取代部分水泥，而可應用於水泥砂漿中使 用，除可解決可能毒害環境之問題，亦能將兩種廢棄 物同時予以資源化再利用，一舉兩得。 本發明之水泥砂漿試體係依CNS1 01 0水硬性水泥 墁料抗壓強度檢驗法，與ASTM C109抗壓強度試驗之 規定’依水泥與砂之重量比為1:2.75，水膠比（W/C)= 0.485 ’灌鑄成5x5x5-cm3之水泥砂漿試體（對照組）。 以MSWI-CMPS熔渣取代部分水泥之砂漿，依熔渣取 代水泥之重量百分率予以編號；例如SBCM(10%)代表 以MS WI-CMPS熔渣取代1 〇 %水泥後，依前述的水泥 與砂之重量比、水膠比，製作成5x5 x5-cm3的熔渣砂 漿試體（試驗組），其它以此類推。 各種試體灌鑄後先置於可控式恆溫恆濕箱 (23°C，溼度95°/〇)—天’再取出脫模後置於恆溫養護This is not easy to control and has no practicality. The MSWI-CMPS slag concrete of the present invention is not affected, and can be demolished according to the time of general construction work without safety concerns. References: 1. V. Herck, PBVan der Bruggen, G. Vogel, and C. Vandecasteele, "Application of computer modeling to predict the leaching behaviour of heavy metals from MSWI fly ash and comparison with a sequential extraction method Waste Management Vol. 20, pp. 203~210 (2000). 2. Lai CL, Lin SH. Treatment of chemical mechanical polishing wastewater by electrocoagulation: system performances and sludge settling characteristics. Chemosphere 2004; 54: 235-242. Den W, Huang C. Electrocoagulation for removal of silica nano-particles from chemical -mechanical-planarization wastewater. Colloids Surf A 2005; 254: 81-89. 4. Nazanin R. Yacobi, Harish C. Phuleria, Lucas Demaio, Chi H Liang, Ching-An Peng, Edward D. Crandall, “Nanoparticle effects on rat alveolar epithelial cell monolayer barrier properties”, Toxicology in Vitro, 21, PP. 1373-1381 (2007). 5. Weisheng Lin, Yue-wern Hung , Xiao-Dong Zhou, Yinfa Ma, uIn vitro toxicity of silica nanoparticles in human lung ca Ncer cells'',Toxicology and Applied pharmacology, 217, PP. 252-259 (2006). 8 201245103 6. Min Chen, Anna von Mikecz, “Formation of nucleoplasmic protein aggregates impairs nuclear function in response to Si〇2 nanoparticles' Experimental Cell Research, 305, pp. 51-62 (2005). 7. .. N. Moor, “Do nanoparticles present ecotoxicological risks for the health of the aquatic environment”, Environment International, 32, PP. 967-976 (2006) 8. J. Pera, L. Coutaz, J. Ambroise, M. Chababbet, "Use of incinerator bottom ash in concrete", Cement and Concrete Research, Vol. 27, No. 1, pp. 1~5 (1997) 9. Luca Bertolini, Maddalena Carsana, Davide Cassago, Alessandro Quadrio Cuzio, Carsana, Mario collepardi, "MSWI ashes as mineral additions in concrete", Cement and Concrete Research, Vol. 34, pp. 1899-1906 (2004). 10. Amer Ali al-rawas, Abdel Wahid Hago, Ramzi Taha, Khalid Al-Kharousi, “Use of incinerator ash as replacement for cement and sand in cement mortars”, Bui Lding and Environment, Vol. 40, pp. 1261-1266 (2005). ll.KL Lin, KS Wang, BY Tzeng, CY Lin, “The reuse of municipal solid waste incinerator fly ash slag as a cement substitute”, Resources, Conservation and Recycling, Vol. 39, pp. 315~324 (2003). 12.KL Lin, et al, “Effect of AI2O3 on the hydration activity of municipal solid waste incinerator fly ash slag55, Cement and Concrete Research, Vol. 30 , pp. 587~592 (2004). 201245103 13. KL Lin, KS Wang and CH Lin, “The hydration properties of pastes containing municipal solid waste incinerator fly ash slag55, Journal of Hazardous Materials, B109, pp. 173 to 181 ( 2004). 14. Kae-Log Lin, “The influence of municipal Solid waste incinerator fly ash slag blended in cement pastes'', Cement and concrete Research, Vol. 35, pp. 979~953 (2005). 15. Li Zengqin, Wang Weizhe, Wu Yixiang, “Discussion on Compressive Strength of Additives for Adding Waste Incineration Fly Ash and Slag Powder Cement Mortar”, Journal of Union University, No. 2, Pp. 20~30 (2005). 16. Tzen-Chin Lee, Wei-Jer Wang, Ping-Yu Shih, KL Lin, “Enhancement in early strengths of slag-cement mortars by adjusting basicity of the slag prepared from fly-ash of MSWP5, Cement and Concrete Research, Vol 39, pp. 651-658 (2009). 17. Tzen-Chin Lee, Wei-Jer Wang, Ping-Yu Shih, “Slag-cement mortar made with cement and slag vitrified from MSWI fly-ash/scrubber-ash and Glass frit", Constr. Build. Mater. 22, 1914-1921 (2008). 18. Tzen-Chin Lee, Μ. K. Rao, "Recycling municipal incinerator fly- and scrubber-ash into fused slag for the substantial replacement of Cement in cement-mortars, Waste Management 29, 1952-1959 (2009). 19. Tzen-Chin Lee, ZS Li, “Conditioned MSWI ash-slag-mix as a replacement for cement in cement mortar”, Construction and Building Materials, 24, pp. 201245103 970-979 (2010). 20.Tzen-Chin Lee, Chieh-Jen, Ming-Kang Rao, Xun-Wei Su, “Modified MSWI ash-mix slag for use in cement concrete”, Construction and Building Materials, 25, pp. 1513-1520 (2011). SUMMARY OF THE INVENTION The main object of the present invention is to provide a recycled cement material using a hazardous business waste as a material and a method for regenerating the same, which is a waste industrial waste such as waste incineration mixed ash and chemical mechanical polishing sludge. Replacing part of the cement, the effect of the 岚 岚 reaction on its compressive strength is very good, and it can be directly used for the construction of concrete projects, and its heavy metal dissolution is far below the regulatory value, safe and flawless, and it is very wasteful. And environmental protection benefits of resource reuse. Therefore, in order to achieve the above object, the present invention provides a recycled cement material using hazardous industrial waste as a material, which is a sludge dry powder produced by chemical incineration of waste incineration mixed ash and semiconductor process, according to the required salt base. The mixture is blended and obtained by melting and grinding. In addition, the present invention further provides a method for regenerating the above-mentioned recycled cement material, which is to mix the fly ash and the washing ash of the garbage incinerator into mixed ash, and then add the semiconductor chemical mechanical grinding sludge dry powder of different weight ratios, and then mix and carry out After the melt treatment, and then grinding, a recycled cement material which can replace part of the cement is obtained. [Embodiment] 201245103 The following is a second preferred embodiment of the present invention, and further detailed description will be made with reference to the following: The present invention - a preferred embodiment of a recycled cement material using hazardous industrial waste as a material, It is produced by chemical mechanical grinding of waste-burning tMSWI mixed ash and semiconductor process. The sludge dry powder is prepared by mixing, mixing, melting, and grinding according to the required salt base degree S (S=Ca0/SiO2). In detail, the waste incineration mixed ash system is passed through the #1 sieve. Garbage incineration fly ash (light gray yellow, specific gravity 2.91) and washing ash (close to white and slightly gray, specific gravity 2.62) by weight ratio! : 3 uniformly mixed, the specific gravity is 2.69. The dry sludge produced by the chemical mechanical polishing of the semiconductor process is taken from the CMPS sludge cake of the semiconductor wafer manufacturer, dried and then rolled into a powder by the Los Angeles tester. Take the #1 sieve, called CMPS sludge powder, color milk white, specific gravity of 2.4 〇, specific surface area of 10640 cm2 / g. Waste incineration (MSWI) mixed ash and CMPS sludge are uniformly mixed according to the predetermined weight ratio (1 · 0 · 5, 1. 〇. 7 5 and 1. 〇: 1. 〇), and then placed in an alumina crucible and then placed in electric heating. In the high-temperature furnace, gradually increase the temperature to 1350 °C according to the program setting, and then air-cool (or water quench) after half an hour of holding the temperature, and obtain the tempered mixed ash slag (MS WI-CMPS slag), which is a light The yellow-brown vitreous solidified material was ground by a ball mill to a powder of '400 ivory' which had a specific gravity of 2.71 and a specific surface area of 6657 cm2/g. 12 201245103 The mixing ratio before the MS WI mixed ash and CMPS sludge smelting treatment is preferably between 0.54.8 and the salt base degree S (S=CaO/Si〇2). In the first month of the month, the relevant valleys are shown in Table 1. Among them, the cement is made of Portland's first type cement, with a specific gravity of 3.15 and a fineness of 3520 cm2/g. Table 1 Analysis of chemical composition of cement, garbage fly ash, fly ash slag and CMP sludge Cement mixed ash CMP sludge slag (]: 〇·5) Dissolved fish (1: 0.75) Hyun (1:1) Al203 (wt%) 5.29 5.85 14.95 9.16 14.18 16.48 Si〇2 (wt%) 21.21 3.09 50.56 24.33 38.58 49.16 S〇3 (wt%) — 4.49 1.78 1.60 1.72 1.78 Cr(wt%) — 27.63 一一— _ K20(wt °/〇) A 3.55 - 0.84 0.85 1.07 CaO (wt%) 63.71 40.49 28.37 45.18 32.73 23.30 Ti02 (wt%) — 0.76 — 0.91 One FeO (wt%) 3.36 1.46 — 0.92 1.52 1.41 ZnO(wt%) — 4.04 I———————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————————— Recycled cement material can be used to replace part of cement material, replacing the amount of cement between 5% and 30% (by weight) of general cement. 'Previously, the preferred weight ratio of MSWI mixed ash to CMPS sludge is 1: 〇.5 to 1: between 0.75 'the best is 1:0.5, the mixture ratio of MS WI mixed ash and CMPS sludge before melt treatment is better than 0.8-1.8 'water Substituted preferably by an amount between 1〇 and 20%. It can be seen from the above that the present invention also provides the regeneration of the recycled cement material. 13 201245103 The method 'mixes the waste incinerator fly ash and the washing ash into a mixed ash' and then adds the semiconductor chemical mechanical grinding sludge dry powder of different weight ratios. After mixing, it is melted and then ground to obtain a recycled cement material that can replace part of the cement. Hereinafter, the recycled cement material of the present invention replaces Portland, Type I cement of 〇, 5, 10, 20 and 30 wt.%, and is cast into a 5x5x5-cm3 slag cement mortar sample, and refers to the relevant cement. The astm specification of mortar is tested for fluidity, condensation and compressive strength. The test results show that the fluidity and compressive strength are superior to pure cement mortar. The recycled cement material can replace some cement, but can be used in cement mortar. In addition to solving the problem of possible poisoning of the environment, the two kinds of waste can be recycled and reused at the same time. The cement mortar test system of the invention is based on the CNS1 01 0 hydraulic cement concrete compressive strength test method, and the ASTM C109 compressive strength test specification: the weight ratio of cement to sand is 1:2.75, water-to-binder ratio (W/ C) = 0.485 'casting into a 5x5x5-cm3 cement mortar test (control). Replace some cement mortar with MSWI-CMPS slag, and assign it according to the weight percentage of slag instead of cement; for example, SBCM (10%) represents the replacement of 1 〇% cement with MS WI-CMPS slag, according to the above cement and sand The weight ratio and the water-to-binder ratio were made into a 5x5 x5-cm3 slag mortar sample (test group), and so on. After the various specimens are cast, they are placed in a controlled constant temperature and humidity chamber (23 ° C, humidity 95 ° / 〇) - days and then taken out of the mold and placed in a constant temperature curing
S 14 201245103 水槽中，溫度維持在23.0±1.7°C之飽和氫氧化鈣水溶 液槽中，經1天、3天、7天、14天、28天、60天與 90天養護後，再予取出依ASTM C109規範進行抗壓 強度試驗與其他有關試驗。 試驗方法： 新拌水泥砂漿： 依ASTM C143進行流度試驗，並依ASTM C187 水泥標準稠度試驗求得所需添加水量。再依ASTM C191水泥漿凝結時間試驗一維卡針法，進行水泥漿體 之初、終凝試驗，求取初、終凝時間。 硬固水泥砂漿試體： 依ASTM C109標準將每樣本於規定齡期，均取三 個試體進行抗壓強度試驗，並以三個試體抗壓強度之 平均值為該齡期之強度進行分析。 掃瞄式電子顯微鏡/能量分散譜（SEM/EDS)分析： 將MSWI混合灰、CMPS污泥與三種鹽基度之 MSWI-CMPS熔渣試樣，先經80°C真空烘箱中烘乾， 並於乾燥m冷卻後固定於樣本載台，再經表面覆膜鍍 金後，置於場發式掃描式電子顯微鏡（FE-SEM，JEOL JSM-6700F，Japan)中觀測，再以附加裝置之能量分散 譜儀（EDS INCAX-sight)進行化學元素成分之分析。 X 光繞射（X-ray Diffraction Analysis, XRD)分析： X光繞射（XRD)分析係將MSWI混合灰、CMPS污 15 201245103 泥與三種鹽基度之MSWI-CMPS熔渣試樣，先經80°C 真空烘箱中烘乾，並於乾燥皿冷卻後固定於樣本載 台，以日本製之X光粉末繞射儀 （Rigaku， D/Max-2200，Japan)分析試樣之晶相物種型態，其以 CuKal放射X光，並以2Θ掃瞄10。〜80〇之範圍；掃瞄 速率以每秒0.05°之計數進行。 毒性物質溶出試驗（TCLP)分析： 將MSWI飛灰、混合灰CMPS污泥與MSWI-CMPS 熔渣試樣與MS WI-CMPS熔渣取代部份水泥之水泥砂 漿試體，經養抗壓強度試驗後的碎塊，取樣烘乾，磨 成細粉狀後依據SW 846-131 1規範的步驟，進行毒性 特性溶出（TCLP)試驗。 以下，茲說明利用本發明該再生水泥材料製作抗 壓試體之步驟與方式： 抗壓試體係依CNS1010水硬性水泥墁料抗壓強度 檢驗法與ASTM C109抗壓強度試驗之規定，依水泥與 砂之重量比為1:2.75，水膠比W/C = 0.485，灌鑄而成 5x5x5-cm3之水泥砂漿試體（對照組，ordinary Portland cement mortar稱為0PCM試體），再以不同比例之本發 明MSWI-CMPS熔渣粉末取代5%、10%、20%與30%水 泥，灌鑄成相同尺寸之熔渣水泥砂漿試體（試驗組， slag-blended cement mortar稱為 SBCM試體）’其配比如 表2所示。水泥砂漿試體灌鑄後先置於可控式恆溫恆濕 201245103 箱（23°C，溼度95%)—天，再取出脫模後置於恆溫養護 水槽中，溫度維持在23.0±1.7°C之飽和氫氧化鈣水溶液 槽中，經1天、3天、7天、14天、28天、60天與90天養 護後，取出進行ASTM C109抗壓強度試驗與其它他相 關試驗。 在本實施例中係以純水泥砂漿（Ordinary Portland Cement mortar，本發明說明書中簡稱為OPCM，為參 考物系）、炫潰水泥砂漿 (Slag Blended Cement Mortar，稱為SBCM，為試驗物系），各取代水泥5%、 10%、20%與30%(重量百分比），調配成砂漿。所取各 成分重量，如表2所示。 表2 純水泥砂漿試體與熔渣水泥砂漿試體之配比 砂漿試體(5><5x5-cm3) 試體代號 OPCM SBCM (5%) SBCM (10%) SBCM (20%) SBCM (30%) 熔渣取代 水泥之比例 0% 5% 10% 20% 30% 水泥（g) 740 703 666 592 518 砂（g) 2035 2035 2035 2035 2035 MSWI-CM PS炼渣（g) 0 37 74 148 222 水（g) 359 359 359 359 359 熔渣燒失率與減容率： 調質混合灰經1350°C熔融持溫半小時候後，調質 17 201245103 混合灰内所含的有機物和氣會被燃燒與蒸發，依本文 之研究其三種鹽基度之重量的損失平均約為 25.79%。熔融後調質混合灰之容積減少約為73.52%， 亦即約濃縮成原有體積之26.5%，其試驗結果如表3 所示，呈現其減容效果非常優越，利於暫時貯存或掩 埋且安全無虞。 表3調質混合灰之燒失率與減容率 (a) MSWI混合灰與CMPS重量以1 : 0.5混合之燒失 率與減容率： 次數 燒失率(％) 減容率(％) 混合灰體密度 (g/cm3) 熔渣密度 (g/cm3) 1 29.47 77.28 0.92 2.85 2 26.77 77.91 0.92 3.06 3 29.45 73.78 0.92 2.63 4 25.10 78.76 0.91 2.88 5 29.23 76.01 0.93 2.74 6 22.20 71.19 0.91 2.46 平均值 27.04 75.99 0.92 2.77 (b) MSWI混合灰與CMPS重量以 ,1 : 0.75混合之燒失 率與減容率： 次數 燒失率(％) 減容率(％) 混合灰體密度 (g/cm3) 炫潰密度 (g/cm3) 1 20.85 70.07 0.95 2.47 2 25.30 71.19 0.96 2.50 3 24.87 73.59 0.97 2.77 4 20.10 73.43 0.97 2.92 5 33.59 76.09 0.95 2.65 6 20.29 71.36 0.95 2.64 平均值 24.16 72.52 0.96 2.66 (c) MSWI混合灰與CMPS重量以1 : 1混合之燒失率 18 201245103 與減容率： 次數 燒失率(％) 減容率(％) 混合灰體密度 (g/cm3) 熔渣密度 (g/cm3) 1 24.83 72.91 0.89 2.47 2 23.07 73.39 0.85 2.45 3 28.33 74.47 0.89 2.51 4 < 23.00 68.63 0.83 2.45 5 29.03 71.65 0.75 2.64 6 28.71 71.33 0.88 2.52 平均值 26.16 72.06 0.85 2.51 SEM/EDS觀測與分析： MSWI混合灰、CMP污泥與MSWI-CMPS熔渣之 SEM與EDS分析如圖1〜圖3所示。本試驗所取MSWI 混合灰、CMP污泥與MSWI-CMPS熔渣粉末均經選取 微量試樣，以SEM掃描式電子顯微鏡進行觀測，MS WI 混合灰呈團聚土塊狀’如圖1所示。CMP污泥則呈現 團聚之球狀或卵石狀，顆粒尺寸約為200 nm〜6 μηι 間，如圖2所示。MS WI-CMPS熔渣粉末顆粒呈碎石 狀，其尺寸小於38μπι，如圖3所示。其後再以EDS 分析MSWI混合灰、CMP污泥與MSWI-CMPS熔渣之 化學成份，如圖1-圖3與表1所示。MS WI-CMPS熔 渣之化學成份，含非鈣質氧化物Si02、Al2〇3與Fe203 之重量百分比分別為24.33〜49.16°/。、9.16〜16.48%與 0.92〜1.52% ’ 其總和為 34.41 〜67.05%，惟，CaO 含 量亦高達23.30〜45.18°/。接近八8丁1^€618規定（：級飛 灰之含量’非鈣質氧化物為進行卜作嵐反應之主要物 201245103 質，而含鈣質氧化物越多則可能有更佳之反應，亦即 強度可能早期即可發揮出來。 XRD分析： MS WI混合灰、CMP污泥與MS WI-CMPS熔渣經 X光粉末繞射後，所得之分析圖譜如圖4所示，經比 對圖譜得知混合灰最顯著之晶相物質為鈣，分別為 CaS04、CaCl2、CaClOH 與 Ca(OH)2，其次為 K、Na、 Pb、Zn與Si02。而調質混合灰炼渣貝|J為非結晶相之玻 璃態物質，其X光繞射圖譜明顯為寬廣的峰值，具玻 璃態物質之特徵，為典型之卜作嵐材料。 TCLP溶出試驗： 飛灰、洗蘇灰與混合灰均含有Pb、Zn、Cu、Cd 與Cr等有害重金屬成份，易溶出而污染地下水，惟經 高溫熔融處理後，均被-Si-O-之網狀結構所包圍，形成 緻密、耐酸鹼、低溶出率效果之熔渣，本文MS WI-CMPS 熔渣經XRD分析試驗結果為非結晶相之玻璃態物 質，將會形成-Si-O-之網絡包圍著重金屬，因此經TCLP 溶出試驗結果，MS WI混合灰之Pb與Cd溶出量，均 高於美國SW 846-131 1規範之規定值，而MSWI-CMPS溶渣之重金屬溶出量，則遠低於上述法規之規 定值，其試驗結果如表4所示。 表4 MSWI飛灰、混合灰與調質熔渣之TCLP分析S 14 201245103 In the water tank, the temperature is maintained at 23.0 ± 1.7 ° C in a saturated calcium hydroxide aqueous solution tank, after 1 day, 3 days, 7 days, 14 days, 28 days, 60 days and 90 days of maintenance, and then removed The compressive strength test and other related tests are carried out in accordance with ASTM C109. Test method: Fresh cement mortar: Fluidity test according to ASTM C143, and the required amount of water added according to ASTM C187 cement standard consistency test. According to the ASTM C191 cement slurry setting time test, the one-dimensional needle method is used to test the initial and final setting of the cement slurry to obtain the initial and final setting time. Hard-solid cement mortar test body: According to ASTM C109 standard, each sample is subjected to compressive strength test at the specified age, and the average of the three test body compressive strengths is used for the strength of the age. analysis. Scanning electron microscope/energy dispersive spectroscopy (SEM/EDS) analysis: MSWI mixed ash, CMPS sludge and three kinds of salt base MSWI-CMPS slag samples were first dried in a vacuum oven at 80 ° C, and After being cooled by m cooling, it is fixed on the sample stage, and then gold-plated by surface coating, and then placed in a field-scanning scanning electron microscope (FE-SEM, JEOL JSM-6700F, Japan) for observation, and then energy dispersion by an additional device. The spectrometer (EDS INCAX-sight) performs analysis of chemical elemental composition. X-ray Diffraction Analysis (XRD) analysis: X-ray diffraction (XRD) analysis of MSWI mixed ash, CMPS foul 15 201245103 mud and MSWI-CMPS slag samples of three basic degrees, first It was dried in a vacuum oven at 80 ° C, and fixed on a sample stage after cooling in a drying dish. The crystal phase species of the sample were analyzed by a Japanese-made X-ray powder diffraction instrument (Rigaku, D/Max-2200, Japan). State, which emits X-rays with CuKal and scans 10 with 2 Torr. The range is ~80〇; the scanning rate is performed at a count of 0.05° per second. Toxic Substance Dissolution Test (TCLP) Analysis: MSWI fly ash, mixed ash CMPS sludge and MSWI-CMPS slag sample and MS WI-CMPS slag replaced part of cement cement mortar test, strength and compressive strength test After the pieces are sampled and dried, and ground into fine powder, the toxic characteristic dissolution (TCLP) test is carried out according to the procedure of SW 846-131 1 specification. Hereinafter, the steps and modes for preparing the compressive test body by using the recycled cement material of the present invention are described: The compressive test system is based on the CNS1010 hydraulic cement concrete compressive strength test method and the ASTM C109 compressive strength test, according to the cement and The weight ratio of sand is 1:2.75, the water-to-binder ratio is W/C = 0.485, and the cement mortar sample of 5x5x5-cm3 is cast and cast (control group, nominal Portland cement mortar is called 0PCM sample), and then in different proportions. The MSWI-CMPS slag powder of the present invention replaces 5%, 10%, 20% and 30% cement, and is cast into the same size slag cement mortar sample (test group, slag-blended cement mortar is called SBCM test body) Its configuration is shown in Table 2. After the cement mortar sample is cast, it is placed in a controlled constant temperature and humidity 201245103 box (23 ° C, humidity 95%) - day, and then taken out of the mold and placed in a constant temperature maintenance tank, the temperature is maintained at 23.0 ± 1.7 ° C In the saturated calcium hydroxide aqueous solution tank, after 1 day, 3 days, 7 days, 14 days, 28 days, 60 days and 90 days of curing, the ASTM C109 compressive strength test and other related tests were taken out. In this embodiment, the pure cement mortar (Ordinary Portland Cement mortar, referred to as OPCM in the specification of the present invention), and the Slag Blended Cement Mortar (referred to as SBCM, the test system) are used. Instead of cement 5%, 10%, 20% and 30% (by weight), it is formulated into a mortar. The weight of each component taken is shown in Table 2. Table 2 Ratio of pure cement mortar sample to slag cement mortar sample mortar (5><5x5-cm3) Sample code: OPCM SBCM (5%) SBCM (10%) SBCM (20%) SBCM ( 30%) Proportion of slag to replace cement 0% 5% 10% 20% 30% Cement (g) 740 703 666 592 518 Sand (g) 2035 2035 2035 2035 2035 MSWI-CM PS Refining slag (g) 0 37 74 148 222 Water (g) 359 359 359 359 359 Slag burnout rate and volume reduction ratio: The tempering mixed ash is melted at 1350 °C for half an hour, and then the organic matter and gas contained in the mixed ash will be burned. With evaporation, the loss of the weight of the three bases based on the study herein averaged about 25.79%. The volume of the tempered mixed ash after melting is reduced by about 73.52%, that is, it is concentrated to 26.5% of the original volume. The test results are shown in Table 3. The reduction effect is excellent, which is convenient for temporary storage or burial and safe. Innocent. Table 3: Loss rate and volume reduction ratio of quenched and mixed ash (a) Burn-off rate and volume reduction ratio of MSWI mixed ash and CMPS weight of 1:0.5: Number of burnouts (%) Volume reduction (%) Mixed gray body density (g/cm3) Slag density (g/cm3) 1 29.47 77.28 0.92 2.85 2 26.77 77.91 0.92 3.06 3 29.45 73.78 0.92 2.63 4 25.10 78.76 0.91 2.88 5 29.23 76.01 0.93 2.74 6 22.20 71.19 0.91 2.46 Average 27.04 75.99 0.92 2.77 (b) MSWI mixed ash and CMPS weight, 1:0.75 mixing loss rate and volume reduction rate: number of burnout rate (%) volume reduction rate (%) mixed gray body density (g/cm3) Crush density (g/cm3) 1 20.85 70.07 0.95 2.47 2 25.30 71.19 0.96 2.50 3 24.87 73.59 0.97 2.77 4 20.10 73.43 0.97 2.92 5 33.59 76.09 0.95 2.65 6 20.29 71.36 0.95 2.64 Average 24.16 72.52 0.96 2.66 (c) MSWI mixed ash and The CMPS weight is 1:1 mixed loss rate 18 201245103 and volume reduction rate: number of burnout rate (%) volume reduction rate (%) mixed gray body density (g/cm3) slag density (g/cm3) 1 24.83 72.91 0.89 2.47 2 23.07 73.39 0.85 2.45 3 28.33 74.47 0.89 2.51 4 < 23.00 68.6 3 0.83 2.45 5 29.03 71.65 0.75 2.64 6 28.71 71.33 0.88 2.52 Average 26.16 72.06 0.85 2.51 SEM/EDS Observation and Analysis: SEM and EDS analysis of MSWI mixed ash, CMP sludge and MSWI-CMPS slag Figure 1~3 Shown. The MSWI mixed ash, CMP sludge and MSWI-CMPS slag powder obtained in this experiment were selected by micro-samples and observed by SEM scanning electron microscope. The MS WI mixed ash was agglomerated as shown in Figure 1. The CMP sludge is agglomerated in a spherical or pebbled shape with a particle size of approximately 200 nm to 6 μηι, as shown in Figure 2. The MS WI-CMPS slag powder particles are in the form of a crushed stone having a size of less than 38 μm, as shown in FIG. The chemical composition of the MSWI mixed ash, CMP sludge and MSWI-CMPS slag was then analyzed by EDS, as shown in Figures 1-3 and Table 1. The chemical composition of the MS WI-CMPS slag containing the non-calcium oxides SiO 2 , Al 2 〇 3 and Fe 203 was 24.33 to 49.16 ° / respectively. The sum of 9.16~16.48% and 0.92~1.52%' is 34.41~67.05%, but the CaO content is also as high as 23.30~45.18°/. Close to eight 8 □ 1 ^ € 618 regulations (: the content of grade fly ash 'non-calcium oxide is the main substance of the reaction of 201245103, and the more calcium oxides, there may be better reaction, that is, the strength It may be used in the early stage. XRD analysis: The MS WI mixed ash, CMP sludge and MS WI-CMPS slag are diffracted by X-ray powder, and the obtained analytical spectrum is shown in Figure 4. The most prominent phase material of ash is calcium, which are CaS04, CaCl2, CaClOH and Ca(OH)2, followed by K, Na, Pb, Zn and SiO2. Quenched and tempered mixed ash slag shell|J is amorphous phase The glassy material has a broad X-ray diffraction pattern and is characterized by a glassy substance, which is a typical material. TCLP dissolution test: Fly ash, washed ash and mixed ash all contain Pb, Zn, Cu Hazardous heavy metal components such as Cd and Cr are easily dissolved and contaminate groundwater. However, after high temperature melting treatment, they are surrounded by a network structure of -Si-O- to form a slag with dense, acid and alkali resistance and low dissolution rate effect. The MS WI-CMPS slag is non-crystalline by XRD analysis. The glassy substance will form a network of -Si-O- surrounded by heavy metals. Therefore, the results of TCLP dissolution test, the amount of Pb and Cd dissolved in MS WI mixed ash are higher than the values specified in US SW 846-131 1 specification. The amount of heavy metal dissolved in MSWI-CMPS slag is much lower than the values specified in the above regulations. The test results are shown in Table 4. Table 4 TCLP analysis of MSWI fly ash, mixed ash and quenched slag
Pb Cd Cr Cu Zn 20 201245103 MSWI飛灰 ND 0.42 ND ND 5.22 MSWI混合灰 5.96 4.73 ND 1.41 17.60 調質溶渣(1 : 0.5) ND 0.036 ND 0.14 0.51 調質溶渣(1 :0.75) ND 0.048 ND 0.12 0.39 調質溶渣(1 : 1) ND 0.031 ND 0.08 0.45 法規值 <5.0 < 1.0 <5.0 < 15.0 — 流度試驗： 依ASTM C230規範以波特蘭I型水泥拌合成純水 泥砂漿與各種配比之熔渣水泥砂漿，經流度試驗量測 結果，其流度值如表5所示： (a) . MSWI-CMPS(1 : 0.5)熔渣之 SBCM 試驗組：純水 泥砂漿之流度值為54.50%，而各種取代率之熔渣水 泥砂漿之流度值介於62.11 %〜71.90%之間，顯示流 度值有略高之現象，對施工工作度有變成更好之影 響，其流度值如表5(a)所示。 (b) MSWI-CMPS(1 : 0.75)熔渣之 SBCM 試驗組：純 水泥砂漿之流度值為62.3%，而各種取代率之熔渣 水泥砂漿之流度值介於63.2%〜69.3%之間，顯示流 度值相近之現象，對施工工作度有變好之影響，其 流度值如表5(b)所示。 (c) MSWI-CMPS(1 : 1)熔渣之SBCM試驗組：純水泥 砂漿之流度值為75.8%，而各種取代率之熔渣水泥 砂漿之流度值介於75.8%〜89.7%之間，顯示流度值 有略高之現象，對施工工作度有變好之影響，其流 度值如表5(c)所示。 21 201245103 表5 OPCM與SBCM砂漿試體之流度值 試體名稱 OPCM SBCM(5%) SBCM(10%) SBCM(20%) SBCM(30%) ⑻ 平均值(mm) 169 179 184 186 190 流度值(％) 54.5 62.1 66.0 67.5 71.9 (b) 平均值(mm) 180 185 181 181 187 流度值(％) 62.3 67.0 63.9 63.2 69.3 (c) 平均值(mm) 195 194 205 201 210 流度值(％) 75.8 75.8 85.2 82.1 89.7 初終凝試驗： (a). MSWI-CMPS(1 : 0.5)熔渣水泥漿： 依ASTM C1 87水泥標準稠度試驗，恆溫恆濕機溫 度需保持於23.0±1.7°C，其相對濕度亦需保持90%以 上之情況進行試拌，求得水泥標準稠度之水量為 171.6g，水泥為650g，水膠比W/C= 26.4%，其初凝之 時間為21 6分鐘與終凝時間為243分鐘。添加熔渣之 水泥漿試樣則隨添加量之增加，而有初凝和終凝時間 縮短之趨勢，因炼造之比表面積為6657 cm2/g，比水 泥3520 cm2/g大甚多，其顆粒會吸附較多之水分，使 漿體於水泥之水化過程中之稠度降低，而使凝結時間 較對照組提早，凝結時間最短為取代30%者，初凝時 間為155分鐘與終凝時間為190分鐘，其初凝比對照 組快61分鐘，終凝則快58分鐘，亦即添加30%的吸 附水量最多，而使其凝結時間縮短，惟取代20%以内 則SBCP與OPCP之初、終凝時間相差不多，如表6 所示。 s 22 201245103 表 6 MSWI-CMPS(1 : 0.5)熔渣之 OPCP 與 SBCP 水 泥漿凝結試驗（單位：分鐘） 水泥砂漿試體 OPCP SBCP(5%) SBCP(10%) SBCP(20%) SBCP(30%) 用水量(g) 171.6 170.3 172.9 171.6 188.5 水膠比 0.264 0.262 0.266 0.264 0.290 初凝(分鐘） 216 214 191 179 155 終凝(分鐘） 243 239 234 215 190 (b). MSWI-CMPS(1 : 0.75)熔渣水泥漿： 依ASTM C1 87水泥標準稠度試驗，恆溫恆濕機溫 度需保持於23.0±1.7°C，其相對濕度亦需保持90%以 上之情況進行試拌，求得水泥標準稠度之水量為 174.2g ,水泥為650g，水膠比W/O 26.8%，其初凝之 時間為216分鐘與終凝時間為288分鐘。添加熔渣之 水泥漿試樣則隨添加量之增加，而有初凝和終凝時間 縮短之趨勢，因炼潰之比表面積為6657cm2/g，比水 泥3570 cm2/g大甚多，其顆粒會吸附較多之水分，使 漿體於水泥之水化過程中之稠度降低，而使凝結時間 較對照組提早，凝結時間最短為取代30%者，初凝時 間為147分鐘與終凝時間為231分鐘，其初凝比對照 組快69分鐘，終凝則快57分鐘，亦即添加30%的吸 附水量最多，而使其凝結時間縮短，惟取代20%以内 則SBCP與OPCP之初、終凝時間相差不多，如表7 所示。 表 7 MSWI-CMPS(1 : 0.75)熔渣之 OPCP 與 SBCP 水 23 201245103 泥漿凝結試驗（單位：分鐘） 水泥砂漿試體 OPCP SBCP(5°/〇) SBCP(10%) SBCP(20%) SBCP(30%) 用水量(g) 174.2 170.3 172.9 171.6 188.5 水膠比 0.268 0.262 0.266 0.264 0.29 初凝(分鐘） 216 210 189 178 147 終凝(分鐘） 288 279 270 255 231 (c). MSWI-CMPS(1 : 1)熔渣水泥漿： 依ASTM C1 87水泥標準稠度試驗，恆溫恆濕機溫 度需保持於23.0±1.7°C，其相對濕度亦需保持90%以 上之情況進行試拌，求得水泥標準稠度之水量為 174.2g，水泥為650g，水膠比W/C= 26.8%，其初凝之 時間為21 5分鐘與終凝時間為3 1 8分鐘。添加熔渣之 水泥漿試樣則隨添加量之增加，而有初凝和終凝時間 縮短之趨勢，因炫潰之比表面積為 6657 cm2/g，比水 泥3520 cm2/g大甚多，其顆粒會吸附較多之水分，使 漿體於水泥之水化過程中之稠度降低，而使凝結時間 較對照組提早，凝結時間最短為取代30%者，初凝時 間為1 55分鐘與終凝時間為25 1分鐘，其初凝比對照 組快61分鐘，終凝則快6 7分鐘，亦即添加3 0 %的吸 附水量最多， 而使其凝結時間縮短，惟取代20%以内則SBCP與 OPCP之初、終凝時間相差不多，如表8所示。 表 8 MSWI-CMPS(1 : 1)熔渣之 OPCP 與 SBCP 水 泥漿凝結試驗（單位：分鐘） 24 201245103 水泥砂漿試體 OPCP SBCP(5%) SBCP(10%) SBCP(20%) SBCP(30%) 用水量(g) 174.2 170.3 172.9 171.6 188.5 水膠比 0.264 0.262 0.266 0.264 0.29 初凝(分鐘） 215 207 186 183 155 終凝(分鐘） 318 299 290 285 251 抗壓強度試驗： 水泥砂漿試體抗壓強度試驗，均於各種齡期分別 取三顆試體進行抗壓強度試驗，並以三顆抗壓強度之 平均值進行比對。經試驗後SB CM水泥砂黎試體（實驗 組）與OPCM純水泥砂漿試體（對照組）之抗壓強度試驗 結果，如圖5-圖7與表9-表11所示。 以MSWI- CMPS(1 : 0.5)熔渣取代〇〜30%水泥灌鑄 成5x5x5-cm3砂漿試體進行抗壓試驗，其養護齡期7 天以刖除了取代3 0 %的試體抗壓強度較純水泥砂聚 (對照組）略低外，其餘的試體均高過對照組，約為對 照組之105〜120% ’而於14天後之齡期時因卜作嵐反 應而高過對照組’約為其110〇/。〜121 %。取代5、10 與20 wt·%水泥之砂漿試體，其於丨_9〇天養護齡期之 抗壓強度’均高於對照組試體’約為其1 〇 5〜1 21 〇/〇， 實驗成果相當優越’其抗壓強度值如圖5與表9所示。 表9 〇pCM與SBCM熔渣水泥砂漿試體抗壓強度成 長表 (a)MSWI-CMP (1··0.5)熔渣水泥砂漿試體抗壓強度成 長表 25 201245103 MSWI-CMP (1 ：〇.5) 齡期(天） 1天 3天 7天 14天 28天 60天 90天 OPCM 110.8 257.6 345.2 388.7 451.0 487.1 517.5 (100%) (100%) (100%) (100%) (100%) (100%) (100%) SBCM(5%) 127.2 280.8 381.8 429.2 521.1 543.6 575.5 (115%) (109%) (111%) (110%) (116%) (112%) (111%) SBCM(10%) 133.0 308.7 410.3 477.8 545.7 578.0 626.1 (120%) (120%) (119%) (123%) (121%) (119%) (121%) SBCM(20%) 119.2 270.7 377.2 445.6 536.4 571.5 615.3 (108%) (105%) (109%) (115%) (119%) (117%) (119%) SBCM(30%) 98.6 230.0 329.1 433.8 522.2 566.4 602.0 (89%) (89%) (95%) (112%) (116%) (116%) (116%) 註：括弧内百分比係以OPCM試體(對照組)各齡期之強度為100%，進行比對同齡期其 他SBCM試體強度為標準(OPCM)試體多少百分比之用。 ' 以MSWI-CMPS(1 : 0.75)熔渣取代0〜30%水泥灌 鑄成5x5x5 -cm3砂漿試體進行抗壓試驗，其養護齡期 7天以前除了取代30%的試體抗壓強度較純水泥砂漿 (對照組）略低外，其餘的試體均高過對照組，約為對 照組之102〜112°/。，而於14天後之齡期時因卜作嵐反 應而高過對照組，約為其107%〜120%。取代5、10 與20 wt.%水泥之砂漿試體，其於1-90天養護齡期之 抗壓強度，均高於對照組試體，約為其102〜120%，實 驗成果相當優越，其抗壓強度值如圖6與表10所示。 表10 OPCM與SBCM熔渣水泥砂漿試體抗壓強度成 長表 (b) MSWI-CMP(1:0.75)熔渣水泥砂漿試體抗壓強度 成長表 MS WI-CMP(1:0.75) 齡期(天） 1天 3天 7天 14天 28天 60天 90天 OPCM 174.6 315.5 360.2 414.3 446.7 483.0 503.3 (100%) (100%) (100%) (100%) (100%) (100%) (100%) 26 201245103 SBCM(5%) 178.1 337.7 387.3 453.3 500.0 555.0 585.6 (102%) (107%) (108%) (i〇9〇/0) (112%) (115%) (116%) SBCM(10%) 202.9 365.2 419·5 478.6 523.2 570.6 603.7 (116%) (116%) (116%) ("6%) (117%) (118%) (120%) SBCM(20%) 195.2 349.9 395.7 458.3 518.9 575.5 601.9 (112%) (111%) (110%) (111%) (116%) (119%) (120%) SBCM(30%) 159.8 290.3 342.0 442.7 478.3 546.7 578.2 (92%) (92%) (95%) (107%) (107%) (113%) (115%) 註：括弧内百分比係以OPCM試體(對照組)各齡期之強度為loo%，進行比對同齡期其 他SBCM試體強度為標準(OPCM)試體多少百分比之用。 以MSWI- CMPS (1 : 1)熔渣取代〇〜30°/。水泥灌鑄 成5x5x5 -cm3砂漿試體進行抗壓試驗，其養護齡期1 天之強度均略低於純水泥砂漿試體，3-7天時除了取代 30%的試體抗壓強度較純水泥砂漿（對照組）略低外，其 餘的試體均高過對照組，約為對照組之102〜1 15%， 而於14天齡期以後時則因卜作嵐反應而高過對照 組，約為其103 %〜116%。取代5、10與20 wt.%水泥 之砂漿試體，其於1 -90天養護齡期之抗壓強度，除第 1天外均高於對照組試體，約為其105〜116%，實驗 成果相當優越，其抗壓強度值如圖7與表11所示。 表11 OPCM與SBCM熔渣水泥砂漿試體抗壓強度成 長表 (C) MSWI-CMP(1:1)熔渣水泥砂漿試體抗壓強度成長表 MSWI-CMP(1 ： 1) 齡期(天） 1天 3天 7天 14天 28天 60天 90天 OPCM 177.3 290.7 348.5 424.4 455.7 489.8 509.7 (100%) (100%) (100%) (100%) (100%) (100%) (100%) SBCM(5%) 168.4 312.2 364.9 451.5 478.3 520.9 546.1 (95%) (107%) (105%) (106%) (105%) (106%) (107%) SBCM(10%) 169.6 333.1 398.4 486.0 530.1 558.1 585.5 27 201245103 (96%) (115%) (114%) (115%) (Π 6%) (114%) (115%) SBCM(20%) 159.6 296.8 370.0 450.7 479.7 562.7 589.1 (90%) (102%) (106%) (106%) (105%) (115%) (116%) SBCM(30%) 144.2 266.2 332.7 438.4 475.1 519.1 576.7 (81%) (92%) (95%) (103%) (104%) (106%) (113%) 註：括弧内百分比係以OPCM試體(對照組)各齡期之強度為100%，進行比對同齡期其 他SBCM試體強度為標準(OPCM)試體多少百分比之用。 綜觀實驗組與對照組水泥砂漿試體抗壓強.度之成 長，實驗組僅少部份試體於齡期1天時其強度比對照 組相仿而略低，其餘大部份試體則均比對照組為高， 此現象已突破習知技術均有早期強度（1-28天）不足之 問題，依本發明該再生水泥材料製作之SBCM試體， 大部分SBCM試體於1 -90天之所有養護齡期，其抗壓 強度均高於OPCM試體，約高 2-21%，此表示 MSWI-CMPS熔渣替代部份水泥使用之優越性。 由上可知，本發明利用有害事業廢棄物為材料之 再生水泥材料及其再生方法可獲致至少以下之效果： (1 )本發明揭露一種將化學機械研磨污泥（CMPS ) 取代水泥，製成砂漿，養護後，此砂漿經毒性溶出實驗 (TCLP)，無毒性物質溶出；且所得到的強度，在某些取代 範圍可以明顯高於一般水泥砂漿，具有顯著的新穎性。 (2 )本發明進一步揭露將化學機械研磨污泥與垃圾 焚化混合灰之共融熔渣取代部分水泥，所得到的砂漿養護 後總強化量可以高於純水泥砂漿試體，或僅用飛灰熔渣之 砂漿試體者；而且1天養護強度即可以跟一般水泥砂漿相 28 201245103 等或略高；其進步性非常明顯。 (3 )本發明可將垃圾焚化廠之飛灰與洗滌灰悉數處 理，其減容率高達73.5°/。，而可將有害環境的廢棄物，熔 融成炼〉查後才棄置而無害環境。故本發明具有良好綠色、 環保與永續發展之意義。 (4 )本發明再生水泥材料配成砂漿或混凝土，可成 為比一般水泥砂漿或混凝土更強上2〇%的建材，具有很大 的工程實用價值。 綜上所述’本發明將垃圾焚化廠所產生之有害事 業廢棄物飛灰與洗；條灰（亦稱反應灰或反應生成物）予 以悉數混合’再添加適量的半導體化學機械研磨製程 之廢污泥粉末，予以均勻混合後進行熔融處理所形成 之玻璃質熔潰具-Si-O-之網狀構造，能將殘留於熔渣晶 格中之重金屬予以包絡’致使重金屬不易溶出，俾可 取代部分水泥’與砂、水等調配成水泥砂漿，於取代 量5〜30°/。之範圍，養護強度可以高於純水泥砂漿，且 其流度值（施工軟度）較純水泥砂漿為佳，凝結時間則 相近。由抗壓強度之s式驗結果發現，此炼渣可以大幅 提升早期（1〜7天）之強度’因此炼潰砂衆試體之早期強 度大部分比純水泥砂漿為高，其餘部分試體則相仿， 而14〜90天齡期則均高於純水泥砂漿之強度，超出約 7〜21 % ’功效非常良好。又，該熔渣粉末經毒性特性 溶出试驗分析結果’其重金屬之溶出量遠低於環保署 29 201245103 規定之法規值。試驗結果顯現該溶渣可取代5〜30%水 泥使用，可作為環保水泥使用。基此，本發明可將垃 圾焚化廠之飛灰與洗滌灰全數予以資源化再利用，既 可減少飛灰、洗滌灰與化學機械研磨污泥掩埋場之需 求，亦利於防止上述有害事業廢棄物，於不適當棄置 時造成之環境污染，並可將這兩種廢棄物轉化成為水 泥使用，而無二次污染之疑慮。更可減少水泥製造所 產生之環境污染與破壞問題；緣是，本發明確實符合 發明專利之規定，爰依法提出申請。 【圖式簡單說明】 圖一：垃圾焚化混合灰之（a)SEM微觀影像與 (b)EDS成份分析圖。 圖二：CMP污泥之（a) SEM微觀影像與（b) EDS成 份分析圖。 圖三：MS WI-CMPS熔渣之（a) SEM微觀影像與（b) EDS成份分析圖。 圖四：MSWI混合灰、CMP污泥與MSWI-CMPS 熔渣之XRD分析圖，其中MSWI-CMPS熔渣依重量配 比分為1:0.5、1:0.75與1:1三種。 圖五：MSWI-CMPS(1 : 0.5)熔渣砂漿試體之（a)強 度成長柱狀圖與（b)強度成長趨勢圖。 圖六：MSWI-CMPS(1 : 0.75)熔渣砂漿試體之（a) 201245103 強度成長柱狀圖與（b)強度成長趨勢圖。 圖七為MSWI-CMPS(1 : 1)熔渣砂漿試體之（a)強度 成長柱狀圖與（b)強度成長趨勢圖。 【主要元件符號說明】 無圖號 31Pb Cd Cr Cu Zn 20 201245103 MSWI fly ash 0.42 ND ND 5.22 MSWI mixed ash 5.96 4.73 ND 1.41 17.60 tempering slag (1 : 0.5) ND 0.036 ND 0.14 0.51 smelting slag (1:0.75) ND 0.048 ND 0.12 0.39 tempering slag (1 : 1) ND 0.031 ND 0.08 0.45 Regulatory value <5.0 < 1.0 <5.0 < 5.0 < 15.0 - Fluidity test: Synthetic pure cement mortar with Portland I type cement according to ASTM C230 specification The fluidity values of the slag cement mortars with various ratios are shown in Table 5. (a) . SBCM test group of MSWI-CMPS (1: 0.5) slag: pure cement mortar The fluidity value is 54.50%, and the fluidity values of the slag cement mortars of various substitution rates are between 62.11% and 71.90%, indicating that the fluidity value is slightly higher, and the construction workability becomes better. The effect is shown in Table 5(a). (b) SBCM test group of MSWI-CMPS (1: 0.75) slag: the fluidity value of pure cement mortar is 62.3%, and the fluidity value of slag cement mortar with various substitution rates is between 63.2% and 69.3%. In the meantime, the phenomenon that the fluidity values are similar is displayed, and the construction work degree is improved. The fluidity value is shown in Table 5(b). (c) MSWI-CMPS (1: 1) slag SBCM test group: the fluidity value of pure cement mortar is 75.8%, and the fluidity value of slag cement mortar of various substitution rates is between 75.8% and 89.7%. In the meantime, the liquidity value is slightly higher, and the construction workability is better. The fluidity value is shown in Table 5(c). 21 201245103 Table 5 Flow values of OPCM and SBCM mortar specimens Test name OPCM SBCM (5%) SBCM (10%) SBCM (20%) SBCM (30%) (8) Average (mm) 169 179 184 186 190 flow Degree (%) 54.5 62.1 66.0 67.5 71.9 (b) Average (mm) 180 185 181 181 187 Fluid value (%) 62.3 67.0 63.9 63.2 69.3 (c) Average (mm) 195 194 205 201 210 Fluidity value (%) 75.8 75.8 85.2 82.1 89.7 Initial setting test: (a). MSWI-CMPS (1: 0.5) slag cement slurry: According to ASTM C1 87 cement standard consistency test, the temperature of constant temperature and humidity machine should be maintained at 23.0±1.7 °C, the relative humidity should also be maintained above 90% for the test mixture, the water standard of the cement is 171.6g, the cement is 650g, the water-to-gel ratio is W/C = 26.4%, and the initial setting time is 21 The 6 minute and final setting time was 243 minutes. The cement slurry sample with slag added has a tendency to shorten the initial setting and final setting time with the addition amount, because the specific surface area of the refining is 6657 cm2/g, which is much larger than the cement 3520 cm2/g. The particles will adsorb more water, which will reduce the consistency of the slurry in the hydration process of the cement, and make the setting time earlier than the control group. The shortest setting time is 30%, and the initial setting time is 155 minutes and the final setting time. For 190 minutes, the initial setting is 61 minutes faster than the control group, and the final setting is 58 minutes faster, that is, 30% of the adsorbed water is added the most, and the setting time is shortened, but the replacement of SBCP and OPCP is less than 20%. The final setting time is similar, as shown in Table 6. s 22 201245103 Table 6 COPP and SBCP cement slurry coagulation test for MSWI-CMPS (1: 0.5) slag (unit: minute) Cement mortar test body OPCP SBCP (5%) SBCP (10%) SBCP (20%) SBCP ( 30%) Water consumption (g) 171.6 170.3 172.9 171.6 188.5 Water-to-binder ratio 0.264 0.262 0.266 0.264 0.290 Initial setting (minutes) 216 214 191 179 155 Final setting (minutes) 243 239 234 215 190 (b). MSWI-CMPS (1) : 0.75) slag cement slurry: According to ASTM C1 87 cement standard consistency test, the temperature of constant temperature and humidity machine should be maintained at 23.0±1.7°C, and the relative humidity should be maintained at more than 90% for test mixing. The water content of the consistency is 174.2 g, the cement is 650 g, the water-gel ratio is 26.8%, and the initial setting time is 216 minutes and the final setting time is 288 minutes. The cement slurry sample with slag added has a tendency to shorten the initial setting and final setting time with the addition amount. The specific surface area of the refining is 6657cm2/g, which is much larger than the cement 3570 cm2/g. Will absorb more water, so that the consistency of the slurry in the hydration process of the cement, and the coagulation time is earlier than the control group, the coagulation time is the shortest to replace 30%, the initial setting time is 147 minutes and the final setting time is In 231 minutes, the initial setting was 69 minutes faster than the control group, and the final setting was 57 minutes faster, that is, 30% of the adsorbed water was added the most, and the setting time was shortened. However, the replacement of SBCP and OPCP was replaced by 20% or less. The condensing time is similar, as shown in Table 7. Table 7 MSWI-CMPS (1: 0.75) slag OOPC and SBCP water 23 201245103 Mud coagulation test (unit: minute) Cement mortar test body OPCP SBCP (5 ° / 〇) SBCP (10%) SBCP (20%) SBCP (30%) Water consumption (g) 174.2 170.3 172.9 171.6 188.5 Water-to-binder ratio 0.268 0.262 0.266 0.264 0.29 Initial setting (minutes) 216 210 189 178 147 Final setting (minutes) 288 279 270 255 231 (c). MSWI-CMPS ( 1 : 1) slag cement slurry: According to ASTM C1 87 cement standard consistency test, the temperature of constant temperature and humidity machine should be maintained at 23.0±1.7°C, and the relative humidity should be maintained at more than 90% for test mixing. The standard consistency water volume is 174.2 g, the cement is 650 g, the water-binder ratio W/C = 26.8%, and the initial setting time is 21 5 minutes and the final setting time is 3 18 minutes. The cement slurry sample with slag added has a tendency to shorten the initial setting and final setting time with the increase of the added amount. The specific surface area of the smashing is 6657 cm2/g, which is much larger than the cement 3520 cm2/g. The particles will adsorb more water, so that the consistency of the slurry in the hydration process of the cement is reduced, and the setting time is earlier than the control group. The minimum setting time is 30%, the initial setting time is 1 55 minutes and the final setting is completed. The time is 25 minutes, the initial setting is 61 minutes faster than the control group, and the final setting is 6 7 minutes faster, that is, adding 30% of the adsorbed water is the most, and the condensation time is shortened, but the SBCP is replaced by 20% or less. The initial and final setting times of OPCP are similar, as shown in Table 8. Table 8 COPP and SBCP cement slurry coagulation test of MSWI-CMPS (1:1) slag (unit: minute) 24 201245103 Cement mortar test body OPCP SBCP (5%) SBCP (10%) SBCP (20%) SBCP (30 %) Water consumption (g) 174.2 170.3 172.9 171.6 188.5 Water-to-binder ratio 0.264 0.262 0.266 0.264 0.29 Initial setting (minutes) 215 207 186 183 155 Final setting (minutes) 318 299 290 285 251 Compressive strength test: Cement mortar test body resistance In the compressive strength test, three test pieces were taken at various ages for compressive strength test, and the average of three compressive strengths was compared. The results of the compressive strength test of the SB CM cement sand sample (experimental group) and the OPCM pure cement mortar sample (control group) after the test are shown in Fig. 5 - Fig. 7 and Table 9 - Table 11. The MSWI- CMPS (1: 0.5) slag was used to replace the 〇~30% cement into a 5x5x5-cm3 mortar test for compression test. The curing age was 7 days to replace the 30% test compressive strength. Compared with the pure cement sand poly (control group), the other samples were higher than the control group, which was about 105~120% of the control group, and was higher than the control group at the age of 14 days. 'About its 110〇/. ~121%. Replacing the mortar samples of 5, 10 and 20 wt·% cement, the compressive strength of the 养 〇 〇 〇 养 养 养 均 均 均 均 均 均 均 均 均 均 均 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为 约为The experimental results are quite superior', and their compressive strength values are shown in Figure 5 and Table 9. Table 9 抗pCM and SBCM slag cement mortar test body compressive strength growth table (a) MSWI-CMP (1··0.5) slag cement mortar test body compressive strength growth table 25 201245103 MSWI-CMP (1: 〇. 5) Age (days) 1 day 3 days 7 days 14 days 28 days 60 days 90 days OPCM 110.8 257.6 345.2 388.7 451.0 487.1 517.5 (100%) (100%) (100%) (100%) (100%) ( 100%) (100%) SBCM (5%) 127.2 280.8 381.8 429.2 521.1 543.6 575.5 (115%) (109%) (111%) (110%) (116%) (112%) (111%) SBCM (10 %) 133.0 308.7 410.3 477.8 545.7 578.0 626.1 (120%) (120%) (119%) (123%) (121%) (119%) (121%) SBCM (20%) 119.2 270.7 377.2 445.6 536.4 571.5 615.3 ( 108%) (105%) (109%) (115%) (119%) (117%) (119%) SBCM (30%) 98.6 230.0 329.1 433.8 522.2 566.4 602.0 (89%) (89%) (95% (112%) (116%) (116%) (116%) Note: The percentage of brackets is 100% of the strength of each age of the OPCM specimen (control group), and the strength of other SBCM specimens of the same age is compared. What percentage of the standard (OPCM) test is used. ' With MSWI-CMPS (1: 0.75) slag instead of 0~30% cement cast into 5x5x5 -cm3 mortar test for compression test, the maintenance age 7 days before the replacement of 30% of the test body compressive strength The pure cement mortar (control group) was slightly lower, and the rest of the samples were higher than the control group, which was about 102 to 112 °/ of the control group. At the age of 14 days later, it was higher than the control group due to the response, which was about 107% to 120%. Replacing the mortars of 5, 10 and 20 wt.% cement, the compressive strength of the aged 1 to 90 days was higher than that of the control group, which was about 102~120%. The experimental results were quite excellent. The compressive strength values are shown in Fig. 6 and Table 10. Table 10 OPCM and SBCM slag cement mortar test body compressive strength growth table (b) MSWI-CMP (1:0.75) slag cement mortar test body compressive strength growth table MS WI-CMP (1:0.75) age ( Day) 1 day 3 days 7 days 14 days 28 days 60 days 90 days OPCM 174.6 315.5 360.2 414.3 446.7 483.0 503.3 (100%) (100%) (100%) (100%) (100%) (100%) (100 %) 26 201245103 SBCM(5%) 178.1 337.7 387.3 453.3 500.0 555.0 585.6 (102%) (107%) (108%) (i〇9〇/0) (112%) (115%) (116%) SBCM( 10%) 202.9 365.2 419·5 478.6 523.2 570.6 603.7 (116%) (116%) (116%) ("6%) (117%) (118%) (120%) SBCM (20%) 195.2 349.9 395.7 458.3 518.9 575.5 601.9 (112%) (111%) (110%) (111%) (116%) (119%) (120%) SBCM (30%) 159.8 290.3 342.0 442.7 478.3 546.7 578.2 (92%) (92 %) (95%) (107%) (107%) (113%) (115%) Note: The percentage in parentheses is based on the intensity of each age of the OPCM specimen (control group). The other SBCM test body strength is used as a percentage of the standard (OPCM) test body. Replace 〇~30°/ with MSWI- CMPS (1:1) slag. The cement was cast into a 5x5x5-cm3 mortar test piece for compressive test. The strength of the curing period of 1 day was slightly lower than that of the pure cement mortar sample. In addition to replacing 30% of the test piece, the compressive strength of the test piece was 3-7 days. The cement mortar (control group) was slightly lower, and the other samples were higher than the control group, which was about 102~1 15% of the control group, and after the 14-day-old period, it was higher than the control group due to the sputum reaction. It is 103%~116%. Replacing the mortar strength of 5, 10 and 20 wt.% cement, the compressive strength of the curing age from 1 to 90 days was higher than that of the control group except for the first day, about 105~116%. The results are quite excellent, and the compressive strength values are shown in Fig. 7 and Table 11. Table 11 OPCM and SBCM slag cement mortar test body compressive strength growth table (C) MSWI-CMP (1:1) slag cement mortar test body compressive strength growth table MSWI-CMP (1: 1) age (day 1 day 3 days 7 days 14 days 28 days 60 days 90 days OPCM 177.3 290.7 348.5 424.4 455.7 489.8 509.7 (100%) (100%) (100%) (100%) (100%) (100%) (100% SBCM (5%) 168.4 312.2 364.9 451.5 478.3 520.9 546.1 (95%) (107%) (105%) (106%) (105%) (106%) (107%) SBCM (10%) 169.6 333.1 398.4 486.0 530.1 558.1 585.5 27 201245103 (96%) (115%) (114%) (115%) (Π 6%) (114%) (115%) SBCM (20%) 159.6 296.8 370.0 450.7 479.7 562.7 589.1 (90%) (102%) (106%) (106%) (105%) (115%) (116%) SBCM (30%) 144.2 266.2 332.7 438.4 475.1 519.1 576.7 (81%) (92%) (95%) (103 %) (104%) (106%) (113%) Note: The percentage of parentheses is 100% of the intensity of each age of the OPCM test body (control group), and the other SBCM test body strengths of the same age are compared. OPCM) What percentage of the test is used. Looking at the growth of the cement mortar in the experimental group and the control group, only a small part of the experimental group had a slightly lower intensity than the control group at the first day of the test, and most of the other samples were compared. The control group is high. This phenomenon has broken through the problem that the prior art has insufficient early strength (1-28 days). According to the SBCM test piece made of the recycled cement material of the present invention, most of the SBCM test bodies are in the range of 1-90 days. At all curing ages, the compressive strength is higher than that of the OPCM specimen, which is about 2-21% higher. This indicates the superiority of MSWI-CMPS slag to replace some cement. It can be seen from the above that the regenerated cement material using the hazardous business waste as a material and the regeneration method thereof can at least achieve the following effects: (1) The present invention discloses that a chemical mechanical polishing sludge (CMPS) is used instead of cement to form a mortar. After curing, the mortar is subjected to toxic dissolution test (TCLP), and the non-toxic substance is dissolved; and the obtained strength can be significantly higher than the general cement mortar in some substitution ranges, and has remarkable novelty. (2) The present invention further discloses that the co-melting slag of the chemical mechanical grinding sludge and the garbage incineration mixed ash is substituted for part of the cement, and the total strengthening amount of the obtained mortar after curing can be higher than that of the pure cement mortar sample, or only the fly ash is used. The slag mortar tester; and the 1-day curing strength can be slightly higher than the general cement mortar phase 28 201245103; its progress is very obvious. (3) According to the present invention, the fly ash and the washing ash of the waste incineration plant can be processed in a complete manner, and the capacity reduction rate is as high as 73.5°/. The waste that is harmful to the environment can be melted into a refining and then discarded before being harmless. Therefore, the invention has the meaning of good green, environmental protection and sustainable development. (4) The recycled cement material of the present invention is formulated into mortar or concrete, which can be a building material which is 2% more than the general cement mortar or concrete, and has great engineering practical value. In summary, the invention relates to the waste ash and washing of the hazardous business waste generated by the waste incineration plant; the ash (also known as the reaction ash or the reaction product) is mixed in combination, and the appropriate amount of the semiconductor chemical mechanical polishing process is added. The sludge powder is uniformly mixed and then melt-treated to form a glass-melt-Si-O-mesh structure, which can envelop the heavy metals remaining in the slag lattice, so that heavy metals are not easily dissolved. Replace part of the cement' with sand, water, etc. into a cement mortar, in the amount of substitution 5~30 ° /. The range of curing strength can be higher than that of pure cement mortar, and its fluidity value (construction softness) is better than that of pure cement mortar, and the setting time is similar. It is found from the test results of compressive strength that the refining slag can greatly improve the strength of the early (1~7 days). Therefore, the early strength of the refining sand test body is mostly higher than that of the pure cement mortar, and the rest of the samples are tested. It is similar, and the 14~90 day age is higher than the strength of pure cement mortar, exceeding about 7~21%. The effect is very good. Moreover, the slag powder has been subjected to toxicity analysis and dissolution test results. The amount of heavy metal dissolved is much lower than the regulatory value stipulated by the Environmental Protection Agency 29 201245103. The test results show that the slag can be used in place of 5 to 30% of cement and can be used as an environmentally friendly cement. Accordingly, the present invention can recycle and utilize the fly ash and washing ash of the waste incineration plant, thereby reducing the demand for fly ash, washing ash and chemical mechanical grinding sludge landfill, and also preventing the above-mentioned harmful business waste. Environmental pollution caused by improper disposal, and the two kinds of waste can be converted into cement use without doubt of secondary pollution. It can reduce the environmental pollution and damage caused by cement manufacturing; the reason is that the invention does meet the requirements of the invention patent and submits an application according to law. [Simple diagram of the diagram] Figure 1: (a) SEM microscopic image of waste incineration mixed ash and (b) EDS composition analysis diagram. Figure 2: (a) SEM microscopic image of CMP sludge and (b) EDS component analysis chart. Figure 3: (a) SEM microscopic image of MS WI-CMPS slag and (b) EDS composition analysis chart. Figure 4: XRD analysis of MSWI mixed ash, CMP sludge and MSWI-CMPS slag. MSWI-CMPS slag is divided into 1:0.5, 1:0.75 and 1:1 by weight. Figure 5: (a) Strong growth histogram and (b) intensity growth trend of MSWI-CMPS (1: 0.5) slag mortar. Figure 6: MSWI-CMPS (1: 0.75) slag mortar sample (a) 201245103 intensity growth histogram and (b) intensity growth trend chart. Figure 7 shows the (a) intensity growth histogram and (b) intensity growth trend of the MSWI-CMPS (1:1) slag mortar sample. [Main component symbol description] No picture number 31