1325795 九、發明說明： 【發明所屬之技術領域】 本發明係關於使用磷酸二鈣二水合物粉末穩定重金屬 及氣味控制之方法。 【先前技術】 發明背景 最近30年來’含重金屬材料及廢料暴露於人類及環境 中及有害氣味的產生及來自固體廢料處理設施之潛在及已 觀察到之危害一直是廣泛性管理控制的基礎。重金屬浸出 及轉移至地表水體及地下水中受到極大關注，因為此將造 成飲用水供給及環境受到污染之危害。含重金屬材料及廢 料’諸如產物或廢料、油漆殘餘物、淤泥、電鍍廢料、沈 積物、鑄造廠粉塵、鑄砂、鋼廠粉塵、粉碎器殘餘物、導 線絕緣物、垃圾焚化爐飛灰、焚化爐底渣、焚化爐混合灰 渣、來自空氣污染控制裝置如旋風除塵器、靜電濾塵器及 衣式集塵器；慮袋之除塵器殘餘物，若含有管制限值以上之 某些可溶性重金屬，則將被美國環保局（U s _ EPA )依照 40 Part 261視為危險性者。任何固體廢料，只要因 為其被“列舉”於40(^.11，卩如2618讣1>如〇中，或因為 其展現-或多種如part 26! Subpart c中所定義之危險性廢 料特徵，均可被定義為危險性的。此等特徵為〇)可燃性， 主(2)腐錄，（3)反應性，以及（4)毒性，毒性係根據 毒性特徵性浸出程序（TCLP)所測試。當含重金屬材料及 5 1325795 廢料非處於襯層填埋場中且暴露於直接地下水、飲用水、 雨水及地表水體時’該等廢料及材料亦可根據州及聯邦地 下水及地表水保護標準來管制，該標準對於重金屬規定的 總限值及浸出限值通常低於TCLP標準。在處理或穩定此等 廢料及材料期間所產生之氣味，諸如來自垃圾焚化爐灰渣 及處理灰渣之操作之氣味，可能給該等設施之操作者帶來 問題，因為許多廢料產生及穩定操作係鄰近於工業、商業 及/或住宅區。氣味散發大多根據當地公害法令規則來管 制’而一些地區則根據聯邦及/或州空氣品質規定來管制。 前對於含有可浸出重金屬 TCLP分析含量在〇 2至 (ppm)以上，則該廢料係 40 CH，part 261 24(a)含有污染物及其相關最大允 許濃度之清單。無機物清單包括As、Ag、Ba、Cd、Cr、Pb、 Hg及Se。若在使用如4〇 c F R pan 261附錄2所說明之 TCLP分析進行測試時污染物超過其最大允許濃度則將此 材料分類為危險性材料。TCLp測試使用於去離子水中之稀 乙酸（TCLP流體2)或於含氫氧化納緩衝液之去離子水中 之稀乙酸（TCLP流體！）。兩種萃取物皆試圖模擬來自分 解垃圾填埋場之浸出液特徵，其中假定受測試之危險性廢 料係在乙酸次出條件下處置且因此經受乙酸浸出條件。目 之廢料而言，若所界定金屬之1325795 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for stabilizing heavy metals and controlling odor using a dicalcium phosphate dihydrate powder. [Prior Art] Background of the Invention The exposure of heavy metal materials and waste materials to humans and the environment and the generation of harmful odors and potential and observed hazards from solid waste treatment facilities have been the basis of extensive management control for the past 30 years. Heavy metal leaching and transfer to surface waters and groundwaters are of great concern as they pose a risk of drinking water supply and environmental pollution. Contains heavy metal materials and waste materials such as products or scraps, paint residues, sludge, electroplating waste, sediments, foundry dust, foundry sand, steel mill dust, pulverizer residues, wire insulation, waste incinerator fly ash, incineration Bottom slag, incinerator mixed ash, air pollution control devices such as cyclone dust collectors, electrostatic precipitators and clothing dust collectors; if the filter residue of the bag is contained, if it contains some soluble heavy metals above the regulatory limit, It will be considered dangerous by the US Environmental Protection Agency (U s EPA) in accordance with 40 Part 261. Any solid waste, as long as it is "listed" in 40 (^.11, such as 2618讣1> as in 〇, or because it exhibits - or a variety of hazardous waste characteristics as defined in part 26! Subpart c, Can be defined as hazardous. These characteristics are: 可 flammability, primary (2) rot, (3) reactivity, and (4) toxicity, toxicity is tested according to the characteristic characteristic leaching procedure (TCLP) . When heavy metal containing materials and 5 1325795 waste are not in a lining landfill and exposed to direct groundwater, drinking water, rainwater and surface waters, such wastes and materials may also be controlled in accordance with state and federal groundwater and surface water protection standards. The standard limits for the heavy metals and the leaching limits are usually lower than the TCLP standard. Odors generated during the handling or stabilization of such waste materials and materials, such as odours from waste incinerator ash and handling ash, may present problems for operators of such facilities as many waste generation and stable operations It is adjacent to industrial, commercial and/or residential areas. Most odours are regulated according to local pollution laws and regulations, while some areas are regulated according to federal and/or state air quality regulations. For the TCLP containing leached heavy metals, the content of the TCLP is above 至 2 to (ppm), then the waste is 40 CH, part 261 24(a) contains a list of contaminants and their associated maximum allowable concentrations. The list of inorganic substances includes As, Ag, Ba, Cd, Cr, Pb, Hg, and Se. If the contaminant exceeds its maximum allowable concentration when tested using the TCLP analysis as described in Appendix 2 of 4 〇 c F R pan 261, the material is classified as a hazardous material. The TCLp test uses dilute acetic acid (TCLP Fluid 2) in deionized water or dilute acetic acid (TCLP Fluid!) in deionized water containing sodium hydroxide buffer. Both extracts attempt to simulate the characteristics of the leachate from the landfill, where it is assumed that the hazardous waste being tested is disposed of under acetic acid secondary and thus subjected to acetic acid leaching conditions. For the purpose of waste, if the metal is defined
6 1325795 用測試作為浸出性之量測方法，諸如臺灣罪律賓、 泰國及加拿大。泰國亦限制Cu及Zn之溶解度，因為此等 金屬關係到泰國的地下太。R丄> 瑞士及大多數歐洲國家亦藉由 使用模擬酸雨水之破龄k M砝、普 及毆K的連續次出方法進行測試來量測 重金屬及鹽，藉此營制因辦麻姐 符此g市j固體廢枓之處理。日本及英國使用 類似的碳酸去離子水浸屮嘴丨4 &县 N次出利β式來量測重金屬之填埋場 潛勢。 另外，美國ΕΡΑ陸地處置限制法規禁止在陸地處置經 執行TCLP分析時浸出超過最大允許濃度之經處理危險性 廢料。陸地處置規定要求，在置於地面蓄水區、廢料堆、 填埋場或如40 C.F.R. 260·10.中所定義之其他陸地處理單 疋中之前，將危險性廢料處理至重金屬不會自在最大允許 濃度以上程度之固體廢料以通用處理標準（UTS)含量浸出。 社會團體擁有管制可能成為公害之氣味之產生的當地 法令，且在一些狀況中管制者已制定最大允許氣味指數程 度。亦已根據美國清潔空氣法案及修正案且已由〇SHA及 NIOSH制定出最大每小時平均及每日平均化學氣體及顆粒 含量。使用不同含量之活性碳與目標廢料或材料混合且利 用一组具有人類嗅覺之人員進行氣味指數測試為一種比較 氣味之方法。詢問該組人員以確認或否認氣味感覺，其與 目標廢料中所用之活性碳量相關而產生氣味指數。指數越 低’可能遇到的氣味就越強。可能因帶有氣味之氣體之散 發及轉移或擴散而存在某些健康及環境釋放風險，且因此 控制及減少該等有味氣體之需要可能超出單純的損害議題 7 1325795 的範圍。舉例而言，具有臭雞蛋氣味之h2s氣體高度有毒 且可在人類暴露於較低致死含量下持續極短時間後造成死 亡。 浸出測試使固趙廢料（包括游泥、灰渣、殘餘物' 料或土壤）經歷稀乙酸浸出（TCLP )、緩衝擰檬酸浸出 (STLC )、蒸餾水、合成雨水（SPLP、MEp )或碳酸水浸 出（曰本、美國、瑞士及USEPA S W-924) »亦常使用合成 雨水浸出測試來量測重金屬溶解度，且將其與地下水及地 表水之州及聯邦標準進行比較，其中材料及廢料可就地再 使用或以襯層填埋場以外之方式處置。 合適之乙酸浸出測試包括USEPA s w_846手冊所描述 之毒性特徵性浸出程序（TCLp)及現在加拿大所採用之萃 取程序毒性測試（ΕΡ τ〇χ )。簡言之，在毒性特徵性浸出 程序（TCLP)測試中，將1〇〇複合樣品公克之負3/8,，大小 的廢料與2000毫升的稀乙酸（TCLp流體#2)或緩衝乙酸 (TCLP流體#1)在翻滾式轉筒（end-over·— tumbler)中 在33啊接觸1M、時。TCLp方法（#1或⑺是藉由TCLp USEPA方法1311中闡明的消化測試測量負3/8，，大小的廢料 相對驗度後選擇。TCLP流體2萃取溶液是由”毫升冰乙 酸以DI水稀釋直_咖毫升而配製。TCLP流體1萃取溶 液是由將5.7毫升冰乙酸與“ 3毫升的1〇當量濃度氫氧化 納的混合物以DI水雜媒 八稀釋直到1000毫升而配製。最危險 料具有低鹼含量及需尊TrT n ^ m 罵要TCLP流體i，包括焚化爐底 要TCLP流體2的廢料 一南 科的起始pH時常高於12_〇單位及一般 1325795 擦有石灰或強驗，諸如石灰除塵器殘餘物或以處理 主的石灰。 ' w 合適之合成酸浸出測試包括現在美國針對在浸出液收 # u $㈣場以外再使用廢料之地點所用的usepa SW_846手冊所描述之合成沈殿劑浸出程序（SPLP)及多重 。簡5之，在SPLP測試中將⑽ 公克廢料與2GG0 ml稀硝酸及硫酸—起翻轉1M、時。將萃6 1325795 Use the test as a measure of leaching, such as Taiwan's criminals, Thailand and Canada. Thailand also limits the solubility of Cu and Zn because these metals are related to the underground in Thailand. R丄> Switzerland and most European countries also measure heavy metals and salt by testing using the age-old k M砝 of simulated acid rain and the continuous secondary method of popularizing 殴K. This g city j solid waste treatment. Japan and the United Kingdom used a similar deionized water-immersed water-immersed sputum 丨 4 & county N times profit beta to measure the potential of heavy metal landfills. In addition, the US Terrestrial Disposal Restriction Regulation prohibits the leaching of hazardous wastes that exceed the maximum allowable concentration when performing TCLP analysis on land. Terrestrial disposal regulations require that hazardous waste be treated to heavy metals without being placed in a surface water storage area, waste dump, landfill or other land treatment unit as defined in 40 CFR 260·10. Solid wastes above the allowable concentration are leached at the Universal Processing Standard (UTS) level. Social groups have local laws that regulate the production of odours that may become nuisances, and in some cases regulators have established maximum allowable odour index levels. The maximum hourly average and daily average chemical gas and particulate content have been developed in accordance with the US Clean Air Act and amendments and have been developed by SHA and NIOSH. Using a different amount of activated carbon mixed with the target waste or material and using a group of people with human odors to test the odour index is a method of comparing odors. The group is asked to confirm or deny the odor perception, which correlates with the amount of activated carbon used in the target waste to produce an odour index. The lower the index, the stronger the odor that may be encountered. There may be some risk of health and environmental release due to the emission and transfer or diffusion of odorous gases, and therefore the need to control and reduce such odorous gases may exceed the scope of the simple damage issue 7 1325795. For example, the h2s gas with the smell of rotten eggs is highly toxic and can cause death after human exposure to lower lethal levels for a very short time. The leaching test subjects the solid waste (including mud, ash, residue or soil) to dilute acetic acid leaching (TCLP), buffered citric acid leaching (STLC), distilled water, synthetic rainwater (SPLP, MEp) or carbonated water. Leaching (Sakamoto, USA, Switzerland, and USEPA S W-924) » Synthetic rainwater leaching tests are often used to measure heavy metal solubility and compare it to state and federal standards for groundwater and surface water, where materials and waste can be Reuse in situ or in a manner other than a lining landfill. Suitable acetic acid leaching tests include the Toxicity Characteristic Leaching Procedure (TCLp) described in the USEPA s w_846 manual and the Extractive Toxicity Test (ΕΡτ〇χ) currently used in Canada. Briefly, in the Toxicity Characteristic Leaching Procedure (TCLP) test, 1 负 of the composite sample is minus 3/8 of the gram, and the size of the waste is 2000 ml of dilute acetic acid (TCLp fluid #2) or buffered acetic acid (TCLP). Fluid #1) In the tumbling drum (end-over-tumbler), when 33 is in contact with 1M. The TCLp method (#1 or (7) is measured by the digestion test described in TCLp USEPA Method 1311 minus 3/8, and the size of the waste is selected after relative verification. The TCLP Fluid 2 extraction solution is diluted with "ml glacial acetic acid in DI water" Prepared in straight cc. The TCLP Fluid 1 extraction solution was prepared by diluting 5.7 ml of glacial acetic acid with a mixture of 3 ml of 1 〇 equivalent concentration of sodium hydroxide in DI water to eight milliliters. The most dangerous material has Low alkali content and TrT n ^ m required TCLP fluid i, including the waste of the TCLP fluid 2 at the bottom of the incinerator. The initial pH of the Nanke family is often higher than 12_〇 unit and generally 1325795 with lime or strong test, Such as lime precipitator residues or to treat the main lime. ' w Suitable synthetic acid leaching tests include the synthetic sinking agents described in the US uspa SW_846 manual for the use of waste in addition to the leachate collection # u $(4) field. The leaching procedure (SPLP) and multiple. Jane 5, in the SPLP test, (10) grams of waste and 2GG0 ml of dilute nitric acid and sulfuric acid - flipped 1M, when
取溶液補足至PH值接近4.8以模擬密西西比州東西部之酸 雨水。膽為多重萃取程序，其在第—次萃取物使用TCLP 型測試，隨後進行^SPLP’所有測試報導浸出液值，且 因此s式圖量測廢料基質之擴散潛勢。 合適之碳酸水浸出測試包括曰本浸出浪m，其在保持 在PH 5.8至6·3的情況下將5〇公克複合廢料樣品於一 水中翻轉6小時，隨後離心並經G45微米過濾之後進行分 析。另-合適之C〇2飽和蒸館水方法為在兩⑺個連續之 2_nU水浴中使用⑽公克i立方公分之膠結廢料的瑞士 =。量測各水浴之重金屬及鹽之濃度且取平均值，隨後 與瑞士標準比較。 合適之檸檬酸浸出測試包括加州健康安全法規之第Μ :第6嶋節“環境健康，，中所述之加州廢料萃取測試 =Τ)β簡言之，在醫測試中，將5q公克廢料與_ 么克檸檬酸納溶液在1000 mi滾筒中一起翻轉則、時之一 段時間。接著在經45微米之玻璃珠過濾器過遽i〇〇mi來自 滾筒之等分試樣之後，藉由感應耦合電漿法（ICP)分析重 9 1325795 金屬濃度。 合適之氣味量度測試將包括經活性碳改質之樣品，其 具有由人員組所得氣味之比較嗅覺量度。 本發明特別關注及注意的是，在TCLP、SPLP、MEP、 CALWET、酸雨水及酸雨源地表水條件下及在試圖模擬稀酸 水浸出以測定焚化爐灰渣殘餘物之危險性之管制測試下， 包括 Ag、Ba、Se、Zn、As、Hg、Cd、Cr、以及 pb 之個別 重金屬基團及其組合之浸出。另外，需要降低由處理及穩 疋灰渣所產生之氣味，因為焚化爐灰渣之處理及穩定通常 係緊密靠近相鄰工業、商業及住宅區。在一特定狀況中， 焚化爐灰渣處理及穩定引起強烈氣味，其繼而導致向管制 者的申訴，且因此研發本發明用以降低氣味且允許進行穩 定化。 〜 本發明提供一種降低在TCLP、SPLP、MEP、CALj WET、 酸雨水及酸雨源地表水浸出條件下包括As、Hg、cd、cr、 Cu及Pb基團及其組合之材料或廢料之浸出性及減少該穩 疋化期間所產生之可感覺氣味的方法，該方法使用稀酸半 溶性填酸H合物（DCPDH) [CaHpG4 2H2晴末狀 “晶種”，此物質將經處理材料或廢料之重量增加降至最 低且允許立即進行經敎基質之處理及操作，而無需施用 /c, °無固化要求及相關的臨時儲存堆所需之重複處 理’且同時產生適合於挖掘機或裝載機裝載、卡車卸載及 陸地處置或立即再使用鋪展及虔實之自由流動且更具渗透 性之經穩定材料或廢料。本發明確認稀酸作為浸出流體之 10 1325795 用途，其中將向該等稀酸中添加DCPDH，且因此教示一種 稀酸半溶性穩定劑之用途。 與本發明不同，先前技術已教示藉由添加水溶性或以 水為主之物理封裝劑來穩定重金屬，且尚未能認知到不溶 於水或具有有限水溶性，而在稀乙酸（TCLp)、稀硫酸及 硝酸（SPLP/MEP)及稀擰檬酸（CALWET)中為半溶性或 可用性之穩定劑之價值，且未能提供具有降低氣味產生之 _ 穩定方法。特定言之 ’ CTHara ( 4,737,356 )及 Forrester (5,245，114及5,430,233 )教示需要向焚化爐灰渣、廢機動 車輛粉碎物及導線絕緣物廢料及焚化爐底渣中添加水溶性 磷酸鹽，其水溶性為至少5 gm/丨〇〇 ml，在較佳具體實例中 為100%水溶性磷酸，且其增加来自焚化爐灰渣之氣味。先 别技術中使用波特蘭水泥、石灰、水泥窯灰、碟酸及組合 之穩定方法，亦因為了代表穩定後處理及處置困難之化學 反應向穩定配方中添加水（組合或作為水溶性試劑之部分 φ 添加），而產生滲透性降低之基質或固體材料形式，然而， 本發明使用粉末狀DCPDH來降低金屬溶解度而不會顯著降 低廢料滲透性，不會形成水泥樣非自由流動之材料或廢 料，無需固化時間，不會發生水合作用及相關的材料及廢 料重里增加，無需固化貯料堆所需之重複材料及土壤處 理’從而允許直接進行經穩定材料或廢料之處理、裝載、 處置或再使用。粉末狀DCPDH半溶性晶種穩定方法以基本 原理操作，材料或廢料與DCPDH之間的充分濕潤稀酸環境 接觸及混合將在TCLP、SPLP、MEP或CALWET萃取容器 1325795The solution was made up to a pH of approximately 4.8 to simulate acid rain in the east and west of Mississippi. The biliary is a multiple extraction procedure that uses the TCLP type test in the first extraction, followed by all SPLP' tests to report the leachate value, and thus the s-pattern measures the diffusion potential of the waste matrix. A suitable carbonated water leaching test consists of a sputum leaching wave m which is inverted in a water for 6 hours while maintaining a pH of 5.8 to 6.3, followed by centrifugation and filtration after G45 micron analysis. . Another suitable C〇2 saturated steaming water method is to use (10) grams of i cubic centimeter of cemented scrap in two (7) consecutive 2_nU water baths. The concentrations of heavy metals and salts in each water bath were measured and averaged and subsequently compared to Swiss standards. A suitable citric acid leaching test includes the California Health and Safety Regulations: Section 6 “Environmental Health,” California Waste Extraction Test = Τ) β In short, in medical tests, 5q grams of waste is _ The gram of sodium citrate solution was flipped together in a 1000 mi roller for a period of time. Then, after passing through a 45 micron glass bead filter, the aliquot from the roller was inductively coupled. Electrochemical ICP (ICP) analysis weighs 9 1325795 metal concentration. Suitable odour metric tests will include activated carbon modified samples with a comparative olfactory measure of the odor obtained by the group of people. The present invention is particularly concerned and noted that TCLP, SPLP, MEP, CALWET, acid rainwater and acid rain source under surface water conditions and under the control test of attempting to simulate the dilute acid water leaching to determine the risk of incinerator ash residue, including Ag, Ba, Se, Zn, Leaching of individual heavy metal groups of As, Hg, Cd, Cr, and pb, and combinations thereof. In addition, it is necessary to reduce the odor generated by the treatment and stabilization of ash, because the treatment and stabilization of incinerator ash is usually Close to adjacent industrial, commercial, and residential areas. In a particular situation, incinerator ash disposal and stabilization cause a strong odor, which in turn leads to complaints to regulators, and thus the invention was developed to reduce odor and allow for stabilization ~ The present invention provides a material or waste material which reduces As, Hg, cd, cr, Cu and Pb groups and combinations thereof under surface water leaching conditions of TCLP, SPLP, MEP, CALj WET, acid rain water and acid rain source. Leachability and a method of reducing the sensible odor generated during the stabilization process, using a dilute acid semi-soluble acid-compound H compound (DCPDH) [CaHpG4 2H2 haw-like "seed", which will treat the material Or the weight increase of the waste is minimized and the handling and operation of the warp-knitted substrate is allowed immediately, without the need to apply /c, ° no curing requirements and the repetitive treatment required for the associated temporary storage piles' and at the same time produce suitable for excavators or Loader loading, truck unloading and land disposal or immediate reuse of spread and tamped free-flowing and more permeable stabilized materials or waste. The present invention confirms dilute acid as The use of fluid 10 1325795 in which DCPDH will be added to such dilute acids, and thus teaches the use of a dilute acid semi-soluble stabilizer. Unlike the present invention, the prior art has taught that by adding water soluble or water-based Physical encapsulant to stabilize heavy metals, and has not yet been known to be insoluble in water or have limited water solubility, but in dilute acetic acid (TCLp), dilute sulfuric acid and nitric acid (SPLP/MEP) and citrate (CALWET) The value of a semi-soluble or usable stabilizer and fails to provide a stable method for reducing odor generation. In particular, 'CTHara (4, 737, 356) and Forrester (5, 245, 114 and 5, 430, 233) teach the need for incinerator ash, waste maneuver Water-soluble phosphate is added to the vehicle pulverized material and the wire insulation waste and the incinerator bottom slag, and the water solubility is at least 5 gm/丨〇〇ml, and in a preferred embodiment is 100% water-soluble phosphoric acid, and the increase is from The smell of incinerator ash. The stabilization method of Portland cement, lime, cement kiln dust, dish acid and combination is also used in the prior art, and water is added to the stable formulation due to the chemical reaction which is difficult to handle and handle after stabilization (combination or as a water-soluble reagent) Part φ is added) to produce a matrix or solid material form with reduced permeability. However, the present invention uses powdered DCPDH to reduce metal solubility without significantly reducing waste permeability, and does not form cement-like non-free flowing materials or Waste, no curing time, no hydration and associated material and waste increase, no need to cure the repetitive materials and soil treatment required for the storage pile', allowing direct handling, loading and disposal of stabilized materials or waste materials Or use it again. The powdered DCPDH semi-soluble seed stabilization method operates on a basic principle, with a sufficiently wet dilute acid environment between the material or waste and DCPDH. Contact and mixing will be in TCLP, SPLP, MEP or CALWET extraction vessels 1325795
中發生。儘管目前尚不瞭解氣味降低之確切原因，但假定 氣味降低係由於充當由灰㈣產生之有機物及硫化物之吸 附劍的DCPDH之精細粉末及中性性質所致。用於預測浸出 潛勢之萃取方法均假定現場材料或廢料處置條件因酸雨水 或酸浸出液而經歷水合作用，且涉及一定程度的重金屬與 萃取流體在飽和環境中歷經一段最短時間的間歇混合，且 該水合作用可藉由萃取溶質添加及混合時期來模擬。 DCPDH晶種穩定方法因此利用管制萃取程序來允許穩定後 材料或廢料水合作用、重金屬與DCPDH之間的混合及濕潤 化學稀酸環境接觸。萃取測試因此充當稀酸攪拌槽反應 器’其向材料及廢料表面上之重金屬以及擴散至酸溶液中 者&供機會’以有充足的機會與DCPDH晶種接觸，DCPDH 晶種亦具有與稀酸可溶性及/或可用性重金屬形成表面活性 及/或可溶性礦物之潛勢。本發明者研究發現較低表面積非 粉末形式之DCPDH在降低重金屬溶解度方面不太有效，此 證實DCPDH之暴露表面積之表面積及半溶性對礦物形成潛 勢發揮重要作用。乾燥晶種技術之一獨特益處為可在現場 將SPLP、MEP、TCLP及CALWET萃取流體酸可溶性及粉 末狀DCPDH施用於廢料或材料並乾燥混合均勻，且因此使 該等穩定劑之測試樣品在萃取溶液中在重金屬存在下自由 翻轉或混合一段既定萃取時間。此非膠結且未反應之酸半 溶性DCPDH粉末表面混合極大地改良諸如pb、Cd、Cr、 Ni及As之重金屬進入磷酸鈣磷灰石表面之濕潤環境取代。 萃取裝置有效地使重金屬進入溶液中以及使一部分DCPDH 12 J325795 進入溶液中並且使剩餘dcpdh表面得以潤濕接觸且因此 提供目前溶液可溶性及溶液表面反應性重金屬優良的表面 取代、吸附及沈澱之機會。在此化學機制下，一部分或所 有穩定劑因酸溶液而在溶液中可用，且番么屈 儿里隻屬離子在溶液Happened in. Although the exact cause of the odor reduction is not known at present, it is assumed that the odor reduction is caused by the fine powder and neutral nature of DCPDH which acts as an adsorption sword for the organic matter and sulfide produced by ash (4). The extraction methods used to predict the leaching potential assume that the on-site materials or waste disposal conditions undergo hydration due to acid rain or acid leachate, and involve a certain degree of intermittent mixing of the heavy metal and the extraction fluid in a saturated environment for a short period of time, And the hydration can be simulated by extracting the solute addition and mixing period. The DCPDH seed stabilization method therefore utilizes a controlled extraction procedure to allow for stable post-material or waste hydration, mixing between heavy metals and DCPDH, and wet chemical acid environment contact. The extraction test thus acts as a dilute acid stirred tank reactor's heavy metals on the surface of the material and waste as well as diffused into the acid solution & opportunity to have sufficient opportunity to contact the DCPDH seed crystal, DCPDH seed crystals also have The potential for acid solubility and/or availability of heavy metals to form surface active and/or soluble minerals. The inventors have found that DCPDH in a lower surface area non-powder form is less effective in reducing the solubility of heavy metals, which confirms that the surface area and semi-solubility of the exposed surface area of DCPDH play an important role in mineral formation potential. One of the unique benefits of dry seeding technology is the ability to apply SPLP, MEP, TCLP, and CALWET extraction fluids to the waste or powdered DCPDH in the field and dry and mix evenly, and thus the test samples of the stabilizers are extracted. The solution is free to flip or mix for a given extraction time in the presence of heavy metals. The surface mixing of this non-cemented and unreacted acid semi-soluble DCPDH powder greatly improves the wet environment substitution of heavy metals such as pb, Cd, Cr, Ni and As into the calcium phosphate apatite surface. The extraction unit effectively introduces heavy metals into the solution and allows a portion of DCPDH 12 J325795 to enter the solution and allow the remaining dcpdh surface to be wet contacted and thus provides excellent surface substitution, adsorption and precipitation opportunities for solution solubility and solution surface reactive heavy metals. Under this chemical mechanism, some or all of the stabilizers are available in solution due to the acid solution, and only the ions in the solution are in solution.
t可用，其繼而取代及交換不溶性磷灰石志二L π久石表面上之鈣並與 穩定劑一起在酸溶液中沈澱。 ' 美國專利第5,202’033號描述-種使用固體廢料添加劑 與來自磷酸鹽、碳酸鹽及硫酸鹽來源之額外ρΗ控制劑之組 合來減少固體廢料之Pb TCLP浸出的原位方法。 美國專利第5,037,479號揭示一種處理含有不可接受含 量之TCLP Pb (諸如錯）之高度危險性廢料的方法其係藉 由將固體廢料與選自由氧化鎂、氫氧化鎂、反應性碳酸^ 及反應性碳酸鎂組成之群之緩衝劑及額外試劑混合，其中 該額外試劑為選自由三過磷酸鈣（TSP)、磷酸銨、磷酸二 知：磷硼心及金屬鐵組成之群的含有陰離子之酸或鹽。 美國專利第4,889,640號揭示一種處理TCLp危險性鉛 之方法及混合物，其係藉由將固體廢料與選自由反應性碳 酸鈣、反應性碳酸鎂及反應性碳酸鎂鈣組成之群之試劑混 合。 美國專利第4,652,381號揭示一種處理受電池廠廢料如 硫酸及重金屬污染之工業廢水之方法，其係藉由用碳酸 鈣、硫酸鈣、氫氧化鈣處理該廢水以完成重金屬分離。然 而，此方法不適用於固體廢料情形。 然而’與本發明不同，先前技術解決方案無一教示用 13 1325795 特定的稀酸半溶性乾燥粉末狀DCPDH晶種穩定含有一或多 種重金屬之含重金屬材料或廢料，同時亦形成適合於裝 載、運輸、處置及再使用之自由流動、更具滲透性之經穩 定基質’而不會產生水泥樣降低之滲透性及強度，且不會 帶來固化及相關的重複廢料處理的負擔，且不降低氣味的 方法。特定言之，先前技術未能教示酸半溶性及粉末狀 DCPDH晶種使得重金屬有目的地浸入管制萃取容器中且隨 後該等金屬取代至DCPDH表面上並與特定酸半溶量之 DCPDH —起在酸溶液中沈澱及形成錯合物的機制。 【發明内容】 發明摘述 本發明揭示一種含重金屬材料或廢料之穩定方法，其 係經由使材料或廢料與酸半溶性DCPDH粉末狀晶種接觸， 該晶種補充材料或廢料之浸出潛勢及所需自由流動及更具 滲透性之材料或廢料之處理特徵而無需水合作用、固化及 相關的額外廢料或材料臨時儲存'處理、運輸、處置成本， 且k供廢料氣味降低。本發明特別關注粉末狀DCPDH在管 制萃取程序期間藉由表面取代或藉由與酸半溶性DCpdh 一 起沈澱來提供重金屬穩定作用。DCPDH係以乾燥粉末狀化 學形態提供’且因此可與含重金屬材料在廢料產生之前， 諸如在液流中在產生淤泥之廢水設施中或在管道中在空氣 污染控制及灰渣收集裝置之前接觸，或在廢料產生之後在 材料收集裝置中或廢料堆中接觸。 14 1325795 預期粉末狀DCPDH可用於RCRA遵守行動，使得自廢 水設施、熔爐、焚化爐及其他設施產生之廢料或材料不超 過根據TCLP之TCLP危險性廢料標準，或用於CERCLA (Superfund )反應，其中將穩定劑添加至先前產生之廢料 堆中或儲存容器中。施用粉末狀DCPDH之較佳方法為在產 生含重金屬材料之場所及設施内管線内使用，且因此根據 RCRA被接受為完全封閉的槽内或豁免TCLP穩定方法而無 需RCRA Part B危險性廢料處理及儲存設施許可。 • 【實施方式】 詳細說明 全世界的環境法規，諸如由USEPA根據CAA、RCRA 及CERCLA頒布之法規，要求含重金屬廢料及材料製造者 以對環境安全且保護人類健康之方式處理該等材料及廢 料，並降低有害及毒性氣味之散發。回應於此等法規，環 境工程師及科學家已研發多種方法來控制重金屬及氣味散 發，其大多係經由施用化學品將材料及廢料之溶解度特徵 ® 轉變為低溶形式，從而通過浸出測試且使廢料可就地再使 用或在當地填埋場處置，而無需另外及較為昂貴的控制措 施，諸如設計為提供金屬穩定及藉由空氣稀釋、添加氣味 遮蔽劑或氣體破壞來提供氣味及散發降低之危險性廢料處 置填埋場或設施。科學家以往主要集中於諸如鉛、鎘、鉻、 砷及采之單一重金屬，因為此等重金屬曾經且仍然是土壤 中金屬污染之最重要物質。諸如含錯油漆、焚化爐灰清、 鑄造廠及工廠飛灰、廢機動車輛粉碎物及導線粉碎殘餘物 15 1325795 之材料及清理地點廢料，諸如電池酸液及 廢料，為主要的錯來源。然，，近來需要一種控= 料、廢水淤泥、粉碎器廢料、導線絕緣物、焚化爐飛灰、 焚化爐底渣、焚化爐混合灰渣、鑄造廠粉塵、鋼廠粉塵及 文巧染土壞中諸如As、Hg、Cd、Cr、Pb、Cu及其組合之 各種重金屬之氣味散發及浸出的控制方法，以符合關於氣 味之公害管制及TCLP以及SPLp、MEP、DI及其他意欲量 測現場條件下金屬消化時之浸出及/或溶解度之措施，該方 法係以快速、低操作者風險、低機械處理設備影響、低成 本、避免臨時儲存及固化時間以及允許就地或易地再使用 及在低於或處於對於壓實及處理而言最佳之水分含量下處 理之方式進行。 本發明揭示一種含重金屬材料或廢料之穩定方法及氣 味降低方法，其係經由使材料或廢料與粉末狀DCPDH酸半 溶性穩定劑接觸。DCPDH可有效地以乾燥粉末形式使用， 並且較大粒控顆粒具有較低有效性，且因此可與含重金屬 材料在廢料產生之前，諸如在液流中在產生廢水淤泥之工 廠中或在管道中在空氣污染控制及灰渣收集裝置之前接 觸’或在廢料產生之後在諸如料斗、放卸閥、運送機、鄧 普斯特爾罐（dumpster )或廢料堆之收集裝置中接觸。 DCPDH係以乾燥形式施用’從而使得經穩定材料及廢料仍 可適合於充填材料或鬆散處理且仍具有較低滲透性，從而 允許浸出液或水流傳輸。當將經穩定廢料或材料用作基底 填料、覆盍物、堤壞或工程填料時，水流傳輸變得重要及 16 1325795 必需，由此消除擋水或浸出液產生棲留水位作用。 酸半溶性粉末狀DCPDH乾燥晶種穩定方法降低在 TCLP、SPLP、猜、CAL術、m、雨水以及地表水浸出 條件下以及在如由英國、泰國、日本、瑞士、德國、瑞典、 荷蘭之廢料控制規定所界定之管制水萃取測試條件下及在 關於廢料連續浸出之美國核協會標準下来自廢料之氣味及 包括As、Hg、Cd、Cr、Pb及Cu基團及其組合之含重金屬 廢料之浸出性’其中使用酸半溶性乾燥化學粉末狀DCPDH “晶種，，將經處理廢料之重量增加降至最低且允許立即進 行經穩U質之處理及㈣^固化要纟5戈臨時储存所需 之重複處理，且產生適合於挖掘機或裝載機裝載、卡車卸 載及陸地處置或立即再使用鋪展及壓實之自由流動且更具 滲透性之經穩定材料或廢料。 〃 本發明提供一種降低在TCLP、SPLP、MEP、CAi^ WET、 酸雨水及酸雨源地表水浸出條件下廢料氣味及包括As、 Hg、Cd、Cr、Pb A Cu基團及其組合之材料或廢料之浸出 性的方法，其使用稀酸半溶性DCPDH粉末狀晶種此物質 將經處理材料或廢料之重量增加降至最低且允許立即進行 經穩定基質之處理及操作而無需施用水及混合，無固化要 求及相關的臨時儲存堆所需之重複處理，且同時產生適合 於挖掘機或裝載機裝载、卡車卸載及陸地處置或直接再使 用鋪展及壓實之自φ流動且更具滲透性t經穩定材料或廢 料。本發明確認稀酸作為浸出流體之用途，其中將向該等 稀酸中添加粉末狀DCPDH，且因此教示一種稀酸半溶性穩 17 1325795 定劑之用途。 與本發明不同，先則技術已教示藉由添加水溶性或以 水為主之物理封裝劑來穩定重金屬，且尚未能認知到不溶 於水，而在稀乙酸（TCLP )、稀硫酸及硝酸（spLp/MEp ) 及稀檸檬酸（CALWET)中可溶且具有表面可用性之粉末狀 DCPDH之價值。特定言之，〇，Hara( 4 737 356 )及⑹⑴如 (5,245，114 & 5,430,233 )教示需要向焚化爐灰潰、廢機動 車輛粉碎物及導線絕緣物廢料及焚化爐底渣中添加水溶性 磷酸鹽，其水溶性為至少5 gm/1〇〇 ml，在較佳具體實例中 為100。/。水溶性鱗酸，其增加氣味。先前技術中使用波特蘭 水泥、石灰、水泥窯灰、磷酸及組合之穩定方法亦因為 了代表穩定後處理及處置困難之化學反應向穩定配方中添 加水（組合或作為水溶性試劑之部分添加），而產生滲透 性降低之基質或固體材料形式’ ^而’本發明使用粉末狀 DCPDH來降低氣味及金屬溶解度而不會㈣降低或增加渗 透性’不會形成水泥樣非自由流動之材料或廢料，無需固 化時間不會發生水合作用及相關的材料及廢料重量增 加，無需固化貯料堆所需之重複材料及土壤處理，從而允 許直接進行經穩定材料或廢料之處理、裝載、處置或再使 用及緊密靠近住宅及商業區進行處理。粉末狀DCPDH酸半 溶性晶種穩定方法以基本原理操作，材料或廢料與粉末狀 DCPDH之間的充分濕潤稀酸環境接觸及混合將在TCLp、 SPLP、MEP或CALWET萃取容器中發生。用於預測浸出潛 勢之萃取方法均假定現場材料或廢料處置條件因酸雨水或 1325795 酸浸出液而經歷水合作用，且涉及一定程度的重金屬與萃 取流體在飽和環境中歷經一段最短時間的間歇混合，且該 水合作用可藉由萃取溶質添加及混合時期來模擬。粉末狀 DCPDH穩定方法因此利用管制萃取程序來允許穩定後材料 或廢料之水合作用、重金屬與粉末狀DCPDH晶種之間的混 合及濕潤化學稀酸環境接觸。萃取測試因此充當稀酸攪拌 槽反應器，其向材料及廢料表面上之重金屬以及擴散至酸 溶液中者提供機會，以有充足的機會與粉末狀DCPDH晶種 接觸，DCPDH晶種亦具有與稀酸可溶性及/或可用性之重金 屬形成表面活性及/或半溶性礦物之潛勢。粉末狀DCPDH 技術之一獨特益處為可在現場將SPLP、MEP、TCLP及 CALWET萃取流體酸半溶性粉末狀DCPDH施用於廢料或 材料並乾燥混合均勻，且因此使該等穩定劑之測試樣品在 萃取溶液中在重金屬存在下自由翻轉或混合一段既定萃取 時間。此非膠結且未反應之酸半溶性粉末狀DCPDH表面混 合極大地改良諸如Pb、Cd' Cr、及Cu之重金屬進入DCPDH 表面之濕潤環境中取代。萃取裝置有效地使重金屬進入懸 浮液溶液中以及使酸半溶性粉末狀DCPDH進入懸浮液及溶 液中，且因此提供目前溶液可溶性重金屬優良的表面取 代、吸附及沈澱之機會。在此化學機制下，一部分粉末狀 DCPDH因酸溶液而在溶液中可用，且重金屬離子在溶液中 可用，其繼而取代及交換不溶性DCPDH表面上之鈣並與某 些半溶性DCPDH —起在萃取酸溶液中沈澱。 預期粉末狀DCPDH及有效程度較低之精細顆粒 19 1325795 Η可用於RCRA遵守行動，使得自採礦作業廢水設 炫爐《化爐及其他設施產生之材料不超過根據 之適田TCLP危險性廢料標準，或用於Cercla(⑽d ) 反應，其中將穩定劑添加至先前產生且現在根冑rcra作 為危險性廢料預處置來管制之廢料堆或儲存容器_。施用 DCPDH之較佳方法為以粉末形式且在產生含重金屬材料之 場所及設施内管線内使用，且因此根據rcra被接受為完 全封閉的槽内或絡免TCLP穩定方法而無需RCRA Part b危 險性廢料處理及儲存設施許可。 視其他廢料處理要求，諸如強度、滲透性、氣味控制 及其他重金屬控制而定，DCPDH亦可與以下各物組合使 用.波特蘭水泥、水泥窯灰、石灰窯灰、石夕酸鹽、石灰、 白雲石石灰、氧化鎂、生石灰、磷酸鹽、石灰、硫酸鐵、 硫酸亞鐵、氯化鐵、鐵粉、鐵屑、氣化物、碳酸鹽、磷酸 一銨（MAP)、磷酸二銨（DAP)、過磷酸鈣（ssp)、三 過磷酸鈣（TSP)、六偏磷酸鹽（HMP)、多磷酸四斜、填 酸二鈣、磷酸三鈣、磷酸一鈣、磷岩、所有上述乾燥磷酸 鹽之粉末形式及其組合。在某些狀況中，可提供數種諸如 鐵、鋁及其他錯合劑之添加劑，其亦可提供錯合碟灰石或 低容解度礦物（諸如填氯錯礦、水碌鋁錯礦或麟硫鋁鐵礦） 之單步驟形成。穩定劑組合類型、尺寸、劑量率、接觸持 續時間及施用方式可針對各類型之含重金屬材料或廢料進 行設計。 儘管目前確切的穩定形成分子尚未知，但預期當重金 20 ^25795 ’、私末狀DCPDH穩劑在萃取分析期間在所用之萃取流 ，下接觸時，化合物開始經由分子取代、水性沈澱或 面吸附形成’諸如It磷灰石及金屬賴鹽錢物，其溶 ，於原先在材料或廢料中之重金屬元素或分子。特定 之As Hg、Pb、Cr、Cu & Cd進入鱗氣錯礦及約墙灰 f錯口及/或雙曰曰作用，最可能藉由在標準溫度及壓力下 在萃取器流體中將DCPDH添加至材料或廢料中發生。確切 參的氣味控制方法目前尚未知，但預期係由於DcpDH之吸附 本質及中性pH值範圍。亦可能是改變溫度及壓力可加速或 辅助礦物形成，但若需要限制成本及為可能因需要壓力及 溫度控制裝置及纟器而複雜化之選用場地為主之穩定操作 做準備，則對於本申請“言該等方法並未被視為最佳的。 合適穩定劑之實例包括但不限於粉末形式及各種精細 顆粒形式之麟酸二辦二水合物（DcpDH)。根據本發明之 方法，所用之DCPDH試劑量及所選擇之粒徑視多種因素而 _ 疋，包括與毒物學及地點環境控制目標相關之所需溶解度 降低潛勢、所需氣味控制、所需鑛物毒性及所需礦物形成。 已發現焚化爐底渣廢料中〇5重量％粉末狀DCPDH之量及 混合焚化爐灰渣中2.0重量％粉末狀DCPDH之量，足以達 成初始TCLPPb及TCLPPb& Cd穩定，使其分別低於5 〇 及1.0之RCRA限值並降低氣味。然而，前述内容並不意欲 排除DCPDH或與其他試劑（若需要）之組合之更高或更低 的用量’因為已證實廢料中大於2重量％DCPDH之量亦有 效’但成本較咼。以下實施例僅用於說明本發明，而並不 21 1325795 意欲藉此以任何方式限制本發明β 實施例1 在本實施例中’用不同量之磷酸（75〇/0 η3Ρ04 )及 DCPDH穩定垃圾焚化爐底渣，其中在TCLP萃取前進行〇 天樣品固化。隨後測試經穩定及未經穩定之灰渣之TCLP Pb、Cd、Cr及Cu及灰渣產物之可感覺氣味。根據危險廢 料 g 理系統（Hazardous Waste Management System);危險 廢料之識別與列表（Identification and Listing of Hazardous Waste );毒性特徵性修訂本（Toxicity Characteristict is available, which in turn replaces and exchanges the calcium on the surface of the insoluble apatite ergium L π 久石 and precipitates in an acid solution together with the stabilizer. U.S. Patent No. 5,202,033 describes an in situ process for reducing Pb TCLP leaching of solid waste using a combination of solid waste additive and additional pH control from phosphate, carbonate and sulfate sources. U.S. Patent No. 5,037,479 discloses a method of treating highly hazardous waste containing unacceptable levels of TCLP Pb (such as a fault) by reacting solid waste with magnesium oxide, magnesium hydroxide, reactive carbonic acid and reactivity. a buffer of a group consisting of magnesium carbonate and an additional reagent, wherein the additional reagent is an anion-containing acid selected from the group consisting of trisodium superphosphate (TSP), ammonium phosphate, phosphoric acid: boron boron core, and metallic iron salt. U.S. Patent No. 4,889,640 discloses a method and mixture for treating TCLp hazardous lead by mixing solid waste with a reagent selected from the group consisting of reactive calcium carbonate, reactive magnesium carbonate, and reactive calcium magnesium carbonate. U.S. Patent No. 4,652,381 discloses a method of treating industrial waste water contaminated with battery waste, such as sulfuric acid and heavy metals, by treating the waste water with calcium carbonate, calcium sulfate, or calcium hydroxide to complete heavy metal separation. However, this method does not apply to solid waste situations. However, unlike the present invention, none of the prior art solutions teach 13 1325795 specific dilute acid semi-soluble dry powdered DCPDH seed crystals to stabilize heavy metal-containing materials or wastes containing one or more heavy metals, and also form suitable for loading and transportation. , a free-flowing, more permeable, stable matrix that is disposed of and reused without the cement-like reduced permeability and strength, without the burden of curing and associated repeated waste disposal, without reducing odor Methods. In particular, prior art failed to teach acid semi-soluble and powdered DCPDH seed crystals such that heavy metals are purposefully immersed in a controlled extraction vessel and then the metal is substituted onto the DCPDH surface and is associated with a specific acid half-soluble DCPDH. The mechanism of precipitation and formation of a complex in an acid solution. SUMMARY OF THE INVENTION The present invention discloses a method for stabilizing a heavy metal-containing material or waste by contacting a material or waste with an acid semi-soluble DCPDH powdered seed crystal, the leaching potential of the seed supplement material or waste material and The free-flowing and more permeable material or waste handling characteristics without the need for hydration, solidification and associated additional waste or material temporary storage 'processing, transportation, disposal costs, and k for waste odor reduction. The present invention is particularly concerned with the fact that powdered DCPDH provides heavy metal stabilization by surface substitution during precipitation extraction procedures or by precipitation with acid semi-soluble DCpdh. DCPDH is provided in a dry powdered chemical form and can therefore be contacted with heavy metal-containing materials prior to waste generation, such as in a liquid stream in a sludge-producing wastewater facility or in a pipeline prior to air pollution control and ash collection devices, Or in the material collection device or in the waste pile after the waste is produced. 14 1325795 It is expected that powdered DCPDH can be used in RCRA compliance actions such that waste or materials from wastewater facilities, furnaces, incinerators and other facilities do not exceed TCLP hazardous waste standards according to TCLP, or for CERCLA (Superfund) reactions, Stabilizers are added to previously produced waste piles or storage containers. The preferred method of applying powdered DCPDH is in the production of pipelines containing heavy metal materials and in pipelines within the facility, and is therefore accepted as a completely closed tank according to RCRA or exempt TCLP stabilization methods without the need for RCRA Part B hazardous waste treatment and Storage facility license. • [Embodiment] Detailed description of environmental regulations worldwide, such as those issued by USEPA under CAA, RCRA and CERCLA, requiring manufacturers of heavy metal scrap and materials to treat such materials and waste in a manner that is environmentally safe and protects human health. And reduce the emission of harmful and toxic odors. In response to these regulations, environmental engineers and scientists have developed a variety of methods to control heavy metals and odour emissions, mostly by applying chemicals to convert the solubility characteristics of materials and wastes into low-soluble forms, thereby passing leaching tests and making waste available. Reuse in situ or at a local landfill without additional and more expensive controls, such as designing to provide metal stability and dilution by air, addition of odor masking or gas damage to provide odour and reduce the risk of emission Waste disposal of landfills or facilities. In the past, scientists have focused on single heavy metals such as lead, cadmium, chromium, arsenic and mining, as these heavy metals were and still remain the most important substances in metal pollution in the soil. Materials such as mis-paints, incinerator ash, foundry and factory fly ash, waste motor vehicle pulverized material and wire pulverization residue 15 1325795 and cleaning site waste, such as battery acid and waste, are the main source of error. However, recently, there is a need for a control material, wastewater sludge, pulverizer waste, wire insulation, incinerator fly ash, incinerator bottom slag, incinerator mixed ash, foundry dust, steel mill dust, and dirty soil. Control methods for odor emission and leaching of various heavy metals such as As, Hg, Cd, Cr, Pb, Cu and combinations thereof to comply with toxic pollution control and TCLP and SPLp, MEP, DI and other intended field conditions The leaching and/or solubility measures of the lower metal digestion, which are fast, low operator risk, low mechanical processing equipment, low cost, avoiding temporary storage and curing times, and allowing for local or easy reuse and It is carried out below or in a manner that is processed at the optimum moisture content for compaction and processing. The present invention discloses a method for stabilizing a heavy metal-containing material or waste material and a method for reducing gas odor by contacting a material or waste with a powdery DCPDH acid semi-soluble stabilizer. DCPDH can be effectively used in the form of a dry powder, and larger granules have lower effectiveness and can therefore be used with heavy metal containing materials prior to waste generation, such as in a liquid stream in a plant that produces wastewater sludge or in a pipeline. The air pollution control and ash collection device are in contact with 'either before or after the waste is generated in a collection device such as a hopper, dump valve, conveyor, dumpster or waste stack. The DCPDH is applied in a dry form so that the stabilized material and waste can still be adapted to the filling material or loosely treated and still have a lower permeability, thereby allowing the leachate or water stream to be transported. When stabilized waste or materials are used as base packing, coverings, dikes or engineered packing, water transport becomes important and 16 1325795 is necessary, thereby eliminating the retention of water or leachate from the water level. Acid semi-soluble powdered DCPDH dry seed stabilization method reduces waste in TCLP, SPLP, guess, CAL, m, rain and surface water leaching conditions as well as in waste such as the United Kingdom, Thailand, Japan, Switzerland, Germany, Sweden, and the Netherlands Under the controlled water extraction test conditions defined by the Control Regulations and under the American Nuclear Society standards for continuous leaching of waste materials, the odours from waste and heavy metal-containing wastes including As, Hg, Cd, Cr, Pb and Cu groups and combinations thereof Leachability 'In which the acid semi-soluble dry chemical powdered DCPDH "seeds are used, the weight gain of the treated waste is minimized and the treatment of the stabilized U is allowed immediately and (4) curing is required for temporary storage of 5 Ge The process is repeated and produces a free flowing and more permeable stabilized material or waste suitable for excavator or loader loading, truck unloading and land disposal or immediate reuse of spreading and compaction. 〃 The present invention provides a reduction in Odors of waste materials including As, Hg, Cd, Cr, Pb A Cu groups and their surface leaching conditions under TCLP, SPLP, MEP, CAi^ WET, acid rainwater and acid rain source A method of leaching the material or waste using a dilute acid semi-soluble DCPDH powdered seed which minimizes the weight increase of the treated material or waste and allows immediate handling and handling of the stabilized substrate without application Water and mixing, no curing requirements and repetitive treatment required for associated temporary storage reactors, and at the same time produce φ flow suitable for excavator or loader loading, truck unloading and land disposal or direct reuse of spreading and compaction More permeable t stabilized material or waste. The present invention recognizes the use of dilute acid as a leaching fluid in which powdered DCPDH will be added to the dilute acid, and thus teaches the use of a dilute acid semi-soluble stable 17 1325795 formulation Unlike the present invention, the prior art has taught to stabilize heavy metals by adding water-soluble or water-based physical encapsulants, and has not yet been known to be insoluble in water, but in dilute acetic acid (TCLP), dilute sulfuric acid and The value of powdered DCPDH that is soluble and has surface availability in nitric acid (spLp/MEp) and dilute citric acid (CALWET). In particular, 〇, Hara (4 737 356) and (1) If (5,245,114 & 5,430,233) teaches the need to add water-soluble phosphate to the incinerator ash, waste motor vehicle pulverized material and wire insulation waste and incinerator bottom slag, the water solubility is at least 5 gm / 1 〇 〇ml, in a preferred embodiment, is 100% water-soluble tartaric acid which increases odor. The prior art uses Portland cement, lime, cement kiln ash, phosphoric acid and a combination of stabilization methods because of the representative stability Handling and Disposing of Difficult Chemical Reactions Adding water (in combination or as part of a water-soluble reagent) to a stable formulation results in a reduced permeability matrix or solid material form. The present invention uses powdered DCPDH to reduce odor and Metal solubility without (4) reduced or increased permeability 'will not form cement-like non-free-flowing materials or waste, no curing time will not occur hydration and related materials and waste weight increase, no need to solidify the storage pile Repetitive materials and soil treatment to allow direct handling, loading, disposal or reuse of stabilized materials or waste materials and close proximity Residential and commercial areas for processing. The powdered DCPDH acid semi-soluble seed stabilization process operates on a fundamental principle, and a sufficiently wet dilute acid environment contact and mixing between the material or waste material and the powdered DCPDH will occur in the TCLp, SPLP, MEP or CALWET extraction vessel. The extraction methods used to predict the leaching potential assume that the on-site materials or waste disposal conditions are subject to hydration due to acid rain or 1325795 acid leachate, and involve a certain degree of intermittent mixing of heavy metals and extraction fluids in a saturated environment for a short period of time. And the hydration can be simulated by extracting the solute addition and mixing period. The powdered DCPDH stabilization method thus utilizes a controlled extraction procedure to allow for hydration of stabilized materials or waste, mixing between heavy metals and powdered DCPDH seeds, and contact with a wet chemically dilute acid environment. The extraction test thus acts as a dilute acid stirred tank reactor that provides opportunities for heavy metals on the surface of materials and waste as well as for diffusion into acid solutions, with sufficient opportunity to contact the powdered DCPDH seeds, and DCPDH seeds are also The acid soluble and/or usable heavy metals form the potential of surface active and/or semi-soluble minerals. One of the unique benefits of powdered DCPDH technology is the ability to apply SPLP, MEP, TCLP, and CALWET extraction fluid acid semi-soluble powdered DCPDH to waste or materials in the field and dry and mix evenly, and thus the test samples of these stabilizers are extracted. The solution is free to flip or mix for a given extraction time in the presence of heavy metals. This non-cemented and unreacted acid semi-soluble powdered DCPDH surface mixture greatly improves the substitution of heavy metals such as Pb, Cd'Cr, and Cu into the wet environment of the DCPDH surface. The extraction unit effectively allows heavy metals to enter the suspension solution and the acid semi-soluble powdered DCPDH into the suspension and solution, and thus provides an excellent opportunity for surface replacement, adsorption and precipitation of solution soluble heavy metals. Under this chemical mechanism, a portion of the powdered DCPDH is available in solution due to the acid solution, and heavy metal ions are available in solution, which in turn replaces and exchanges calcium on the surface of the insoluble DCPDH and extracts acid from some semi-soluble DCPDH. Precipitate in solution. It is expected that powdered DCPDH and the less effective fine particles 19 1325795 Η can be used for RCRA compliance actions, so that the materials produced by the furnaces and other facilities from the mining operation wastewater do not exceed the TCLP hazardous waste standards according to the field. Or for use in a Cercla ((10)d) reaction in which a stabilizer is added to a waste heap or storage container previously produced and now controlled by the rcra as a pre-disposal of hazardous waste. A preferred method of applying DCPDH is in powder form and in the production of pipelines containing heavy metal materials and in pipelines within the facility, and thus is accepted as a completely closed tank or TCLP stabilization method according to rcra without the need for RCRA Part b hazard Waste treatment and storage facility permits. Depending on other waste disposal requirements, such as strength, permeability, odour control and other heavy metal controls, DCPDH can also be used in combination with Portland cement, cement kiln dust, lime kiln dust, lime mud, lime. , dolomite lime, magnesia, quicklime, phosphate, lime, ferric sulfate, ferrous sulfate, ferric chloride, iron powder, iron filings, vapors, carbonates, monoammonium phosphate (MAP), diammonium phosphate (DAP) ), superphosphate (ssp), trisodium superphosphate (TSP), hexametaphosphate (HMP), polyphosphate tetraclinate, dicalcium phosphate, tricalcium phosphate, monocalcium phosphate, phosphate rock, all of the above dried phosphoric acid The powder form of the salt and combinations thereof. In some cases, several additives such as iron, aluminum and other complexing agents may be provided, which may also provide mismatched discite or low-reactivity minerals (such as chlorine-filled ore, Shuilu aluminum ore or Lin). Sulphiite is formed in a single step. The type, size, dosage rate, duration of contact, and mode of application of the stabilizer combination can be designed for each type of heavy metal containing material or waste. Although the exact stable formation molecules are not known at present, it is expected that when heavy gold 20 ^ 25795 ', cryptic DCPDH stabilizer is used in the extraction stream used during the extraction analysis, the compound begins to undergo molecular substitution, aqueous precipitation or surface adsorption. Forming 'such as It's apatite and metal lysate, which dissolves in heavy metal elements or molecules originally in materials or waste. The specific As Hg, Pb, Cr, Cu & Cd enters the scale gas and the wall ash and/or the double enthalpy effect, most likely by DCPDH in the extractor fluid at standard temperature and pressure. Adding to material or scrap occurs. The exact odour control method is currently unknown, but is expected to be due to the adsorption nature of DcpDH and the neutral pH range. It may also be that changing the temperature and pressure may accelerate or assist in the formation of minerals, but if it is necessary to limit the cost and prepare for the stable operation that may be complicated by the need for pressure and temperature control devices and devices, then this application is for this application. "These methods are not considered to be optimal. Examples of suitable stabilizers include, but are not limited to, powdered forms and various fine particle forms of linonic acid dihydrate (DcpDH). According to the method of the present invention, The amount of DCPDH reagent and the selected particle size depend on a number of factors, including the desired solubility reduction potential associated with toxicological and site environmental control objectives, desired odour control, desired mineral toxicity, and desired mineral formation. It was found that the amount of 5% by weight of powdered DCPDH in the bottom slag waste of the incinerator and the amount of 2.0% by weight of powdered DCPDH in the mixed incinerator ash were sufficient to achieve the initial TCLPPb and TCLPPb& Cd stability, respectively, below 5 〇 and 1.0 RCRA limit and reduced odor. However, the foregoing is not intended to exclude higher or lower amounts of DCPDH or combinations with other reagents (if needed). Since it has been confirmed that the amount of greater than 2% by weight of DCPDH in the waste is also effective 'but the cost is relatively low. The following examples are merely illustrative of the invention, and 21 2125795 is not intended to limit the invention in any way. In the examples, 'different amounts of phosphoric acid (75〇/0 η3Ρ04) and DCPDH were used to stabilize the waste incinerator bottom slag, wherein the celestial sample was solidified before TCLP extraction. Then the TCLP Pb with stable and unstabilized ash was tested. , Cd, Cr and Cu and the odor of ash products. According to Hazardous Waste Management System; Identification and Listing of Hazardous Waste; Toxic Characteristic Revision (Toxicity Characteristic
Revisions) ’ 55 Fed· Reg. 26,986 ( 1990 年 6 月 29 日）（擬 編在 40 C.F.R. pt 261、264、268、271 及 302)(其以引用 的方式併入本文中）中所述之TCLP程序萃取樣品。在藉由 icp分析之前消化浸出液。磷酸鹽混合物形成具有低於2〇 PSI無側限強度之適合於陸地處置、通過油漆過濾測試之自 由流動性灰漬。樣品氣味藉由將灰渣與不同含量之活性碳 混合且隨後由一組9名人員感覺氣味來測試。藉由將平均 氣味感覺指數乘以33且得到〇至99之最大氣味指數來計 算各樣品之氣味指數。指數數值越低，小組人員所遇到的 氣味就越強。 表1 穩定劑劑量（％) 0 0.4% H3P〇4 TCLP Cd/Pb/Cr/As (ppm)氣味程度 0.148/8.03/0.23/0.005 35.3 (基線） 0.140/0.80/0.48/0.036 31.5 (最大氣味） 22 1325795 69.2 (最小氣味） 0.4%粉末狀 DCPDH 0.09/0.73/<0.〇!/<〇.〇1 表1中之上述結果容易地確立本發明方法用以乾燥穩 定金屬’從而降低浸出性及氣味，同時亦產生適合於處理 及處置之廢料而無需固化時間的操作性。根據如表1中所 提供之粉末狀及精細顆粒DCPDH使重金屬穩定及降低氣味 之有效性，據信等同於低於1重量％含重金屬材料或廢料之 量的粉末狀DCPDH應為有效的。 • 雖然已參考本發明之較佳具體實例特定展示及描述本 發明’但熟習此項技術者應瞭解可在不背離如所附申請專 利範圍所界定之本發明之精神及範疇的情況下對其作出多 種形式及細節上的修改。 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） 23Revisions) '55 Fed. Reg. 26,986 (June 29, 1990) (TCLP as described in 40 CFR pt 261, 264, 268, 271, and 302), which is incorporated herein by reference. The program extracts the sample. The leachate was digested prior to analysis by icp. The phosphate mixture forms a free-flowing gray stain suitable for terrestrial disposal, tested by paint filtration, having an unconfined strength of less than 2 〇 PSI. The sample odor was tested by mixing the ash with varying amounts of activated carbon and then feeling the odor by a group of nine people. The odor index of each sample was calculated by multiplying the average odor sensation index by 33 and obtaining a maximum odor index of 〇 to 99. The lower the index value, the stronger the scent encountered by the team. Table 1 Stabilizer dose (%) 0 0.4% H3P〇4 TCLP Cd/Pb/Cr/As (ppm) Odor degree 0.148/8.03/0.23/0.005 35.3 (baseline) 0.140/0.80/0.48/0.036 31.5 (maximum odor) 22 1325795 69.2 (minimum odor) 0.4% powdered DCPDH 0.09/0.73/<0.〇!/<〇.〇1 The above results in Table 1 readily establish the method of the invention for drying stable metals' thereby reducing leaching Sexuality and odour, while also producing workability suitable for disposal and disposal without the need for curing time. Powdered DCPDH, which is believed to be equivalent to less than 1% by weight of heavy metal-containing material or waste, should be effective in accordance with the effectiveness of powdered and fine-grained DCPDH as provided in Table 1 to stabilize heavy metals and reduce odor. The present invention has been particularly shown and described with respect to the preferred embodiments of the present invention, but it is understood by those skilled in the art that the invention can be practiced without departing from the spirit and scope of the invention as defined by the appended claims. Make changes in various forms and details. [Simple description of the diagram] (None) [Description of main component symbols] (None) 23