1243697 A7 ___ B7 __ 五、發明說明（丨） 本發明關於一種將重金屬氯化物作可廢棄處理方式的 處理的方法，該重金屬氯化物係在用氯化物程序製造二氧 化鈦時呈旋風塵形式產生，其中，首先從該拌和以水或酸 的旋風塵將不溶的成份分離，然後藉加入一種中和劑將溶 液的pH値升高到9〜12範圍，該重金屬呈氫氧化物形式 沉澱，將該呈污泥的方式的氫氧化物壓縮並進一步脫水。 在德國專利案DE 41 31 577 A1發表了一種此類的方 法。其中提到，用氯化物程序製造二氧化鈦時，如果在將 污泥中和之前未將旋風塵中也含有的惰性成份分離而係寧 可讓廢棄處理物的體積大得多並且連該旋風塵的可再使用 惰性成份也丟棄，則不可避免地要將產生的（重）金屬氯化 物 除了氯化鐵外--轉變成可廢棄處理的產物，且得 到一種可廢棄處理的濾渣。如果我們使用DE 41 31 577 A1 所述技術內容，則即使沒有惰性材料當作支持骨架，在溶 渣或熔渣/金紅石(Rutil)混合物(熔渣大部分當作使用的原料 )’則得到一種適合作廢棄處理的濾渣，其乾殘餘物在4〇 %以下，一般爲35 %。但是如果在氯化物程序時從天然的 或合成的金紅石著手，則在此習用的處理方法中，在污泥 脫水時乾殘餘物降到觸變性(Thixotropie)的界限以下：這 種濾渣不堪使用及不適作廢棄處理。 本發明的目的在於提供一種將鈦礦氯化時產生的重金 屬氯化物作經濟且大工程規模的處理的方法，特別是不受 來自旋風塵的原料影響地，在將該惰性成份分離後，要得 到一種可廢棄處理的產物，其乾殘餘物超過40 %。 本紙張尺度適用中國國家標準（CNS)A4規格（2ΐθ χ ^7公釐） (請先閱讀背面之注意事項再填寫本頁) --訂---------線邊 A7 B7 1243697 ___^ 五、發明説明（） 這種目的達成之道’係在程序進行時產生一種可良好 地過濾的膠羽（絮凝物)(Flocke)，這點可利用以下的改良方 法之一(或最好是這些改良方法的組合)達成： 在中和階段時將PH値調整到9〜12之前，先作一道快速 而均勻的預中和作業調到pH値6〜9的範圍。 在壓縮（濃縮)(Eindicken)之前，把一種膠羽化輔助劑( 宜爲陰離子性者)混入該帶有沉澱的金屬氫氧化物的懸浮液 中。 該污泥宜在一種薄膜壓機中脫水，過瀘器壓力宜超過 4巴，後壓機壓力宜超過10巴。利用這各種措施[這些措 施可個別地實施或組合使用]--不受該供入該氯化反應器 的原料影響地——可得到一種可廢棄處理的濾渣，其乾燥 殘餘物過40%重量，而不需用惰性物質作支持骨架。 本發明在以下利用圖式中例示並在以下詳細舉例說明 。圖式中： [圖式的簡單說明] 第1圖係一種用於處理旋風塵的方法示意圖。 (請先閱讀背面之注意事項再填寫本頁) -4^^^--I I I I--訂--------- [圖號說明] ⑴ 揮發性金屬氯化物 ⑺ 旋風 (3) 氣態的四氯化鈦 (4) 旋風塵 (5) 容器 (6) 水及/或酸性程序水 用中國國家標準（CNS)A4規格（210 X 297公釐） A7 1243697 _B7 五、發明說明（）） ⑺ 酸性的懸浮液 ⑻ 惰性的固體粒子 ⑼ 過濾器 (10) 溶液 (11) 攪拌器 (12) 預混合槽 (13) 中和槽 (14) 懸浮液 (15) 石灰乳 (16) 容器 (17) pH値調節裝置 (18) 濃縮器(沉降槽） (19) 污泥 (20) 泵 (21) 過濾壓機 (22) 第一成膠羽輔助劑 (23) 第二成膠羽輔助劑 (24) 容器 (25) 泵 (26) 濾渣 (請先閱讀背面之注意事項再填寫本頁) [實施例的說明] 在用氯化物程序製造二氧化鈦時，把在該氯化反應器 中形成揮發性金屬氯化物（1)冷卻到使得除了四氯化鈦外， 所有礦石-及焦碳粒子（它們呈濃縮的形式，且它們大多與 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 1243697 A7 __B7____ 五、發明說明（W) 該惰性成分未反應）在一道旋風(2)中分離。在這種溫度仍 呈氣態的四氯化鈦(3)(此處未圖示)在隨後冷凝，且留下的 氯化廢氣送到一個廢氣淨化裝置。在旋風中分離的固體混 合物稱爲「旋風塵」（4)。 當在一容器(5)中藉著加入水及/或酸性程序水(6)[該程 序水係在操作時產生者，且不需由於要使用在這裏而作繁 複的淨化作業]將該旋風塵拌合時，產生一種酸性的懸浮液 (7):所有的金屬氯化物都溶解，惰性的固體粒子(8)，焦炭 ，及未反應的礦石則保持不變且可進一步使用。它們可毫 無問題地一過濾器(9)中分離。 在此圖中略描述了本發明的方法，其中在溶液（10)中 的重金屬都不需選擇性地回收，所有重金屬離子都要當作 不能再利用的物質廢棄處理。它們藉中和轉變成金屬氫氧 化物。在這裏或許可在此位置將個別的離子或離子組(例如 鐵或釩)選擇性地分離。這種習知的方法步驟並不會妨礙或 改變本發明的方法，因此不作進一步的討論。 如果將該中和作業分成二個階段：一道「快速的」預 中和作業及一道後調整作業，則對於在此程序結束時所需 的脫水作業顯得特別有利。該快速的預中和作業在一個有 攪拌器（11)的預混合槽（12)中達成，如此，可使pH快速上 升，且在各空間及時間中都是均勻地上升，且即使在操作 過程有波動時，不會在任何部分體積中有晶核或膠羽的形 成作用在空間及時間上不是最適當者。在預中和作業中pH 値上升到6〜9。爲了作穩定化及細微調整，設有一個第二 — —______2______ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注咅？事項再填寫本頁)1243697 A7 ___ B7 __ V. Description of the invention (丨) The present invention relates to a method for treating heavy metal chlorides as a disposable treatment method. The heavy metal chlorides are produced in the form of cyclone dust when the titanium dioxide is produced by the chloride process, where First, the insoluble ingredients are separated from the mixed cyclone dust with water or acid, and then the pH of the solution is raised to the range of 9 ~ 12 by adding a neutralizing agent. The heavy metal is precipitated in the form of a hydroxide. The hydroxide of the sludge is compressed and further dehydrated. One such method is published in German patent case DE 41 31 577 A1. It was mentioned that when the titanium dioxide was produced by the chloride process, if the inert components also contained in the cyclone dust were not separated before neutralizing the sludge, the volume of the waste treatment material would be much larger and the cyclone dust may be connected. If the inert ingredients are reused and discarded, the (heavy) metal chlorides produced inevitably, in addition to ferric chloride, will be converted into disposable products and a disposable filter residue will be obtained. If we use the technical content described in DE 41 31 577 A1, even if there is no inert material as the supporting skeleton, in the slag or slag / rutile mixture (the slag is mostly used as the raw material), we get A kind of filter residue suitable for waste disposal, whose dry residue is below 40%, generally 35%. However, if starting with natural or synthetic rutile during the chloride process, in this conventional treatment method, the dry residue falls below the threshold of thixotropie when the sludge is dehydrated: this filter residue is unusable And not suitable for disposal. The purpose of the present invention is to provide a method for economically and large-scale treatment of heavy metal chlorides generated during the chlorination of titanium ore, especially without being affected by raw materials from cyclone dust. A disposable product was obtained with a dry residue of more than 40%. This paper size applies to China National Standard (CNS) A4 specification (2ΐθ χ ^ 7mm) (Please read the precautions on the back before filling this page)-Order ---------- Line Edge A7 B7 1243697 ___ ^ 5. Description of the invention () The way to achieve this purpose is to produce a well-filterable rubber plume (Flocke) during the process. This can be achieved by using one of the following improvement methods (or the most Fortunately, a combination of these improved methods) is achieved: Before the pH 値 is adjusted to 9 ~ 12 during the neutralization stage, a quick and uniform pre-neutralization operation is adjusted to the range of pH 値 6 ~ 9. Prior to compression (concentration) (Eindicken), a gel feathering aid (preferably anionic) is mixed into the suspension with the precipitated metal hydroxide. The sludge should be dewatered in a film press, the pressure of the translator should exceed 4 bar, and the pressure of the rear press should exceed 10 bar. Utilizing these various measures [these measures can be implemented individually or in combination]-without being affected by the raw materials supplied to the chlorination reactor-a disposable filter residue can be obtained, the dry residue of which exceeds 40% by weight , Without the need to use inert materials as a supporting framework. The present invention is exemplified in the following drawings and illustrated in detail below. In the drawings: [A brief description of the drawings] Figure 1 is a schematic diagram of a method for treating cyclone dust. (Please read the precautions on the back before filling in this page) -4 ^^^-III I--Order --------- [Illustration of drawing number] ⑴ Volatile metal chloride ⑺ Cyclone (3) Gaseous titanium tetrachloride (4) Cyclone dust (5) Container (6) Chinese National Standard (CNS) A4 for water and / or acidic process water (210 X 297 mm) A7 1243697 _B7 V. Description of the invention () ) ⑺ Acidic suspension ⑻ Inert solid particles 过滤 Filter (10) Solution (11) Stirrer (12) Premix tank (13) Neutralization tank (14) Suspension (15) Lime milk (16) Container ( 17) pH controller (18) Concentrator (sedimentation tank) (19) Sludge (20) Pump (21) Filter press (22) First rubber feather auxiliary (23) Second rubber feather auxiliary (24) Container (25) Pump (26) Filter residue (please read the precautions on the back before filling this page) [Explanation of the Example] When titanium dioxide is produced by the chloride process, the chlorination reactor is used to form volatiles. The basic metal chloride (1) is cooled so that all ore- and coke particles (they are in a concentrated form, except for titanium tetrachloride) Applicable Chinese National Standard (CNS) A4 size (210 X 297 mm) 1243697 A7 __B7____ V. invention is described in (W) which inert unreacted components) in a cyclone separation in (2). Titanium tetrachloride (3) (not shown here), which is still gaseous at this temperature, is subsequently condensed, and the remaining chlorinated exhaust gas is sent to an exhaust gas purification device. The solid mixture separated in the cyclone is called "cyclone dust" (4). When a container (5) is added with water and / or acidic process water (6) [the process water is generated during operation and does not require complicated purification operations because it is used here] When the dust is mixed, an acidic suspension (7) is produced: all metal chlorides are dissolved, inert solid particles (8), coke, and unreacted ore remain unchanged and can be further used. They can be separated in a filter (9) without any problems. The method of the present invention is briefly described in this figure, in which heavy metals in the solution (10) do not need to be selectively recovered, and all heavy metal ions are disposed of as unrecyclable substances. They are converted into metal hydroxides by neutralization. It is possible here to selectively separate individual ions or groups of ions (e.g., iron or vanadium). This conventional method step does not hinder or change the method of the present invention and will not be discussed further. If the neutralization operation is divided into two phases: a "quick" pre-neutralization operation and a post-adjustment operation, it is particularly advantageous for the dehydration operation required at the end of this process. This rapid pre-neutralization operation is achieved in a pre-mixing tank (12) with a stirrer (11). In this way, the pH can be rapidly increased, and it can be uniformly increased in each space and time, and even during operation When the process fluctuates, the formation of crystal nuclei or rubber plumes in any part of the volume is not the most suitable in space and time. During pre-neutralization, pH 値 rises to 6-9. For the purpose of stabilization and fine adjustment, there is a second — ______2______ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first? Matters before filling out this page)
丨丨丨丨丨丨丨訂------— II 1243697 A7 ___B7 ____ 五、發明說明（< ) (較大的）中和槽（13);由該處出來的懸浮液（14)有一致的 pH値，在9〜12間，且宜爲10。此中和作業宜用來自一 容器（16)的石灰乳（15)達成。圖中顯示一個PH値調節裝置 (17) 〇 來自該旋風塵的重金屬離子利用該中和作業而呈氫氧 化物形式沉澱。在中間接以該具有攪拌器的預混合槽（12) ，對於膠羽形成的作用有影響，它似乎主要正面地影響該 膠羽的均勻度。 在一濃縮器（18)中有一種污泥（19)從懸浮液（14)沉澱’ 該污泥（19)用一泵(20)經一容器(24)及一泵(25)運送到一個 過濾壓機(21)。 利用二道另外的措施，可有利地影響該膠羽形成作用 ，且影響可過濾性。 在沉降槽(池)(18)前可將第一種成膠羽輔助劑(22)(宜爲 一種陰離子性成膠羽輔助劑)加入。所用陰離子成膠羽輔助 劑，舉例而言，可爲丙烯醯胺與丙烯酸鈉的共聚物’其較 佳的量在5〜3 0 ppm範圍(相對於該濃縮的污泥量）。 又，在濃縮級（18)後，可將第二種成膠羽輔助劑（23)( 宜爲一種陽離子性成膠羽輔助劑)加入。所用陽離子成膠羽 輔助劑，舉例而言，可爲陽離子性丙烯醯胺共聚物，其較 佳的量在5〜30 ppm範圍(相對於該濃縮的污泥量）。 對於所要作廢棄處理的濾渣(26)的乾燥殘餘物有影響 的還有脫水作業，該脫水作業宜用一薄膜過濾壓機達成。 該塡充壓力要大於4巴，且宜爲10〜15巴。污泥的後壓 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------% A7 1243697 ___B7 _ 五、發明說明（U ) 作業宜在10〜15巴進行。 在這一道例示的程序之後，在濾澄中的乾燥殘餘物可 提高到超過45%以上。此値可不受所用原料影響地達成。 在此例示的程序中顯示，在天然的及人造的金紅石，所產 生的要氯化的礦石係爲一種可廢棄處理的非觸變性的濾澄 。當使用鈦鐵礦的場合或熔渣/金紅石混合物當作起始材料 (有或無氯化鐵的選擇性再處理）時，其優點只見於濾渣的 高乾燥物質含量，該濾渣係在該金屬氯化物中和及處理時 產生者。 以下說明在純金紅石的場合可達成的乾燥殘餘物及所 要廢棄處理的量： [方法A](背景技術） 當將初始懸浮液作中和而不將惰性成份分離時，該濾 渣爲非觸變性，乾燥殘餘物達46.5%，所要廢棄處理量在 1115公斤/每噸Ti02。 [方法B](背景技術） 如果把來方法A的懸浮液將惰性的成份分離，則該濾 渣爲觸變性(不能作廢棄處理），該乾燥殘餘物只達26.9 % ’所要廢棄處理的量爲1270公斤/每噸Ti02。 [方法C](背景技術） 當依德國專利案DE 41 31 577 A1所述的方法ill將懸 浮液處理時，該濾渣爲非觸變性，乾燥殘餘物達38.6 %， 所要廢棄處理量在627公斤/每噸Ti02。 [方法D] ____ 9_____ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) — — — — — — — 象#· A7 1243697 _B7 五、發明說明（]) / ' 利用本發明的方法得到一種非觸變性的濾渣，它具有 45 %的乾燥殘餘物。所要廢棄處理量還只有538公斤/噸 Ti02。 (請先閱讀背面之注意事項再填寫本頁) 訂---------% __10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）丨 丨 丨 丨 丨 丨 丨 Order -------- II 1243697 A7 ___B7 ____ V. Description of the invention (<) (larger) Neutralization tank (13); Suspension from there (14) Have a consistent pH, between 9 and 12, and preferably 10. This neutralization operation is preferably achieved with lime milk (15) from a container (16). The figure shows a PH 値 adjusting device (17). Heavy metal ions from the cyclone dust are precipitated in the form of hydroxides by the neutralization operation. Indirectly, the premixing tank (12) with agitator has an effect on the formation of rubber plume, and it seems to mainly affect the uniformity of the rubber plume. A sludge (19) settles from the suspension (14) in a concentrator (18). The sludge (19) is transported by a pump (20) via a container (24) and a pump (25) to a Filter press (21). The use of two additional measures can advantageously affect the rubber plume formation and affect the filterability. The first rubber feather forming auxiliary (22) (preferably an anionic rubber feather forming auxiliary) can be added before the sedimentation tank (pool) (18). The anionic feather forming aid used may, for example, be a copolymer of acrylamide and sodium acrylate ', and its preferred amount is in the range of 5 to 30 ppm (relative to the concentrated sludge amount). In addition, after the concentration level (18), a second rubber feather forming auxiliary (23) (preferably a cationic rubber feather forming auxiliary) may be added. The cationic feather forming auxiliary used may, for example, be a cationic acrylamide copolymer, and its preferred amount is in the range of 5 to 30 ppm (relative to the concentrated sludge amount). A dewatering operation is also affected by the dry residue of the filter residue (26) to be discarded. This dewatering operation should be achieved by a membrane filter press. The charging pressure should be greater than 4 bar, and preferably 10-15 bar. The paper size of the sludge after pressing applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Order ---------% A7 1243697 ___B7 _ 5. Description of the invention (U) The operation should be performed at 10 ~ 15 bar. After this exemplified procedure, the dry residue in filtration can be increased to more than 45%. This can be achieved independently of the raw materials used. The exemplified procedure shows that in natural and man-made rutile, the ore to be chlorinated is a non-thixotropic filter that can be disposed of. When ilmenite is used or a slag / rutile mixture is used as a starting material (with or without selective reprocessing of ferric chloride), its advantages are only seen in the high dry matter content of the filter residue, which is Produced during metal chloride neutralization and processing. The following describes the dry residue that can be achieved in the case of pure rutile and the amount of waste disposal required: [Method A] (Background Art) When the initial suspension is neutralized without separating the inert components, the filter residue is non-thixotropic , The dry residue reaches 46.5%, and the waste disposal capacity is 1115 kg / ton of Ti02. [Method B] (Background technology) If the suspension from Method A is used to separate inert components, the filter residue is thixotropic (cannot be discarded), and the dry residue is only 26.9%. 'The amount to be discarded is 1270 kg / ton of Ti02. [Method C] (Background Art) When the suspension is processed according to the method ill described in German patent case DE 41 31 577 A1, the filter residue is non-thixotropic, the dry residue reaches 38.6%, and the waste disposal capacity is 627 kg / Ti02 per ton. [Method D] ____ 9_____ This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling this page) — — — — — — — 象 # · A7 1243697 _B7 V. Description of the invention (]) / 'Using the method of the present invention, a non-thixotropic filter residue is obtained, which has a dry residue of 45%. The required disposal capacity is only 538 kg / t Ti02. (Please read the notes on the back before filling out this page) Order ---------% __10 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)