201238646 六、發明說明： 【發明所屬之技術領域】 本發明是關於一種含重金屬的固態物的處理方法。 【先前技術】 在用焚燒爐焚燒一般廢棄物或工業廢棄物等的情況 下，會產生燃燒廢氣等。由於燃燒廢氣中含有有害的氣化 氫或硫氧化物等酸性氣體，因此需要用熟石灰等進行鹼處 理。此外，燃燒廢氣中含有飛灰等含重金屬的固態物，在 該含重金屬的固態物中可能含有鉛、鎘、砷、硒、鉻等重 金屬。由於這類重金屬會從含重金屬的固態物中溶出而污 杂土壤等，因此需要對含重金屬的固態物實施防溶出處 理。 例如，在專利文獻1中記載了下述處理方法，用熟石 灰處理燃燒廢氣中的酸性氣體，用黏結劑（)、螯 合劑、磷酸等重金屬固定劑使從燃燒廢氣中回收到的飛灰 等不溶解。 此外，在專利文獻2和專利文獻3中，作為用來降低 裒兄負擔的有效方法，5己載了利用碳酸氫鈉對酸性氣體進 行處理的方法。 用碳酸氫鈉處理燃燒廢氣時，會從燃燒廢氣中所含有 的飛灰等含重金屬的固態物中溶出六價鉻。在專利文獻4 中，記載有如下方法，從用碳酸氫鈉處理好的酸性氣體中 201238646 回收飛灰，添加磷酸系化合物和 金屬。 二價鐵鹽處理飛灰中的 重 現有技術文獻 專利文獻 專利文獻1 專利文獻2 專利文獻3 專利文獻4 發明内容】 日本專利特開平9-9921 5號公報。 日本專利特表平9-5 0 76 54號公報。 曰本專利特開2000-2 1 8 1 28號公報。 日本專利特開2006-1 1 0423號公報。 疋基於某些理由，現有方法難以充分防止從含 重金屬的固態物中溶出六價鉻。 鑒於上述問題，本發明的目的在於提供一種能夠更加 抑制含重金屬的固態物中六價鉻的溶出，該含重金屬的固 態物是從用碳酸氫鈉等碳酸氫鹽處理了的燃燒廢氣中回 收得到的。 現有技術中一直認為磷酸化合物是有用成分，但本發 月人發現其會妨礙二價鐵鹽的作用，終於完成了本發明。 具體地說，本發明提供以下方案。 (1)含重金屬的固態物的處理方法，該方法包括將 3有鉻化合物的含重金屬的固態物與含有二價鐵鹽的處 理劑進行混合的步驟，在與該處理劑混合前的該含重金屬 的固恶物，是從用碳酸氫鹽處理了的燃燒廢氣中回收的， 201238646 该處理劑中不含有鱗酸化合物。 ^ ( 2 )如（1 )所述的處理方法，該含重金屬的固態物 來自於從該燃燒廢氣中回收到的灰渣。 該二價鐵鹽換 鉻含量的摩爾 (3 )如（1 )或（2 )所述的處理方法， 鼻成鐵的量與該含重金屬的固態物中的總 比為5〜52:1 。 (4) 如⑴〜（3)任意一項所述的處理方法，該處 理劑中的鎂化合物換算成鎂的含量，相對於該含重金屬的 固態物中的總鉻含量的摩爾比為小於30 (包括〇) I。 (5) 如（4)所述的處理方法，該處理劑不含有鹼劑。 (6 )如（1 )〜（5 )任意一項所述的處理方法，該二 、鐵I選自氯化亞鐵、硫酸亞鐵及它們的水合物中的一種 以上。 基於本發明’由於處理劑中不含有填酸化合物，因此 a 。更加抑制從含重金屬的固態物中溶出六價鉻該含重 的固態物是從用碳酸氫鹽處理的燃燒廢氣中回收得 到的。 【實施方式】 本發明的處理 的固態物與後述處 (處理劑） 方法包括將含有鉻化合物的含重金 理劑混合的步驟。201238646 VI. Description of the Invention: [Technical Field] The present invention relates to a method for treating a solid material containing heavy metals. [Prior Art] When general waste or industrial waste is incinerated in an incinerator, combustion exhaust gas or the like is generated. Since the combustion exhaust gas contains harmful acid gas such as vaporized hydrogen or sulfur oxide, it is necessary to carry out alkali treatment with slaked lime or the like. Further, the combustion exhaust gas contains a solid material containing heavy metals such as fly ash, and the heavy metal-containing solid material may contain heavy metals such as lead, cadmium, arsenic, selenium, and chromium. Since such heavy metals are eluted from solid materials containing heavy metals to contaminate soils and the like, it is necessary to carry out a dissolution prevention treatment on solid materials containing heavy metals. For example, Patent Document 1 describes a treatment method in which acid gas in a combustion exhaust gas is treated with slaked lime, and fly ash recovered from combustion exhaust gas is not used by a heavy metal fixing agent such as a binder (), a chelating agent, or phosphoric acid. Dissolved. Further, in Patent Document 2 and Patent Document 3, as an effective method for reducing the burden on the brothers, 5 has carried out a method of treating acid gas with sodium hydrogencarbonate. When the combustion exhaust gas is treated with sodium hydrogencarbonate, hexavalent chromium is eluted from a heavy metal-containing solid such as fly ash contained in the combustion exhaust gas. Patent Document 4 describes a method of recovering fly ash from 201238646 in an acid gas treated with sodium hydrogencarbonate, and adding a phosphoric acid compound and a metal. The weight of the ferrous iron salt in the fly ash is a prior art. Patent Document Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 SUMMARY OF THE INVENTION Japanese Patent Laid-Open No. Hei 9-9921 No. 5-. Japanese Patent Publication No. 9-5 0 76 54. Japanese Patent Laid-Open No. 2000-2 1 8 1 28. Japanese Patent Laid-Open No. 2006-1 1 0423. For some reasons, existing methods are difficult to adequately prevent the dissolution of hexavalent chromium from solids containing heavy metals. In view of the above problems, an object of the present invention is to provide a method for further suppressing the elution of hexavalent chromium in a solid material containing heavy metals which is recovered from combustion exhaust gas treated with hydrogencarbonate such as sodium hydrogencarbonate. of. The phosphoric acid compound has been considered to be a useful component in the prior art, but it has been found in the present invention that it interferes with the action of the divalent iron salt, and the present invention has finally been completed. Specifically, the present invention provides the following scheme. (1) A method for treating a solid material containing a heavy metal, which comprises the step of mixing a solid material containing a heavy metal having a chromium compound with a treating agent containing a ferrous salt, and the mixture before mixing with the treating agent The solid and solid matter of heavy metals is recovered from the combustion exhaust gas treated with bicarbonate. 201238646 The treatment agent does not contain scaly acid compounds. (2) The treatment method according to (1), wherein the heavy metal-containing solid material is derived from ash recovered from the combustion exhaust gas. The molar ratio of the divalent iron salt to the chromium content (3) is as described in (1) or (2), and the total ratio of the amount of the nasal iron to the solid content of the heavy metal is 5 to 52:1. (4) The treatment method according to any one of (1) to (3), wherein the molar ratio of the magnesium compound to the magnesium content in the treatment agent relative to the total chromium content in the heavy metal-containing solid is less than 30 (including 〇) I. (5) The treatment method according to (4), wherein the treatment agent does not contain an alkali agent. (6) The treatment method according to any one of (1) to (5), wherein the iron I is one or more selected from the group consisting of ferrous chloride, ferrous sulfate, and a hydrate thereof. Based on the present invention, since the treating agent does not contain an acid-filling compound, a is. It is further suppressed that the hexavalent chromium is eluted from the heavy metal-containing solid, and the heavy solid is recovered from the combustion waste gas treated with hydrogencarbonate. [Embodiment] The solid matter to be treated of the present invention and the method (treatment agent) described later include a step of mixing a heavy metal-containing agent containing a chromium compound.
二價鐵鹽。處理劑中的二價鐵 本發明中的處理劑含有 201238646 鹽將含重金屬的固態物所含有的钦几人Λ « I 3名的絡化合物中的六價鉻還 原成無害的三價鉻。在現有方法中，π η主你mλ ^ , 巧刀/ίΓ甲’冋時使用磷酸化合物 和二價鐵鹽作為重金屬的處理劊，伯丄，么π 丄 人 处主削但如後所述，磷酸化合 物會阻礙二價鐵鹽的藥劑效果伯β ., 又禾但疋’在本發明中，通過 使用不含磷酸化合物的處理劑，能豹 、王月】此夠防止阻礙二價鐵鹽的 藥劑效果。 [磷酸化合物] 將在燃燒設備中產生的烬焯麻 J u凡曆軋用石厌酸虱鈉等碳酸 氫鹽處理後回收含重金屬的固態物，該含重金屬的固態物 易溶出六價鉻'汞等重金屬。在現有方法中，Θ時使用磷 西文化s物和一價鐵鹽作為這類重金屬的處理劑。但是，基 於本發明人的研究結果發現，處理劑中的磷酸化合物與二 4貝鐵鹽反應，生成磷酸亞鐵Fe^p〇^2等化合物，減少二 價鐵鹽相對於含重金屬的固態物中六價鉻的有效利用 里，阻礙二價鐵鹽的藥劑效果。只要是按照現有方法，盔 論是添加磷酸化合物與二價鐵鹽的混配產品，還是分別添 加磷酸化合物和二價鐵鹽，均會產生上述問題。 在本發明中，通過使用不含磷酸化合物的處理劑（但 包含在處理劑中不可避免地混入極少量磷酸化合物的情 况），旎夠抑制由磷酸化合物引起的對二價鐵鹽及鎂化八 物的藥劑效果的阻礙。據此，與現有方法相比，通過少量 的二價鐵鹽量’就能夠對含重金屬的固態物中的鉻化合物 6 201238646 進行處理。 [二價鐵鹽]Divalent iron salt. The ferrous iron in the treating agent The treating agent in the present invention contains 201238646 salt. The hexavalent chromium in the complex compound of the I3 group contained in the heavy metal-containing solid material is reduced to harmless trivalent chromium. In the existing method, π η is the main m λ ^ , and the knives are used as the treatment of heavy metals, and the π π 丄 处 主 主 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但 但The phosphoric acid compound hinders the effect of the agent of the divalent iron salt. In addition, in the present invention, by using a treatment agent containing no phosphate compound, Leopard, Wang Yue can prevent the ferrous salt from being blocked. Pharmacy effect. [Phosphate compound] The solid material containing heavy metals is recovered by treating the castor, which is produced in the combustion equipment, with bicarbonate such as sodium sulphate, and the solid material containing heavy metals is easily soluble in hexavalent chromium. Heavy metals such as mercury. In the prior art, a phosphorus culture and a monovalent iron salt are used as a treatment agent for such heavy metals. However, based on the findings of the present inventors, it was found that the phosphoric acid compound in the treating agent reacts with the di-Beibei iron salt to form a compound such as ferrous phosphate Fe^p〇^2, which reduces the divalent iron salt relative to the heavy metal-containing solid matter. In the effective use of hexavalent chromium, the effect of the ferrous iron salt is hindered. The above problem arises as long as it is according to the existing method, whether the addition of a phosphoric acid compound and a divalent iron salt, or the addition of a phosphoric acid compound and a divalent iron salt, respectively. In the present invention, by using a treatment agent containing no phosphoric acid compound (but in the case where a very small amount of a phosphate compound is inevitably mixed in the treatment agent), it is possible to suppress the bis-valent iron salt and the magnesiumation caused by the phosphoric acid compound. Obstruction of the effect of the drug. Accordingly, the chromium compound 6 201238646 in the heavy metal-containing solid can be treated by a small amount of divalent iron salt amount as compared with the prior art. [divalent iron salt]
作為二價鐵鹽沒有特別F 艮制’可例舉氣化亞鐵、硫酸亞 鐵，以及它們的水合物等。 二價鐵鹽的性狀沒有牲 卡特別限制，可以是粉末、漿液或 液體等。從容易處理的&1#十< 用度來看，優選為液體。 如前所述，由於處现<*,丨丄 齊j中不含有填酸化合物，因此即 使二價鐵鹽量不過多，士 执各 也此夠處理含重金屬的灰渣。因 此，以含重金屬的灰渣為〗所曰 —马1 〇〇貝$ %計，換算成鐵的量為 3質量。/。以下’優選為2質量％以下。 該二價鐵鹽換算成鐵的量與含重金屬的固態物中的總 鉻含量的摩爾比為5〜52:1。據此 ^ J兄刀抑制六價鉻 專重金屬的溶出。 [其他成分] 由於本發明中的含重金屬的固態物是 又用石反酸虱鹽 處理的燃燒廢氣中回收到的，因此，七☆ 夕絮^情'、只 處理劑中不含有鹼劑’也能夠充分扣 '下，即使 制重金屬的、> 此，使用不含有鹼劑的處理劑經濟會 的溶出。因 具惠。但是， 屬的固態物的驗性弱的情況下，或在 含重金 東金屬含旦、 況下，可能會從含重金屬的固態物中A 1過多的情 ’谷出錯、 止這種溶出，也可以與二價鐵鹽同 ，。為了防 , 守追用鹼劑。 作為驗劑’如果是具有提高含重The ferrous iron salt is not particularly F-made, and examples thereof include gasified ferrous iron, ferrous sulfate, and hydrates thereof. The trait of the divalent iron salt is not particularly limited, and may be a powder, a slurry or a liquid. From the viewpoint of ease of handling &1#10<>, it is preferably a liquid. As mentioned above, since the acid <*, j j j does not contain an acid-filling compound, even if the amount of ferrous iron salt is not excessive, the slag can handle the heavy metal-containing ash. Therefore, the amount of iron converted into iron is 3 masses based on the ash containing heavy metals. /. The following ' is preferably 2% by mass or less. The molar ratio of the amount of iron in the divalent iron salt to the total chromium content in the solid metal-containing solid is 5 to 52:1. According to this, ^J brother knife inhibits the dissolution of hexavalent chromium heavy metals. [Other Ingredients] Since the heavy metal-containing solid matter in the present invention is recovered from the combustion exhaust gas treated with the stone sulphate salt, the VII ^ ^ 、 、 、, only the treating agent does not contain the alkali agent It is also possible to sufficiently deduct the metal, even if it is made of a heavy metal, >, it is economical to use a treatment agent containing no alkali agent. Because of the benefits. However, in the case of weak physical properties of the genus, or in the case of containing heavy gold, the metal may contain too much A 1 from the heavy metal-containing solids, and this dissolution is also caused. It can be the same as the ferrous salt. In order to prevent, use the alkali agent. As an examination, if it has an increased weight
金屬的固態物的pHThe pH of the solid metal
S 7 201238646 的作用’則沒有特別限制 面考慮’優選鎮化合物等 但從pH緩衝作用 的穩定性方 氧化鎮等中的—種以上。氧化…如…化鎭、氫 化鎂和氧氣化鎂能夠接古人 金屬的固態物的pH，且且 ^含重 〆、有緩衝pH的功能 屬的固態物的PH在9 5~1() ς & 使3重金 在9.5 10.5的程度，因此優選。 鎂化合物的性狀沒有特別 液體等。 了 Λ為私末、漿液或 相對於δ亥含重金屬的固 鎂化合物換算成鎂的含量優 果錢化合物的含量在該範圍 鹽導致的pH降低效果。 態物中的總鉻含量，處理劑中 選為小於30 (包括〇) :1。如 内，則能夠充分抑制由二價鐵 此外，處理燃燒廢氣中 丈用的奴酸虱鈉等的添加量多 的情況下’在含重舍属的[5!作 、口也物中可能會殘留大量的鹼性 成分。這種情況下，可以齟士 , /、本七明中的處理劑並用中和劑。 作為這種中和密丨丨，你丨與女& 例舉有虱化鋁、聚合氯化鋁、鹽酸、 硫酸紹等。由於這此φ知亦I丨你 (含重金屬的固態物） 、士 T和劑便宜，因此優選。 作為3重金屬的固態物，如果是含有鉻的含重金屬的 固態物’就沒有特別㈣，可以是在廢棄物焚燒爐（灰炫 融爐、氣化熔融爐、工業廢棄物焚燒爐等）、纟化爐、燃 木屑鍋爐 '發電鍋爐、煉鋼電爐等焚燒、熔融設備等的燃 8 201238646 燒設備中產生的含重金屬的灰渣。具體地說，可例舉從廢 氣處理设備中產生的版灰’或者氣體處理殘渣、煤塵等。 飛灰是在燃燒爐、炫融爐等中，利用袋式過濾器（bag filter )、電集塵器等從燃燒廢氣中回收到的灰渣；氣體處 理殘潰是HCM、SOx等氣體與Ca(〇H)2、NaHC03等氣體 處理劑反應後的反應產物。 本發明的含重金屬的固態物是從用碳酸氫鈉等碳酸 氩鹽處理了的燃燒廢氣中回收到的。通過分析含重金屬的 固態物中的成分（例如，碳酸氫根離子），蓉定該含重金 屬的固態物是否是從利用碳酸氫鹽處理了的燃燒廢氣中 回收到的。 在上述含重金屬的灰渣中，本發明中的灰渣優選來自 於從燃燒廢氣中收集到的灰渣（即，飛灰）。飛灰中含有 特別多的六價鉻等重金屬’通過本發明方法能夠令人滿意 地進行處理。所謂的「來自於灰渣」可以是從燃燒廢氣中 收集到的灰渣這一種成分，也可以是在含有從燃燒廢氣中 收集到的灰渣的同時，還含有其他成分（例如，在處理燃 燒廢氣時使用的處理劑中的成分等）。 作為本發明的含重金屬的灰渣，優選為p_鹼度為5〇 以下的含重金屬的灰渣，或者是P_酸度為〇以上的含重 金屬的灰渣，進一步優選為P_鹼度為20以下的含重金屬 的灰潰。當P-鹼度或p_酸度在上述範圍内時，能夠在抑 201238646 制從含重金屬的灰渣中溶出鉻和汞等的同時， 的二價鐵鹽發揮作用，因此優選。從處理劑中 化合物的需要量減少的角度來看，含重金屬 p -驗度，但可能不能徹底抑制鉻和采等的溶it P -驗度是表示含重金屬的灰渔中未反應 分的鹼度指標。P-鹼度是指加入與含重金屬的 比在10 0以上的純水，擾拌，滴加指示劑（香 滴加1/50N-硫酸水溶液，當顏色從紫色變為 酸滴定量（單位：m g - a s，C a C Ο 3 / g -灰潰）。 P-酸度是表示含重金屬的灰渔中的酸性 指標。P-酸度是指加入與含重金屬的灰渣的質 以上的純水，擾拌後，滴加指示劑（盼酞)，然後 氫氧化鈉水溶液，當顏色從紫色變為無色時的 定量（單位：mg-as，CaC03/g-灰潰）。 含重金屬的固態物中的重金屬含量，在按 法進行前處理後，通過測定在該前處理過程中 中的各種重金屬的含量，換算為每單位試樣 量，從而得出。濾液中的各種重金屬的含量是 量）試樣加入时禍中，添加適量的水、硝酸、 加熱濃縮，接著，加熱溶解後過濾，用原子吸 定過渡後的濾、液。 在飛灰等含重金屬的固態物中，可含有杳 使處理劑中 為驗劑的鎂 的灰渣優選 5 ° 的熟石灰成 灰渣的質量 分酞），然後 無色時的硫 成分的酸度 '量比在1 0 0 滴加1/5 0N-氫氧化納滴 照底質調查 製成的濾液 質量中的含 將數克（適 鹽酸等後， 收光譜法測 古、鎖、坤、 10 201238646 硒、鉻等重金屬。通過操縱含重金屬的固態物的pH，能 夠防止這些重金屬的部分或全部溶出。 另一方面，當錯、鑛、石中、碼、鉻等的量過多時，也 存在難以完全抑制溶出的情況。例如，如果固態物中錯的 量為4000mg/kg以下，則能夠很好地抑制鉛的溶出。同 樣地，如果固態物中鎘的量為4〇mg/kg以下，則能夠很 好地抑制鎘的溶出。 (處理劑的混合方法） 向含重金屬的固態物中混合處理劑的方法沒有特別 限定，但例如可以使用批次處理式混煉機、連續混煉機 等，向飛灰等含重金屬的固態物中同時添加處理劑和少量 水，進行混煉。 此外’從防止飛灰等飛散的角度來看，優選在飛灰和 加濕水的混煉步驟中混合處理劑。 通過本發明方法處理後的含重金屬的固態物可進行 填埋處理等。此外，也可以通過將該含重金屬的固態物的 重金屬進订穩定處理，用作路基材、回填材等資材。 實施例 基於以下貫施例，對本發明進行詳細說明，但本發明 並不限於此。 (含重金屬的固態物試樣） 在動床式Ά化炫融爐中，向燃燒廢氣中添加微粉碳 201238646 酸氣納（商品名：〜心寸―b-200,平均粒徑8//m， 八::株式έ社生產），對醆性氣體進行鹼處理。將鹼 處理後的《I體通人袋式過濾器，採集筛檢程式表面上收集 到的飛灰。進行兩次上述過程’將得到的飛灰用作含重金 屬的固態物試樣。 .;各忒樣在彳女妝底質調查法進行前處理，然後測 定在該前處理過程中製成的濾液中的各種重金屬的含 量，換算為每單位試樣質量中的含量，求出各試樣中的重 金屬的3里。濾液中的各種重金屬的含量是通過將數克 (適里）§式樣加入坩堝中，添加適量的水、硝酸、鹽酸等 後，加熱濃縮，接著’加熱溶解後過濾，用原子吸收光譜 法測疋過濾後的濾液，從而得出。並且，總鉻（)、 船、録、汞、妈和鈉的測定，按照工業廢水試驗法 (JISK-0 1 02 )進行測定，汞按照日本環境廳59號公告進 行測定。結果如表1所示。 飛灰 編號 T-Cr Pb Cd Hg As Se Ca Na (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) 1 201 2980 36 3.6 17 3 90900 144000 2 254 3700 33 0.89 16 5 95200 145000 (實施例和比較例） 向各試樣中添加的處理劑如表2所示。「32%FeCl2」 表示3 2 %氣化亞鐵水溶液（「了 7シa十4卜T- 1 0 1」（栗 田工業株式會社生產））。「FeS04_7H20」表示99%硫酸亞 12 201238646 鐵.7水合物「ns試劑特級」（和光純藥工業株式會社生 產）。「75%H3P04」表示75%磷酸水溶液「7 Vシ二十彳 卜 R-3 03」（栗田工業株式會社生產）。此外，作为 32%FeCl2 与 75%H3P〇4 的混配物（9: 1 )，使用「7 v シ二 十彳卜RT-1 09」（栗田工业株式会社）。以下，表中的「％」 表示「質量％」。 表2 試驗名 飛灰編號 處理劑 實施例1 1 32% FeCl2水溶液 實施例2 2 32% FeCl2水溶液 實施例3 1 FeS04-7H20 比較例1 1 無添加 比較例2 2 無添加 比較例3 1 添加32%FeCl2和75%H3P〇4的混配物（9:1) 比較例4 2 添加32%FeCl2和75%H3P〇4的混配物（9:1 ) 比較例5 1 分別添加 32%FeCl2 和 75%H3P〇4 比較例6 1 分別添加 FeS04 7H20 和 75%H3P〇4 求出各處理劑中含有的二價鐵鹽的量、換算成鐵的 量、構酸化合物的量及換算成構的量。其結構如表3和4 所示。並且，「添加量」表示每單位質量的各試樣中，添 加的藥劑質量。 表3 試驗名 添加 量 (%) 32%FeCl2 FeS04-7H20 Fe添加量 75%H3P〇4 P添加量 Fe/T-Cr (%) (%) (%-asFe ) (%) (%-asP) 摩爾比 1 1.0 - 0.14 - - 7 2 2.0 - 0.28 - - 13 實施例 3 3.0 - 0.42 - - 20 1 4 4.0 - 0.56 - - 26 5 5.0 - 0.70 - - 33 8 8.0 - 1.13 - - 52The action of S 7 201238646 is not particularly limited. It is preferably a kind of a compound or the like which is preferably a town compound or the like, but is stable from a pH buffering action, or the like. Oxidation... such as phlegm, magnesium hydride and magnesium oxymagide can pick up the pH of the solid metal of the ancient metal, and the pH of the solid matter containing the heavy 〆, buffered pH is 9 5~1() ς &; make 3 heavy gold at the level of 9.5 10.5, so it is preferred. The properties of the magnesium compound are not particularly liquid or the like. The content of the magnesium compound in the smear, the slurry or the solid metal relative to the δ hai heavy metal is converted into a magnesium salt in this range. The total chromium content in the state is selected to be less than 30 (including 〇):1 in the treating agent. In the case of the ferrous iron, the addition of the bismuth sulphate and the like in the combustion exhaust gas can be sufficiently suppressed. A large amount of alkaline components remain. In this case, it is possible to use a neutralizing agent in the treatment of the gentleman, /, and Benqiming. As such a neutralizing secret, you and the female & exemplified are bismuth aluminum, polyaluminum chloride, hydrochloric acid, sulphate and the like. Since this φ knows that you (the heavy metal-containing solid matter), the T and the agent are cheap, it is preferable. As a solid material of a triple heavy metal, if it is a solid material containing heavy metals containing chromium, there is no special (four), but it can be in a waste incinerator (ash ash melting furnace, gasification melting furnace, industrial waste incinerator, etc.), 纟Incineration of furnaces, wood-fired boilers, power generation boilers, steel-making electric furnaces, etc., burning, melting equipment, etc. 8 201238646 Burning equipment containing heavy metal-containing ash. Specifically, the ash ash or the gas treatment residue, coal dust, and the like which are generated from the exhaust gas treatment equipment can be exemplified. Fly ash is a ash that is recovered from combustion exhaust gas by a bag filter or an electric dust collector in a combustion furnace, a smelting furnace, etc.; the gas treatment is a gas such as HCM or SOx and Ca (〇H)2, a reaction product after the reaction of a gas treating agent such as NaHC03. The heavy metal-containing solid material of the present invention is recovered from combustion exhaust gas treated with an argon carbonate such as sodium hydrogencarbonate. By analyzing the components of the heavy metal-containing solid (e.g., bicarbonate ions), it is determined whether the heavy metal-containing solid matter is recovered from the combustion exhaust gas treated with hydrogencarbonate. In the above heavy metal-containing ash, the ash in the present invention is preferably derived from ash (i.e., fly ash) collected from the combustion exhaust gas. The fly ash contains a particularly large amount of heavy metals such as hexavalent chromium, which can be satisfactorily processed by the method of the present invention. The so-called "from ash" may be a component of ash collected from combustion exhaust gas, or may contain ash collected from combustion exhaust gas, and may contain other components (for example, in processing combustion). A component in the treatment agent used in the exhaust gas, etc.). The heavy metal-containing ash of the present invention is preferably a heavy metal-containing ash having a p_basicity of 5 Å or less, or a heavy metal-containing ash having a P-acidity of 〇 or more, and more preferably a P_ alkalinity. A ash-crush containing heavy metals below 20. When the P-basicity or the p-acidity is in the above range, it is preferable to dissolve the chromium and mercury in the heavy metal-containing ash from 201238646, and the divalent iron salt acts. From the point of view of the reduction in the amount of the compound in the treatment agent, the heavy metal p-test degree, but may not completely inhibit the dissolution of chromium and the like, and the P-test is a base indicating the unreacted fraction of the heavy metal-containing ash fish. Degree indicator. P-alkalinity means adding pure water with a ratio of heavy metals containing more than 100%, disturbing, adding an indicator (scented with 1/50N-sulphuric acid aqueous solution, when the color changes from purple to acid titration (unit: Mg - as,C a C Ο 3 / g - ash collapse. P-acidity is an acidity indicator in ash fishing containing heavy metals. P-acidity refers to the addition of pure water above the mass of ash containing heavy metals. After the disturbance, add the indicator (predicted), then the aqueous sodium hydroxide solution, when the color changes from purple to colorless (unit: mg-as, CaC03/g-ash collapse). Solids containing heavy metals The heavy metal content is obtained by measuring the content of various heavy metals in the pretreatment process after conversion according to the method, and converting to the amount per unit sample, thereby obtaining the content of various heavy metals in the filtrate. When the sample is added, add an appropriate amount of water, nitric acid, and heat to concentrate. Then, heat and dissolve, filter, and aspirate the filtered liquid after the transition. In a heavy metal-containing solid such as fly ash, the ash of the magnesium which is the test agent in the treatment agent is preferably a mass fraction of ash of 5 ° of slaked lime, and then the acidity of the sulfur component in the absence of color Compared with the drop of 1/5 0N-sodium hydroxide in the bottom of the sediment, the quality of the filtrate will be several grams (after the appropriate hydrochloric acid, etc., the spectroscopy method is used to measure the ancient, lock, kun, 10 201238646 selenium Heavy metals such as chromium, etc. By manipulating the pH of solids containing heavy metals, some or all of these heavy metals can be prevented from being dissolved. On the other hand, when the amount of wrong, ore, stone, code, chromium, etc. is too large, it is difficult to completely In the case where the amount of the solid in the solid is 4000 mg/kg or less, the elution of lead can be satisfactorily suppressed. Similarly, if the amount of cadmium in the solid is 4 〇 mg/kg or less, The cadmium is eluted well. (Method of mixing the treating agent) The method of mixing the treating agent into the heavy metal-containing solid is not particularly limited. For example, a batch processing type kneader, a continuous kneader, or the like may be used. Fly ash, etc. In the solid matter, a treatment agent and a small amount of water are simultaneously added and kneaded. Further, from the viewpoint of preventing scattering of fly ash or the like, it is preferred to mix the treatment agent in the kneading step of fly ash and humidified water. The processed heavy metal-containing solid material may be subjected to landfill treatment, etc. Further, the heavy metal containing the heavy metal-containing solid material may be subjected to a stable treatment to be used as a material for a road substrate, a backfill, etc. The embodiment is based on the following The present invention will be described in detail, but the present invention is not limited thereto. (Solid sample containing heavy metal) In the moving bed type smelting and melting furnace, fine powder carbon 201263846 sour gas is added to the combustion exhaust gas (product Name: ~ heart inch - b-200, average particle size 8 / / m, 8:: produced by the company, the alkali treatment of the inert gas. After the alkali treatment, the "I body pass bag filter, The fly ash collected on the surface of the screening program is collected. The above process is carried out twice. The obtained fly ash is used as a solid sample containing heavy metals. Each sample is pretreated in the prostitute survey method. Then determine the pretreatment The content of various heavy metals in the filtrate prepared in the process is converted into the content per unit mass of the sample, and 3 parts of the heavy metal in each sample is obtained. The content of various heavy metals in the filtrate is determined by a few grams (suitable )) § The pattern is added to the crucible, adding appropriate amount of water, nitric acid, hydrochloric acid, etc., and then heating and concentrating, followed by 'heating and dissolving, filtering, and measuring the filtrate after filtration by atomic absorption spectrometry, and thus, total chromium ( Determination of ship, record, mercury, mother and sodium, according to the industrial wastewater test method (JISK-0 1 02), mercury is measured according to the Japanese Environmental Agency No. 59. The results are shown in Table 1. The fly ash number T-Cr Pb Cd Hg As Se Ca Na (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) 1 201 2980 36 3.6 17 3 90900 144000 2 254 3700 33 0.89 16 5 95200 145000 (Examples and Comparative Examples) The treating agents added to the respective samples are shown in Table 2. "32% FeCl2" indicates a 32% aqueous ferrous solution ("7シa10 4 Bu T-1 1 1" (produced by Kurida Industry Co., Ltd.)). "FeS04_7H20" means 99% sulfuric acid sub- 12 201238646 iron.7 hydrate "ns reagent grade" (produced by Wako Pure Chemical Industries, Ltd.). "75% H3P04" is a 75% phosphoric acid aqueous solution "7 V シ 彳 彳 R R-3 03" (produced by Kurita Industrial Co., Ltd.). In addition, as a compound (9:1) of 32% FeCl2 and 75% H3P〇4, "7 v シ 彳 彳 RT RT-1 09" (Kurita Industrial Co., Ltd.) was used. Hereinafter, "%" in the table indicates "% by mass". Table 2 Test name Fly ash number treatment agent Example 1 1 32% FeCl2 aqueous solution Example 2 2 32% FeCl2 aqueous solution Example 3 1 FeS04-7H20 Comparative Example 1 1 No addition Comparative Example 2 2 No addition Comparative Example 3 1 Add 32 Mixture of %FeCl2 and 75%H3P〇4 (9:1) Comparative Example 4 2 Addition of 32% FeCl2 and 75% H3P〇4 (9:1) Comparative Example 5 1 Add 32% FeCl2 and 75% H3P〇4 Comparative Example 6 1 FeS04 7H20 and 75% H3P〇4 were added, respectively, and the amount of the divalent iron salt contained in each treatment agent, the amount of iron converted, the amount of the acid-forming compound, and the conversion structure were determined. the amount. Its structure is shown in Tables 3 and 4. Further, the "addition amount" indicates the mass of the drug added per sample per unit mass. Table 3 Test name addition amount (%) 32% FeCl2 FeS04-7H20 Fe addition amount 75% H3P〇4 P addition amount Fe/T-Cr (%) (%) (%-asFe) (%) (%-asP) Molar ratio 1 1.0 - 0.14 - - 7 2 2.0 - 0.28 - - 13 Example 3 3.0 - 0.42 - - 20 1 4 4.0 - 0.56 - - 26 5 5.0 - 0.70 - - 33 8 8.0 - 1.13 - - 52
S 13 201238646 實施例 2 1 1.0 - 0.14 - - 5 2 2.0 - 0.28 - - 10 3 3.0 - 0.42 - - 15 4 4.0 - 0.56 - - 21 5 5.0 - 0.70 - - 26 8 8.0 - 1.13 - - 41 實施例 3 - - 2.0 0.40 - - 19 表4 試驗名 添加 量 (%) 32%FeCl2 (%) FeS04 7H20 (%) Fe添加量 (%-asFe) 75%H3P〇4 (%) P添加量 (%-asP) Fe/T-Cr 摩爾比 比較例 1 - - - - - - - 比較例 2 - - - - - - - 比較例 3 1 0.9 - 0.13 0.1 0.02 6 2 1.8 - 0.25 0.2 0.05 12 3 2.7 - 0.38 0.3 0.07 18 4 3.6 _ 0.51 0.4 0.09 24 5 4.5 - 0.63 0.5 0.11 29 8 7.2 - 1.01 0.8 0.18 47 比較例 4 1 0.9 - 0.13 0.1 0.02 5 2 1.8 - 0.25 0.2 0.05 9 3 2.7 - 0.38 0.3 0.07 14 4 3.6 - 0.51 0.4 0.09 19 5 4.5 - 0.63 0.5 0.11 23 8 7.2 - 1.01 0.8 0.18 37 比較例 5 - 0.9 - 0.13 0.1 0.02 6 - 1.8 - 0.25 0.2 0.05 12 - 2.7 0.38 0.3 0.07 18 3.6 0.51 0.4 0.09 24 - 4.5 - 0.63 0.5 0.11 29 - 7.2 - 1.01 0.8 0.18 47 比較例 6 - - 2.0 0.40 0.2 0.05 19 向各5 0 g試樣中添加規定量的處理劑，接著，添加相 14 201238646 對於各試樣20°/。的純水（該純水相當於加入混煉機的加濕 水）’在室溫下用小鏟混煉約5分鐘。 混煉後’將得到的混煉物作為實施了本發明處理的灰 渣（以下，稱為「處理灰」），按照日本環境廳13号公告 試驗（4 )法，實施溶出試驗。本試驗是將5〇g處理灰加 入到1L I乙稀製谷器中’加入5 0 0 m 1純水（固液比： L/S=10 ) ’用震盪機震盪6小时後，用濾紙「GS_25」（孔 徑，ADVANTEC ( 7卜，八y于v夕）東洋株式會社 生產）抽濾，將過濾出的濾液作为溶出液，分析该溶出液 中的重金屬並且，按照工業廢水試驗法（jisk-o 1 ) 測疋溶出液的pH、溶出液中的六價鉻、斜及鑛的含量， 按照曰本環境廳59號公告分析溶出液中的汞含量。該分 析結果如表5及6所示。 表5 PH Cr6+ Pb Cd He - (mg/L) __(mg/L) (mg/L') A A6 (mff/L ^ 填埋處理 基準值 - <1.5 <0.3 <0.3 V lllg/ J <0.005 10.6 0.9 <0.05 <0.05 0 0010 10.6 0.6 <0.05 <0.05 0.0008 實施例1 10.5 0.4 <0.05 <0.05 <0 0005 10.5 0.3 <0.05 <0.05 <0 0005 10.4 <0.2 <0.05 <0.05 <〇 0005 10.2 <0.2 <0.05 <〇.〇5 <Ω OOOS 10.7 1.3 <0.05 <0.05 <0 0005 10.7 1.0 <0.05 <0.05 <0 0005 實施例2 10.6 0.6 <0.05 <0.05 <0 0005 10.6 0.4 <0.05 <0.05 <〇 0005 10.5 0.3 <0.05 <0.05 <0.0005 10.2 <0.2 <0.05 <0 〇5 <〇 000S 實施例3 10.6 0.4 ^ <0.05 <0.05 0.0006 15 201238646 表6 PH Cr6+ Pb Cd Hg - (mg/L) (mg/L) (mg/L ) (mg/L ) 填埋處理 基準值 - <1.5 <0.3 <0.3 <0.005 比較例1 10.7 4.6 <0.05 <0.05 0.0066 比較例2 10.9 6.7 <0.05 <0.05 0.0006 比較例3 10.7 2.5 <0.05 <0.05 0.0024 10.7 1.9 <0.05 <0.05 0.0017 10.6 1.4 <0.05 <0.05 0.0015 10.6 1.1 <0.05 <0.05 0.0014 10.5 0.8 <0.05 <0.05 0.0013 10.3 0.6 <0.05 <0.05 0.0010 比較例4 10.9 3.6 <0.05 <0.05 0.0005 10.8 2.3 <0.05 <0.05 0.0005 10.8 2.3 <0.05 <0.05 0.0006 10.7 1.5 <0.05 <0.05 0.0006 10.7 0.9 <0.05 <0.05 <0.0005 10.5 0.7 <0.05 <0.05 <0.0005 比較例5 10.7 2.2 <0.05 <0.05 0.0024 10.6 1.6 <0.05 <0.05 0.0015 10.5 1.3 <0.05 <0.05 0.0015 10.4 0.9 <0.05 <0.05 0.0012 10.4 0.7 <0.05 <0.05 0.0013 10.3 0.5 <0.05 <0.05 0.0007 比較例6 10.6 1.4 <0.05 <0.05 0.0012 如表5和6所示，基於本發明能夠對含重金屬的固態 物中的六價鉻、錯、録、汞等重金屬進行防溶出處理。 以上該僅為本發明之較佳實施例，並非用來限定本發 明之實施範圍；如果不脫離本發明之精神和範圍，對本發 明進行修改或者等同替換，均應涵蓋在本發明 申請專 利範圍的保護範圍當中。 【圖式簡單說明】 16 201238646 【主要元件符號說明】 益 ”》、S 13 201238646 Example 2 1 1.0 - 0.14 - - 5 2 2.0 - 0.28 - - 10 3 3.0 - 0.42 - - 15 4 4.0 - 0.56 - - 21 5 5.0 - 0.70 - - 26 8 8.0 - 1.13 - - 41 Example 3 - - 2.0 0.40 - - 19 Table 4 Addition amount of test name (%) 32% FeCl2 (%) FeS04 7H20 (%) Fe addition amount (%-asFe) 75% H3P〇4 (%) P addition amount (%- asP) Fe/T-Cr molar ratio Comparative Example 1 - - - - - - - Comparative Example 2 - - - - - - - Comparative Example 3 1 0.9 - 0.13 0.1 0.02 6 2 1.8 - 0.25 0.2 0.05 12 3 2.7 - 0.38 0.3 0.07 18 4 3.6 _ 0.51 0.4 0.09 24 5 4.5 - 0.63 0.5 0.11 29 8 7.2 - 1.01 0.8 0.18 47 Comparative Example 4 1 0.9 - 0.13 0.1 0.02 5 2 1.8 - 0.25 0.2 0.05 9 3 2.7 - 0.38 0.3 0.07 14 4 3.6 - 0.51 0.4 0.09 19 5 4.5 - 0.63 0.5 0.11 23 8 7.2 - 1.01 0.8 0.18 37 Comparative Example 5 - 0.9 - 0.13 0.1 0.02 6 - 1.8 - 0.25 0.2 0.05 12 - 2.7 0.38 0.3 0.07 18 3.6 0.51 0.4 0.09 24 - 4.5 - 0.63 0.5 0.11 29 - 7.2 - 1.01 0.8 0.18 47 Comparative Example 6 - - 2.0 0.40 0.2 0.05 19 A predetermined amount of the treatment agent was added to each of the 50 g samples, followed by the addition of the phase 14 201238646. 20 ° /. The pure water (this pure water is equivalent to the humidified water added to the mixer) was kneaded with a spatula at room temperature for about 5 minutes. After the kneading, the obtained kneaded product was used as the ash (hereinafter referred to as "treated ash") subjected to the treatment of the present invention, and the dissolution test was carried out in accordance with the Japanese Environmental Agency No. 13 publication test (4). In this test, 5 〇g of treated ash was added to a 1 L I ethyl gluten granulator. 'Add 500 mM of pure water (solid-liquid ratio: L/S=10)' After shaking with a oscillating machine for 6 hours, filter paper was used. "GS_25" (aperture, ADVANTEC (7b, yy), manufactured by Toyo Co., Ltd.) was suction filtered, and the filtered filtrate was used as an eluate to analyze heavy metals in the eluate and, according to the industrial wastewater test method (jisk -o 1 ) Measure the pH of the eluate, the hexavalent chromium in the eluate, the content of the smear and the ore, and analyze the mercury content in the eluate according to the publication of the Environmental Protection Agency No. 59. The analysis results are shown in Tables 5 and 6. Table 5 PH Cr6+ Pb Cd He - (mg/L) __(mg/L) (mg/L') A A6 (mff/L ^ Landfill treatment reference value - <1.5 <0.3 <0.3 V lllg/ J <0.005 10.6 0.9 <0.05 <0.05 0 0010 10.6 0.6 <0.05 <0.05 0.0008 Example 1 10.5 0.4 <0.05 <0.05 <0 0005 10.5 0.3 <0.05 <0.05 <0 0005 10.4 <0.2 < 0.05 < 0.05 < 〇 0005 10.2 < 0.2 < 0.05 < 〇. 〇 5 < Ω OOOS 10.7 1.3 < 0.05 < 0.05 < 0 0005 10.7 1.0 < 0.05 < 0.05 < 0 0005 Example 2 10.6 0.6 < 0.05 < 0.05 < 0 0005 10.6 0.4 < 0.05 < 0.05 < 〇 0005 10.5 0.3 < 0.05 < 0.05 < 0.0005 10.2 < 0.2 < 0.05 <0 〇5 <〇000S Example 3 10.6 0.4 ^ <0.05 <0.05 0.0006 15 201238646 Table 6 PH Cr6+ Pb Cd Hg - (mg/L) (mg/L) (mg/L) (mg/ L) Landfill treatment reference value - <1.5 <0.3 <0.3 <0.005 Comparative Example 1 10.7 4.6 <0.05 <0.05 0.0066 Comparative Example 2 10.9 6.7 <0.05 <0.05 0.0006 Comparative Example 3 10.7 2.5 < ;0.05 <0.05 0.0024 10.7 1.9 <0.05 <0.05 0.0017 10.6 1.4 <0.05 <0.05 0.0015 10.6 1.1 <0.05 <0.05 0.0014 10.5 0.8 <0.05 <0.05 0.0013 10.3 0.6 <0.05 <0.05 0.0010 Comparative Example 4 10.9 3.6 <0.05 <0.05 0.0005 10.8 2.3 <0.05 <0.05 0.0005 10.8 2.3 <0.05 <0.05 0.0006 10.7 1.5 <0.05 <0.05 0.0006 10.7 0.9 <0.05 <0.05 <0.055 10.5 0.7 <0.05 <0.05 <0.0005 Comparative Example 5 10.7 2.2 <0.05 <0.05 0.0024 10.6 1.6 <0.05 <0.05 0.0015 10.5 1.3 <0.05 <0.05 0.0015 10.4 0.9 <0.05 <0.05 0.0012 10.4 0.7 <0.05 <0.05 0.0013 10.3 0.5 <0.05 <0.05 0.0007 Comparative Example 6 10.6 1.4 <0.05 <0.05 0.0012 As shown in Tables 5 and 6, based on the present invention, it is possible to prevent dissolution of heavy metals such as hexavalent chromium, argon, and mercury in solids containing heavy metals. deal with. The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; the modifications and equivalents of the present invention are intended to be included in the scope of the present invention without departing from the spirit and scope of the invention. Within the scope of protection. [Simple description of the diagram] 16 201238646 [Description of main component symbols] Benefits",
S 17S 17