TW200538397A - Production of titania - Google Patents

Abstract

A process for producing titania from a solid, iron-containing titaniferous material (such as ilmenite) is disclosed. The process includes a first step of treating iron-containing titaniferous material under conditions that reduce ferric ions to ferrous ions in the titaniferous material. Thereafter the process include steps of leaching treated titaniferous material and forming a leach liquor that includes an acidic solution of titanyl sulfate and iron sulfate and recovering titania from the leach liquor.

Description

•200538397 九、發明說明： 【日月 冷員】 -. 發明領域 • · 本發明係有關一種由含鈦材料製造二氧化鈦之方、去 5 前^:冬好】 發明背景 須瞭解「含鈦」材料一詞於此處表示任_種含鈦材料 ，包括舉例言之礦石、礦石濃縮物、及含鈦礦渣。 • 本發明特別係關於一種由固體含鈦材料製造二氧化鈦 10 之方法，該方法通稱為硫酸鹽法。 須瞭解此處「硫酸」法一詞表示一種由含鈦材料製造 、 二氧化鈦之方法，包含處理固體進給材料，以及至少實質 上溶解該進給材料成為溶液，以及隨後，由溶液回收二氧 化鈦。 15 申請人就硫酸鹽法進行研究與開發工作。研究結果獲 得硫酸鹽法之兩種選項。 ® 一種方法選項說明於國際申請案PCT/AU03/01386，另 一方法選項說明於國際申請案PCT/AU2〇〇4/〇〇1421。 兩種方法選項皆包括下列步驟： 20 (a)使用含硫酸之瀝濾溶液，瀝濾固體含鐵之含鈦材料（ 諸如鈦鐵礦），以及生成瀝濾液其包括硫酸氧鈦(Ti〇S〇4)及 硫酸鐵(FeS〇4)之酸性溶液； (b)由遞濾液分離硫酸氧鈦，例如如國際申請案 PCT/AU03/01386所述藉溶劑萃取分離，或如國際申請案 5 200538397 PCT/AU2〇〇43/001421所述藉沉澱分離；以及 (c)由硫酸氧鈦回收二氧化鈦 研究與開發工作包括於400-750克/升硫酸渥滤棘鐵石廣 。研究工作包括於遞滤步驟(a)期間添加呈鐵屑形式之鐵。 5 添加鐵之主要優點係加速遞濾速率。添加鐵之缺點包拉增 加硫酸鐵成為副產物之含量，且增加製程的複雜度（因此工 廠需要有設備來處理鐵屑，以及處理由於添加鐵結果逸出 之IL氣之ό又備）。此外，鐵屑雖然目前並不昂貴，但增力口製 程上的額外操作成本。此外、速率為即使添加鐵，仍 10然需要於瀝濾步驟前研磨鈦鐵礦來改善瀝濾速率。 申請人進一步進行研究與開發工作，發現可達成瀝濾 速率娘美於瀝渡步驟⑷添加鐵屑戶斤達成之渥滤速率，係經 由遞滤步驟前’於可還原鈦鐵礦之鐵離子成為亞鐵離子之 條件下處理鈦鐵礦。條件包括含鈦材料接觸還原氣體。鈦 15鐵礦處理步驟可避免或至少最小化遞據步驟期間之添加鐵 屑。• 200538397 IX. Description of the invention: [Sun and Moon Cooler]-. Field of invention • The present invention relates to a method for manufacturing titanium dioxide from a titanium-containing material. The term is used herein to denote any titanium-containing material, including by way of example ore, ore concentrate, and titanium-containing slag. • The present invention relates in particular to a method for producing titanium dioxide 10 from a solid titanium-containing material, which method is commonly referred to as the sulfate method. It should be understood that the term "sulfuric acid" method here refers to a method for manufacturing titanium dioxide from a titanium-containing material, which includes processing a solid feed material, and at least substantially dissolving the feed material into a solution, and subsequently recovering titanium dioxide from the solution. 15 The applicant conducted research and development work on the sulfate method. The results of the study yielded two options for the sulfate method. ® One method option is described in the international application PCT / AU03 / 01386, and the other method option is described in the international application PCT / AU22004 / 001421. Both method options include the following steps: 20 (a) leaching a solution containing sulfuric acid, leaching a solid iron-containing titanium-containing material (such as ilmenite), and generating a leachate that includes titanium oxysulfate (TiOS 〇4) and an acidic solution of iron sulfate (FeS〇4); (b) separating titanium oxysulfate from the filtrate, for example, by solvent extraction as described in the international application PCT / AU03 / 01386, or as in international application 5 200538397 PCT / AU20043 / 001421 is separated by precipitation; and (c) the research and development of titanium dioxide recovery from titanium oxysulfate is included in 400-750 g / l wort filter sulfate. The research work involved the addition of iron in the form of iron filings during step (a) of the filtration step. 5 The main advantage of adding iron is to accelerate the filtration rate. The disadvantages of adding iron include increasing the content of iron sulfate as a by-product, and increasing the complexity of the process (so the factory needs equipment to handle iron filings, as well as the IL gas that escapes as a result of adding iron). In addition, iron filings are currently not expensive, but the additional operating costs of the booster process. In addition, the rate is that even if iron is added, it is still necessary to grind ilmenite before the leaching step to improve the leaching rate. The applicant further carried out research and development work and found that the leaching rate can be achieved in the leaching step. The iron leaching rate achieved by the addition of iron filings was achieved by reducing the iron ions in the reducible ilmenite before the filtration step. Treatment of ilmenite under ferrous ion conditions. Conditions include contact of the titanium-containing material with a reducing gas. The titanium 15 iron ore processing step avoids or at least minimizes the addition of iron filings during the delivery step.

t 明内容;J 發明概要 如此本發明提供一種由 鐵礦）製造二氧化鈦之方法， 111體含鐵之含鈦材料（諸如 δ亥方法包括下列步驟： 鈦 體接觸 ⑼遞渡處理後之含鈦㈣，叫軸包減酸氧鈇及 20 200538397 硫酸鐵之酸性溶液之瀝濾液； (c)由遞濾液回收二氧化鈦。 較佳;步驟⑷包含於可獲得亞鐵離子成為含鈦材料中 之主要鐵形式之條件下處理含鈦材料。 10 15 「主要」-詞須瞭解於此處表示亞鐵離子含量係占處 心材料之鐵總量之A部分。以處理後材料之亞鐵離子之 實際含量表示’如此代表亞鐵離子係占處理後材料之鐵她 置至⑽％且典型至少篇重量比。就亞鐵離子比處理步驟 ⑷之哥含輯料之亞鐵離子含量增加而言，如此代表亞鐵 2比處理步驟⑷之前含鈦材料之亞鐵離子含量至少增高 較佳，步驟⑷包含於不會導致實f生成金紅石之條件 :處理含鈦材料，金紅石於轉步驟⑻之條件下無法遞 應0 較佳，步驟⑷包含於下述條件下處理含鈦材料，因而 =該步驟未生成金屬離子’或於該步驟生成選定之相對小 量之金屬離子。 步驟⑷可於適當處理裝置諸如流化床或窯進行。 幸交佳，步驟⑷包含經由含鈦材料與還原氣體於一流化 床接觸來處理含鈦材料。 • •步驟⑷之相關條件包括例如選定(i)還原氣體之組成， G士0還原氣體之溫度’以及㈣還原氣體與含鈇材料之接觸 時間。 一氧化碳、及其 還原氣體可為任一種氣體諸如氣氣 200538397 混合物。 較佳’還原氣體為（a)氫氣及/或一氧化碳及/或曱烷與(b) 另種適當氣體諸如惰性氣體及/或二氧化碳之混合物。 較佳惰性氣體為氮氣。 5 於其中還原氣體包含氫而惰性氣體包含氮之情況下， 較佳氫係占還原氣體高達25%且更佳3-25〇/❶體積比。 於還原氣體包含氫之情況下，較佳還原氣體溫度係低 於7〇〇c來避免實質生成金紅石，金紅石於瀝濾步驟(b)之條 件下無法瀝濾。 10 於其中還原氣體包含氫之條件下，較佳還原氣體溫度 為450-550〇C 〇 於其中還原氣體包含一氧化碳而另一種氣體包含二氧 化碳之情況下，較佳一氧化碳係占還原氣體高達6〇%且更 佳30-60%體積比。 15 於還原氣體包含一氧化碳而惰性氣體包含氮氣之情況 下，較佳還原氣體溫度係低於7〇〇t，更佳係低於65〇°C。 於還原氣體包含一氧化碳而惰性氣體包含氮氣之情況 下，特佳氣體溫度為600°C。 車父佳材料與還原氣體之平均接觸時間少於12〇分鐘，及 20 更佳為20-120分鐘。 步驟（b)及（c)可如國際申請案pCT/AU03/01386及國際 申請案PCT/AU2004/001421之說明。 特別，瀝濾步驟(b)包含多重瀝濾步驟，涉及⑴一第一 步驟，以瀝濾液瀝濾該含鈦材料，以及生成包括硫酸氧鈦 200538397 之酸性溶液之製程溶液；⑼分離該製程溶液與殘餘固相； (⑴)以瀝濾液於瀝濾隨後瀝濾步驟之殘餘固相，以及生成包 括硫酸氧鈦及硫酸鐵之酸性溶液之另一製程溶液八或分 離該製程溶液與殘餘固相；及(v)供給分離所得製程溶液至 5第一瀝濾步驟，及/或混合分離所得製程溶液與得自第一瀝 濾步驟之製程溶液供隨後用於還原步驟(c)之處理。 較佳，瀝濾步驟(b)包括選擇及/或控制瀝濾條件，來 避免非期望數量之過早水解以及避免非期望數量之過早 沉澱。 10 典型地，當於95。(：之沸點範圍之瀝濾溫度操作時，瀝 濾步驟(b)之酸濃度於整個瀝濾步驟須至少為350克/升硫酸 來避免過早水解。 此外典型地，當於95°C之沸點範圍之瀝濾溫度操作時 ’瀝濾步驟(b)結束時之酸濃度須低於450克/升，以免非期 15 望數量之硫酸氧鈦過早沉澱。 瀝遽步驟(b)開始時之酸濃度可南於任何前述期望濃度 ，典型高達700克/升。 特定έ之，步驟(C)由遞濾、液回收二氧化鈦包含下列步 驟：（i)由瀝濾液分離硫酸鐵，（ii)於一步驟⑴之後或之前 20 ，由瀝濾液分離硫酸氧鈦，以及（iii)由硫酸氧鈦回收二氧 化鈦。 更特別，步驟（ii)由瀝濾液分離硫酸氧鈦包含由瀝濾 液藉溶劑萃取硫酸氧鈦，如國際申請案PCT/AU03/01386 所述。 9 200538397 另一可能之選項（但非唯一）步驟(ii)由瀝濾液分離硫酸 氧鈦包含由瀝濾液沉澱硫酸氧鈦，如國際申請案 PCT/AU2004/001421所述。 國際申請案PCT/AU03/01386及國際申請案 5 PCT/AU2004/001421之揭示藉交互參照而併入此處。 步驟(b)及（c)非僅限於國際申請案pCT/Au〇3/〇1386及 國際申請案PCT/AU2004/001421所述步驟。 舉例言之’瀝濾步驟(b)可根據標準硫酸鹽方法，其包 括2段式步驟，第一階段涉及以濃硫酸固態硫酸化得自步驟 1〇 (a)之經前處理之含鈦材料；以及第二階段涉及溶解硫酸化 產物於水/稀酸，以及生成硫酸氧鈦及硫酸鐵之酸性溶液。 申請人所進行之有關處理鈦鐵礦之研究與開發工作注 意焦.點集中於使用氫氣及一氧化碳。 t實施方式】 15 較佳實施例之詳細說明 後文說明係有關於申請人之新城技術中心所進行之研 究開發工作。 與實驗參數之綜論 涉及含氫還原氣體之第一組處理實驗係於畢南 (Beenup)鈦鐵礦進行。於畢南鈦鐵摘進行之實驗細節討論 於此處。 — 基於對畢南鈦鐵礦進行實驗所得之展望性結果，使用 侍自一批次史查布洛(Stradbr〇ke)鈦鐵礦進行第二組處理實 驗。後文說明討論此等實驗。 20 200538397 對庫哲（Cruzor)(商品名）鈦鐵礦進行另一組包括含一氧 化碳之還原氣體之實驗。後文說明討論此等實驗。 • 史查布洛鈦鐵礦實驗 於第一批次史查布洛鈦鐵礦所進行之實驗注意焦點集 5 中在三項變數對鈦鐵礦處理之影響。該等變數為··t Description; J Summary of the invention Thus, the present invention provides a method for manufacturing titanium dioxide from iron ore. The 111-body iron-containing titanium-containing material (such as the delta method) includes the following steps: The titanium body contacts the titanium-containing titanium after the treatment process. It is called the leaching solution of the acid solution of acid and oxygen reduction and 20 200538397 iron sulfate; (c) recovering titanium dioxide from the filtrate. Better; step ⑷ is included in obtaining ferrous ions to become the main form of iron in titanium-containing materials. Titanium-containing materials are processed under the conditions. 10 15 "Main"-the word must be understood here means that the ferrous ion content is part A of the total iron in the core material. It is expressed by the actual content of ferrous ions in the processed material 'This means that the ferrous ion system accounts for the iron content of the treated material to ⑽% and typically at least a weight ratio. As far as the ferrous ion content in the processing step ⑷ is increased, the content of the ferrous ion containing the material is increased. Iron 2 is better than at least the ferrous ion content of the titanium-containing material before processing step 处理. Step ⑷ is included in conditions that will not cause the formation of rutile: processing titanium-containing materials, rutile in the step Under the conditions, it is not possible to respond to 0. Step ⑷ includes processing titanium-containing materials under the following conditions, so = no metal ions are generated in this step 'or a selected relatively small amount of metal ions is generated in this step. Appropriate processing equipment such as a fluidized bed or kiln. Fortunately, step (i) includes processing the titanium-containing material via contacting the titanium-containing material with a reducing gas in a first-rate fluidized bed. • • Related conditions for step (i) include, for example, selection (i) The composition of the reducing gas, the temperature of the reducing gas, and the contact time between the tritium reducing gas and the thorium-containing material. Carbon monoxide and its reducing gas may be any kind of gas such as a gas gas 200538397 mixture. The preferred 'reducing gas is (a ) A mixture of hydrogen and / or carbon monoxide and / or oxane with (b) another suitable gas such as an inert gas and / or carbon dioxide. Preferably the inert gas is nitrogen. 5 In the case where the reducing gas contains hydrogen and the inert gas contains nitrogen In this case, the preferred hydrogen system accounts for up to 25% of the reducing gas and more preferably a volume ratio of 3-25 / ❶. In the case where the reducing gas contains hydrogen, the temperature of the reducing gas is preferred. Below 70 ° C to avoid substantial formation of rutile, rutile cannot be leached under the conditions of leaching step (b). 10 Under the conditions where the reducing gas contains hydrogen, the preferred reducing gas temperature is 450-550. In the case where the reducing gas contains carbon monoxide and the other gas contains carbon dioxide, it is preferable that carbon monoxide accounts for up to 60% and more preferably 30-60% by volume of the reducing gas. 15 The reducing gas contains carbon monoxide and the inert gas contains nitrogen In this case, the temperature of the reducing gas is preferably lower than 700 t, and more preferably lower than 65 ° C. In the case where the reducing gas contains carbon monoxide and the inert gas contains nitrogen, a particularly preferred gas temperature is 600 ° C. The average contact time between Chevrolet material and reducing gas is less than 120 minutes, and 20 is more preferably 20-120 minutes. Steps (b) and (c) can be as described in the international application pCT / AU03 / 01386 and the international application PCT / AU2004 / 001421. In particular, the leaching step (b) includes multiple leaching steps, which involve the first step of leaching the titanium-containing material with the leaching solution and generating a process solution including an acidic solution of titanyl sulfate 200538397; With the residual solid phase; (i) using the leachate in the leaching followed by the leaching step, and producing another process solution including an acidic solution of titanyl sulfate and iron sulfate; or separating the process solution from the residual solid phase ; And (v) supplying the process solution obtained from the separation to 5 first leaching steps, and / or mixing the process solution obtained from the separation and the process solution obtained from the first leaching step for subsequent treatment in the reduction step (c). Preferably, leaching step (b) includes selecting and / or controlling leaching conditions to avoid undesired amounts of premature hydrolysis and to avoid undesired amounts of premature precipitation. 10 is typically at 95. (: When operating at a leaching temperature in the boiling point range, the acid concentration in the leaching step (b) must be at least 350 g / L sulfuric acid throughout the leaching step to avoid premature hydrolysis. In addition, typically, at 95 ° C When operating at the leaching temperature in the boiling point range, the acid concentration at the end of the leaching step (b) must be less than 450 g / l, so as to avoid unexpected precipitation of titanium oxysulfate in an unexpected amount. At the beginning of the leaching step (b) The acid concentration can be as high as any of the aforementioned desired concentrations, typically as high as 700 g / l. Specifically, step (C) recovers titanium dioxide by filtration and liquid containing the following steps: (i) separating iron sulfate from the leachate, (ii) After or before step 20, titanium oxysulfate is separated from the leachate, and (iii) titanium dioxide is recovered from the titanium oxysulfate. More specifically, step (ii) separating titanium oxysulfate from the leachate includes extracting sulfuric acid with the solvent from the leachate. Oxytitanium, as described in the international application PCT / AU03 / 01386. 9 200538397 Another possible option (but not the only) Step (ii) Separation of titanyl sulfate from the leachate contains precipitation of titanyl sulfate from the leachate, as in the international application Case PCT / AU2004 / 001421. The disclosures of International Application PCT / AU03 / 01386 and International Application 5 PCT / AU2004 / 001421 are incorporated herein by cross-reference. Steps (b) and (c) are not limited to the international application pCT / Au〇3 / 〇 The steps described in 1386 and international application PCT / AU2004 / 001421. For example, the 'leaching step (b) can be according to the standard sulfate method, which includes a two-stage step, the first stage involves obtaining from solid sulfuric acid with concentrated sulfuric acid obtained from The pre-treated titanium-containing material of step 10 (a); and the second stage involves dissolving the sulfated product in water / dilute acid, and generating an acidic solution of titanium oxysulfate and iron sulfate. Related processing by the applicant Focus on research and development of iron ore. Focus is on the use of hydrogen and carbon monoxide. Implementation Mode 15 Detailed description of the preferred embodiment The following description refers to the research and development work carried out by the applicant's Xincheng Technology Center. A comprehensive review of experimental parameters The first set of processing experiments involving hydrogen-containing reducing gases was performed at the Benup ilmenite. Details of the experiments performed at the Binan ilmenite extract are discussed here. Mine experiment For the prospective results obtained, a second batch of processing experiments was performed using a batch of Stradbroke ilmenite. These experiments will be discussed later. 20 200538397 Cruzor (trade name) ) Ilmenite carries out another set of experiments including a reducing gas containing carbon monoxide. These experiments will be discussed later. • Schablo's ilmenite experiment performed on the first batch of Schabro's ilmenite Note the effects of three variables in ilmenite treatment in focus set 5. These variables are ...

(a) 還原氣體溫度一450°C及550°C (b) 氣體組成一10%H2KN2及20%H2於N2 ;及 (c) 還原時間一45分鐘及90分鐘 • 於第二批次史查布洛鈦鐵礦所進行之實驗，注意力重 10 點集中於驗證處理對第一批次史查布洛鈦鐵礦之結果，以 ~ 及產生比較資料來提供評比結果之標準。 -. 進給材料之粒子大小 表1列舉第一批次史查布洛鈦鐵礦之粒徑分布。 15 表1、第一批次史查布洛鈦鐵礦之篩選資料 尺寸（毫米） 重量（克） % %通過 1 0 0.000 100.000 0.5 0 0.000 100.000 0.425 0.1 0.023 99.977 0.3 0.8 0.187 99.790 0.25 3.7 0.865 98.925 0.18 43.4 10.143 88.782 0.125 172.8 40.383 48.399 0.109 85.9 20.075 28.324 0.09 88.4 20.659 7.665 0.063 32.4 7.572 0.093 0.053 0.2 0.047 0.047 0.038 0.1 0.023 0.023 總計： 219.2 100 表2列舉第一批次史查布洛鈦鐵礦之粒徑分布。 11 200538397 表2、第2批次史查布洛鈦鐵礦之篩選資料 尺寸（毫米） 重量（克） % %通過 1 0 0.000 100.000 0.5 0 0.000 100.000 0.425 0 0.000 100.00 0.355 0.2 0.044 99.956 0.3 0.7 0.156 99.800 0.25 4.5 1.001 98.799 0.18 43.9 9.763 89.073 0.125 166.6 37.047 51.990 0.106 79.9 17.678 34.312 0.09 105.3 23.416 10.896 0.063 47.3 10.518 0.378 0.053 1.2 0.267 0.111 0.038 0.4 0.089 0.022 -0.038 0.1 0.022 0.000 總計： 449.7 100(a) Reducing gas temperature-450 ° C and 550 ° C (b) Gas composition-10% H2KN2 and 20% H2 in N2; and (c) Reduction time-45 minutes and 90 minutes • In the second batch of historical investigations In the experiments conducted by Buloh ilmenite, 10 points of attention were focused on verifying and processing the results of the first batch of Shichaluo ilmenite, and generating comparative data to provide a criterion for the evaluation results. -. Particle size of feed material Table 1 lists the particle size distribution of the first batch of Shichabulo ilmenite. 15 Table 1. Screening data of the first batch of Shichabulo ilmenite size (mm) Weight (g)%% Pass 1 0 0.000 100.000 0.5 0 0.000 100.000 0.425 0.1 0.023 99.977 0.3 0.8 0.187 99.790 0.25 3.7 0.865 98.925 0.18 43.4 10.143 88.782 0.125 172.8 40.383 48.399 0.109 85.9 20.075 28.324 0.09 88.4 20.659 7.665 0.063 32.4 7.572 0.093 0.053 0.2 0.047 0.047 0.038 0.1 0.023 0.023 Total: 219.2 100 Table 2 lists the particle size distribution of the first batch of Shichabulo ilmenite. 11 200538397 Table 2. Screening data of Shichabulo ilmenite in the second batch Size (mm) Weight (g)%% Pass 1 0 0.000 100.000 0.5 0 0.000 100.000 0.425 0 0.000 100.00 0.355 0.2 0.044 99.956 0.3 0.7 0.156 99.800 0.25 4.5 1.001 98.799 0.18 43.9 9.763 89.073 0.125 166.6 37.047 51.990 0.106 79.9 17.678 34.312 0.09 105.3 23.416 10.896 0.063 47.3 10.518 0.378 0.053 1.2 0.267 0.111 0.038 0.4 0.089 0.022 -0.038 0.1 0.022 0.000 Total: 449.7 100

第一批次及第二批次史查布洛鈦鐵礦具有類似之粒徑 分布，顆粒大小比畢南鈦鐵礦更小。特別隨著上方尺寸為 5 較小，但下方尺寸係與畢南鈦鐵礦之尺寸相同。 熱重分析裝置測試 根據本發明使用還原氣體處理第一批次史查布洛鈦鐵 礦之影響首先係於熱重分析裝置（「TGA」）評比。 如上表1列舉之第一批次史查布洛鈦鐵礦之全部尺寸 10 分量被選用於TGA實驗，原因在於即使最細小之分量也夠 大可耐受於12升/分鐘氣流之端末速度。 此外，使用「如所接受」之尺寸分量也具有於ί廣場或 於工廠規模製造時，經由篩選或軋碎而進一步縮小尺寸之 效果。 15 於10克第一批次史查布洛鈦鐵礦試驗完成8項實驗。實 驗評比前文說明之氣體組成、溫度、及時間等三項變數之 12 200538397 影響。 實驗監視實驗過程對試樣重量損失的影響。 變數矩陣列舉於表3。 表3、TGA測試之變數矩陣 溫度 時間 氣體組成 低 450〇C 45 10%H2 於 n2 1¾ 550〇C 90 20%H2 於 N2The first and second batches of Shichabulo ilmenite had similar particle size distributions, with smaller particle sizes than Binan ilmenite. Especially as the upper dimension is smaller, but the lower dimension is the same as that of Binan Ilmenite. Thermogravimetric Analysis Device Test The effect of using the reducing gas to treat the first batch of Schabro ilmenite in accordance with the present invention was first evaluated by a thermogravimetric analysis device ("TGA"). The full size 10 components of the first batch of Shichabulo ilmenite listed in Table 1 above were selected for the TGA experiment, because even the smallest component is large enough to withstand the terminal velocity of 12 l / min airflow. In addition, the use of "as accepted" size components also has the effect of further reducing the size through screening or crushing when manufacturing at the Plaza or on a factory scale. 15 Completed 8 experiments at 10 grams of the first batch of Schambro's ilmenite test. The experimental evaluation compares the effects of the three variables of the gas composition, temperature, and time described above. The effect of the experimental process on the weight loss of the sample was monitored experimentally. The variable matrix is listed in Table 3. Table 3. Variable matrix of TGA test Temperature Time Gas composition Low 450 ° C 45 10% H2 at n2 1¾ 550 ° C 90 20% H2 at N2

TGA測試處理過程中之實驗條件與重量損失摘要顯示 於表4。 表4、TGA測試之結果摘要 測試 溫度 氣體 時間 重量損失％ STR-IR0-L1 n/a n/a n/a n/a STR-IR1-L1 450 10%H2 於 n2 45 1.35 STR-IR2-L1 450 io%h2 於 n2 90 1.46 STR-IR3-L1 550 io%h2 於 n2 45 1.63 STR-IR4-L1 550 io%h2 於 n2 90 1.74 STR-IR5-L1 450 20%H2 於 N2 45 * 1.37 STR-IR6-L1 450 20%H2 於 N2 90 1.45 STR-IR7-L1 550 20%H2 於 N2 45 1.68 STR-IR8-L1 550 20%H2 於 N2 90 2.04 TGA實驗結果指示，處理步驟可部分還原鈦鐵礦，但 無法完全還原鈦鐵礦，換言之無法還原至生成100%金屬鐵 該點。 就此方面而言之結果範例顯示於第1圖。第1圖顯示實 15 驗之前20分鐘有實質重量耗損，隨後，重量耗損相對於實 驗停止時間呈恆定且相當淺之梯度。恆定梯度之重量耗損 係與鐵離子還原成為亞鐵離子之預期符合一致。若已經完 13 200538397 成還原’換言之生成100%金屬離子，則預期重量耗損作圖 於低水平處變平台化。 於其他測試重複第1圖之趨勢。 於之鈦鐵碡谁彳千瀝瀘測試 處理後之鈦鐵礦由TGA取出，隨後於100°C或恰低於 100°C於431克/升硫酸進行瀝濾（同一日）。瀝濾階段共持續5 小時。固體與液體藉過濾分離，濾液測試自由態酸及鈦。 表5摘述由鈦鐵礦萃取鈦及實驗中耗用之酸。 表5、萃取與酸耗用結果 1原條件 I 瀝濾結果 測試 溫度 氣體 時間 重量損失 萃取 酸耗用 STR-IR0-L1 n/a n/a n/a n/a 5.25 43.11 STR-IR1-L1 450 1〇%Η2 於 N2 45 1.35 6.44 41.97 STR-IR2-L1 450 i〇%h2 於 n2 90 1.46 22.20 28.33 STR-IR3-L1 550 io%h2 於 n2 45 1.63 30.84 22.62 STR-IR4-L1 550 io%h2 於 n2 90 1.74 35.00 18.79 STR-IR5-L1 450 20%H2KN2 45 1.37 27.21 18.07 STR-IR6-L1 450 20%H2 於 N2 90 1.45 32.19 16.94 STR-IR8-L1 550 20%H2 於 N2 90 2.04 36.33 20.42 STR-IR13-L1 550 20%H2 於 N2 45 1.66 48.87 15.80 萃取係相對於實驗開始時由固相所得重量，以遞濾後 液相存在之鈦重量來測定萃取程度。 試樣STR-IR13-L1 為試樣STR-IR7-L1 之重複(55〇°C，20 15 °CH2於N2經歷45分鐘），原因在於原先之結果亦即試樣 STR-IR7-L1之結果係遠低於預期值之故。試樣STR-IR7-L1 之結果未顯示於此處。原先實驗發現有兩項錯誤，亦即試 樣由TGA移出時比預期值更熱（可能造成再度氧化）；以及其 14 200538397 次’遞滤期間由於水洛與盍間之密封不良水浴高度顯著下 降。A summary of the experimental conditions and weight loss during the TGA test process is shown in Table 4. Table 4. Summary of TGA test results. Test temperature gas time weight loss% STR-IR0-L1 n / an / an / an / a STR-IR1-L1 450 10% H2 at n2 45 1.35 STR-IR2-L1 450 io% h2 at n2 90 1.46 STR-IR3-L1 550 io% h2 at n2 45 1.63 STR-IR4-L1 550 io% h2 at n2 90 1.74 STR-IR5-L1 450 20% H2 at N2 45 * 1.37 STR-IR6-L1 450 20% H2 at N2 90 1.45 STR-IR7-L1 550 20% H2 at N2 45 1.68 STR-IR8-L1 550 20% H2 at N2 90 2.04 TGA experimental results indicate that the processing steps can partially reduce ilmenite but cannot Ilmenite is completely reduced, in other words it cannot be reduced to the point where 100% metallic iron is produced. An example of the results in this regard is shown in Figure 1. Figure 1 shows that there was substantial weight loss 20 minutes before the experiment. Subsequently, the weight loss was a constant and fairly shallow gradient with respect to the test stop time. The weight loss of the constant gradient is consistent with the expected reduction of iron ions to ferrous ions. If the reduction has been completed, in other words, 100% of the metal ions are generated, the weight loss mapping is expected to be plateaued at a low level. Repeat the trend of Figure 1 for other tests. After the ilmenite test, the ilmenite was removed by TGA and then leached at 431 g / l sulfuric acid at 100 ° C or just below 100 ° C (on the same day). The leaching phase lasted a total of 5 hours. The solid and liquid are separated by filtration, and the filtrate is tested for free acid and titanium. Table 5 summarizes the extraction of titanium from ilmenite and the acids used in the experiments. Table 5. Extraction and acid consumption results 1 Original conditions I Leaching results Test temperature Gas time Weight loss Extraction acid consumption STR-IR0-L1 n / an / an / an / a 5.25 43.11 STR-IR1-L1 450 1〇 % Η2 at N2 45 1.35 6.44 41.97 STR-IR2-L1 450 i〇% h2 at n2 90 1.46 22.20 28.33 STR-IR3-L1 550 io% h2 at n2 45 1.63 30.84 22.62 STR-IR4-L1 550 io% h2 at n2 90 1.74 35.00 18.79 STR-IR5-L1 450 20% H2KN2 45 1.37 27.21 18.07 STR-IR6-L1 450 20% H2 at N2 90 1.45 32.19 16.94 STR-IR8-L1 550 20% H2 at N2 90 2.04 36.33 20.42 STR-IR13 -L1 550 20% H2 at N2 45 1.66 48.87 15.80 The extraction system is based on the weight obtained from the solid phase at the beginning of the experiment, and the weight of titanium present in the liquid phase after filtration is used to determine the degree of extraction. Sample STR-IR13-L1 is a repetition of sample STR-IR7-L1 (55 ° C, 20 15 ° CH2 for 45 minutes at N2), because the original result is the result of sample STR-IR7-L1 The reason is much lower than expected. Results for sample STR-IR7-L1 are not shown here. The original experiment found two errors, that is, the sample was hotter than expected when it was removed from the TGA (which may cause re-oxidation); and its 14 200538397 'significant reduction in the height of the water bath due to the poor seal between the water and the water during the filtration process' .

參 ifbt—TGAMA 於TGA試驗根據本發明處理之瀝濾鈦鐵礦結果顯示， 5 以接受測試之變數’ (a) 於測試範圍延長時間或提高氫濃度，可改良由鈦鐵 礦之瀝濾萃取鈦’ (b) 兩項變數之組合未顯著進一步改良萃取，以及 Φ (c)全部情況下，於測試範圍提高溫度可改良萃取。 10 經處理材料還原裝置測試以及隨後之瀝濾測試 也於熱還原裝置(HRR)評比根據本發明處理第一批次 - 史查布洛鈦鐵礦之影響。 HRR為管爐，管爐包含一管貫穿肯薩(Kanthal)***爐 中央。管爐有三個主要區段。上區段有旋風器來減速與去 15 除來自氣相之微粒。浸潰腳將此等固體送返床。試樣區段 有一片穿孔板，穿孔板允許固體床藉反應氣流流體化。試 • 樣大小通常重約500克。試樣下方之下區段係以不鏽鋼镟屑 填補。此區設計作為熱交換器，來將反應氣體快速加熱至 要求之反應溫度。 20 HRR與TGA之差異為整個試樣均勻暴露於穩定反應氣 體流。流化床可避免於TGA測試之後期階段之重量轉移效 應。結果’ TGA測試與HRR測試之比較困難，原因在於於 HRR到達某個還原點所需時間比TGA所需時間短。 500克第一批次未經研磨之史查布洛鈦鐵礦於2〇%私 15 200538397 於N2於550 C於HRR，根據本發明處理9〇分鐘。9〇分鐘處理 期結束時，接受處理之樣本於氮下冷卻至桃，移開，隨 後於同-日於2升反應舰内於硫酸遞濾$小時。酸濃度維持 於400克/升。反應瓶維持於11〇。〇溫度。瀝濾開始時固體 5 載量為400克/升。 ' 鈦及鐵溶解速率超過至今為止申請人所作任何其他工 作台測試結果。初步反應速度造成酸濃度降至低於目標酸 度。終溶液含有49克/升鈦，就固體負載量、時間及酸濃度 而a ’超過至目月為止幾乎全部測試之溶液之鈦濃度。由 1〇固體萃取之鈦為34%(當進行取樣調整時為42〇/〇)。 比較效能測詖 -八八二「⑺测、嘴傾運仃貫驗，來證實前文， 明對第-批次史查布洛鈦鐵礦處理所得結果，以及比較々 理結果與其他處理選項。 15 20 5〇〇克第二批次史查布洛鈦_試樣於臟，於加赃 於WC處㈣分鐘。騎鐘處理期結束時，處理後之％ 於氮下冷卻至4代，移出，隨㈣克試樣於2升反應瓶動 出硫酸5小時。反應麟持於U(rc溫度。酸濃度維持於45 克/升。瀝濾開始時之固體負載量為5〇克/升。 如所接受形式之50克第；錢查布隸鐵礦、及$ 克呈研磨形式之第二批次史查布洛鈦鐵礦試樣也於如 缝内於前段所述洲條件下«。㈣情況下皆添Μ 桿至反應瓶。 及分析測定由鈦職 5小時實驗期間對瀝濾液定期採樣， 16 • 200538397 礦萃取一氧化鈦至m結果示於第2圖，萃取係以克/ 升鈦金屬於瀝濾液表示。 由第2圖顯然得自第二批次史查布洛鈦鐵礦萃取之二 氧化鈦係根據本發明處理以及隨後經瀝濾，該結果： (a) 可媲美使用經研磨之鈦鐵礦所得結果；以及 (b) 就最終回收率及萃取率而言顯著優於未經研磨之鈦 鐵礦。 庫哲鈦鎩 500克庫哲鈦鐵礦試樣於流體床反應器使卿2流體化 10反應时加熱至目標溫度，氮氣氣氛以還原氣體(C〇、c〇2 2” H4之、、且口）置換。經規定時間後，還原氣體以氮氣 置換’讓反應器冷卻。 由反應器所得產物即刻於ll〇°C於45G克/升硫酸瀝遽 48小時。於特&間隔純分析，來败㈣速率與萃取。 15See ifbt-TGAMA in the TGA test. The results of leaching ilmenite treated according to the present invention show that 5 is the tested variable. (A) Extending the time or increasing the hydrogen concentration in the test range can improve the leaching extraction of ilmenite. Titanium '(b) The combination of the two variables did not significantly improve the extraction, and in all cases Φ (c), increasing the temperature in the test range can improve the extraction. 10 Treated material reduction unit test and subsequent leaching test The effects of the first batch of treatments according to the present invention-Schachbro ilmenite were also evaluated in a thermal reduction unit (HRR). HRR is a tube furnace, which contains a tube running through the center of the Kanthal split furnace. The tube furnace has three main sections. The upper section has a cyclone to slow down and remove particles from the gas phase. The impregnated feet return these solids to the bed. The sample section has a perforated plate that allows the solid bed to be fluidized by the reactive gas stream. Trials • Sample sizes usually weigh about 500 grams. The lower section below the specimen is filled with stainless steel shavings. This zone is designed as a heat exchanger to rapidly heat the reaction gas to the required reaction temperature. The difference between 20 HRR and TGA is that the entire sample is uniformly exposed to a stable reactive gas flow. The fluidized bed avoids weight transfer effects in the later stages of the TGA test. Result 'The comparison between TGA test and HRR test is difficult because the time required for HRR to reach a certain reduction point is shorter than the time required for TGA. 500 g of the first batch of non-milled schablo ilmenite at 20% private 15 200538397 at N2 at 550 C at HRR and processed according to the invention for 90 minutes. At the end of the 90-minute treatment period, the treated sample was cooled to peach under nitrogen, removed, and then filtered on the same day for 2 hours in sulfuric acid in a 2-liter reactor. The acid concentration was maintained at 400 g / l. The reaction flask was maintained at 110. 〇Temperature. The solid 5 loading at the beginning of leaching was 400 g / l. '' Titanium and iron dissolution rates exceed any other bench test results made by the applicant to date. The initial reaction rate caused the acid concentration to drop below the target acidity. The final solution contained 49 g / l of titanium, and a 'exceeded the titanium concentration of the solution tested almost completely up to the end of the month in terms of solid loading, time, and acid concentration. The titanium extracted from 10 solids was 34% (42/0 when sampling adjustment was performed). Compare the performance test-882 "testing, mouth dumping and running test, to confirm the previous results of the first batch of Shichabulo ilmenite treatment, and to compare the results of the treatment with other processing options. 15 20 500 g of the second batch of Shichabulo titanium samples were dirty, and added to the WC for a few minutes. At the end of the cycle time, the processed% was cooled to 4 generations under nitrogen and removed. Sulfuric acid was removed with a gram sample in a 2 liter reaction bottle for 5 hours. The reaction was held at U (rc temperature. The acid concentration was maintained at 45 g / L. The solid loading at the beginning of leaching was 50 g / L. As accepted in the form of 50 grams, Chanchabli iron ore, and the second batch of Shichabulo ilmenite samples in the form of grinding are also in the seam under the conditions described in the previous paragraph. In the case of all cases, add the M rod to the reaction flask. And the analysis and determination are carried out on the regular sampling of the leachate during the 5 hour experiment. 16 • 200538397 Mine extraction of titanium oxide to m The results are shown in Figure 2. Titanium is shown in the leachate. The titanium dioxide based on the second batch of Schabro The inventive treatment and subsequent leaching resulted in: (a) comparable results obtained using ground ilmenite; and (b) significantly better than unground ilmenite in terms of final recovery and extraction rate. 500 g of Kuzeite ilmenite sample was heated to the target temperature in the fluidized bed reactor when fluidized and reacted, and the nitrogen atmosphere was used to reduce the gas (C0, c0 2 2 ”H4, and After the specified time, the reducing gas was replaced with nitrogen to allow the reactor to cool. The product obtained from the reactor was immediately leached at 45 ° C at 45G g / L sulfuric acid for 48 hours. At special & interval pure analysis, To reduce the rate and extraction. 15

對庫哲欽鐵礦進行實驗選用之還原氣體為-氧化碳所 得結果顯示於第3圖及第4圖。 第3圖為4個试樣於不同溫度條件下還原，進行實驗所 得鈦^取率(％)相對於瀝渡時間（小時)之作圖。該圖目的係 顯不遷原溫度對欽萃取率之影鄉 20 下還原The reduction gas selected for the Kuzhinqin iron ore experiment is carbon dioxide. The results are shown in Figures 3 and 4. Fig. 3 is a graph of the reduction rate (%) of titanium obtained in experiments with different samples under different temperature conditions versus the drain time (hours). The purpose of this figure is to reduce the original temperature to the Yingxiang extraction rate of 20 times.

J^AX) TOO ~60〇 Too 第3圖顯示以於_〇c 鈦萃取。 獲得瀝濾時夂 最倖 17 200538397 特別，第3圖顯示瀝濾於50CTC及700°C還原之試樣時， 鈦萃取率顯著低於於600°C還原試樣之鈦萃取率。 第4圖為4個試樣於不同CO於還原氣體之分壓，進行實 驗所得鈦萃取率（％)相對於瀝濾時間（小時)之作圖。該圖目 的係顯示CO之分壓對鈦萃取率之影響。 還原氣體 溫度（°c) PP CO = 0.6 ·~ 600^ PP CO = 0.45 600~" PP CO = 0.3 ~ 600~ 空白組—只有N2 600 ，還原氣體之CO分壓=0.6時還原之試樣可達成最高欽萃 取率。 10 15J ^ AX) TOO ~ 60〇 Too Figure 3 shows the titanium extraction at _〇c. The leaching time is the best. 17 200538397 In particular, Figure 3 shows that when leaching the sample reduced at 50CTC and 700 ° C, the titanium extraction rate is significantly lower than that of the reduced sample at 600 ° C. Figure 4 is a graph of the titanium extraction rate (%) versus the leaching time (hours) of the four samples at different partial pressures of CO and reducing gas. The figure shows the effect of the partial pressure of CO on the titanium extraction rate. Reducing gas temperature (° c) PP CO = 0.6 · ~ 600 ^ PP CO = 0.45 600 ~ " PP CO = 0.3 ~ 600 ~ Blank group-only N2 600, reducing sample when CO partial pressure of reducing gas = 0.6 Can achieve the highest extraction rate. 10 15

Hi# 前述實驗結果指出根據本發明處理鈦鐵礦可媲美其他 選項用來加速瀝遽速率，以及以比較目前研磨及隨後使用 鐵屑_朗狀選項，比較低酸耗用量可達成二氧化欽 之高回收率。 可未择離本發明之精髓及範圍，對前述本發明做出多 項修改。 【圖式簡單^說^明】 第1圖係TGA實驗結果的一個實例。 第2圖係5小時實驗期間對遞濾液定期採樣及分析測定 由鈦_萃取二氧化鈦至_液的結果。 第3圖係4個試樣於不同溫度條件下還原，進行實驗所 卒取率（％)相對於遞濾時間（小時)之作圖。 20 200538397Hi # The foregoing experimental results indicate that the treatment of ilmenite according to the present invention is comparable to other options for accelerating the leaching rate, and to compare the current grinding and subsequent use of the iron chip_lang-like option, and the lower acid consumption can achieve dioxin. High recovery rate. Many modifications may be made to the foregoing invention without departing from the spirit and scope of the invention. [Schematic simple ^ say ^ clear] Figure 1 is an example of TGA experimental results. Figure 2 is the result of periodic sampling and analysis of the filtrate from the titanium during the 5-hour experiment. Figure 3 is a plot of the reduction rate (%) versus the filtration time (hours) of the four samples under different temperature conditions. 20 200538397

第4圖係4個試樣於不同CO於還原氣體之分壓，進行實 驗所得鈦萃取率（％)相對於瀝濾時間（小時)之作圖。 【主要元件符號說明】 (無） 19Figure 4 is a graph of the titanium extraction rate (%) versus the leaching time (hours) of the four samples at different partial pressures of CO and reducing gas. [Explanation of Symbols of Main Components] (None) 19

Claims (1)

200538397 十、申請專利範圍： 1· -種由固體含鐵之含鈦材 之方法，該方法包括下列步驟：欽鐵石廣）製造二氧化銥 ⑷於可還原含鈦材料之鐵離 件下，處理含鐵之含鈦材料，欠成為亞鐵離子之條 還原氣體接觸； 條件包括含鈦材料與 (b)瀝濾處理後之含鈦材、, 及硫酸鐵之酸性溶液之瀝_^及形成包括硫酸氧鈦 10 15 20 (C)由瀝濾液回收二氧 2·如申請專利範圍第丨項之方法，° 得亞鐵離子成為含鈦材 A A⑷包含於可獲 理含鈦材料。 主要鐵形式之條件下處 3·如申請專利範圍第丨或2項 會導致實質生成金紅石之：其中步驟⑷包含於不 於遞濾步驟㈨之條件下無法主 4·如前述中請專利範圍各項= ⑷包含於下述條件下處 ^方法，其中步驟 生成金屬離子，或於該㈣2料，因而於該步驟未 屬離子。 ^生成選定之相對小量之金 5.如前述申請專利範圍各項 々八rΤ任一項之方法，其中步驟（a) 含鈦材料。 ^植於一流化床接觸來處理 6·如前述申請專利範圍各 、甲住—項之方法，其中還原氣 體可為任一種氣體諸如氯 ^ 匕見、一氧化碳、及其混合物。 20 200538397 7. 如前述申請專利範圍各項中任一項之方法，其中還原氣 體為（a)氫氣及/或一氧化碳及/或甲烷與(b)另一種適當 氣體諸如惰性氣體及/或二氧化碳之混合物。 8. 如申請專利範圍第7項之方法，其中該惰性氣體為氮 5 氣。 9. 如前述申請專利範圍各項中任一項之方法，其中於其中 還原氣體包含氫而惰性氣體包含氮之情況下，氫係占還 原氣體高達25%且更佳3-25%體積比。 10. 如前述申請專利範圍各項中任一項之方法，其中於還原 10 氣體包含氫之情況下，還原氣體溫度係低於700°C來避 免實質生成金紅石，金紅石於瀝濾步驟(b)之條件下無法 遞濾。 11. 如前述申請專利範圍各項中任一項之方法，其中於其 中還原氣體包含氫之條件下，還原氣體溫度為 15 450-550。。。 12. 如申請專利範圍第1至8項中任一項之方法，其中於其中 還原氣體包含一氧化碳而另一種氣體包含二氧化碳之 情況下，一氧化碳係占還原氣體高達60%且更佳30-60% 體積比。 20 13.如申請專利範圍第1至8項中任一項之方法，其中於還原 氣體包含一氧化碳而惰性氣體包含氮氣之情況下，還原 氣體溫度係低於700°C，更佳係低於650°C。 14.如申請專利範圍第1至8項中任一項之方法，其中於還原 氣體包含一氧化碳而惰性氣體包含氮氣之情況下，氣體 21 200538397 溫度為600°C。 15·如前述申請專利範圍各項中任一項之方法，其 ⑷’該含鈦材料與還原氣體之平均接觸相^於步驟 分鐘，更佳為20-120分鐘。 、夕於12〇 16·如前述申請專利範圍各項中任一項之方法，其上 步驟(b)包含多重瀝濾步驟，涉及⑴一第’一牛二中該瀝濾 10 15 20 液瀝渡該含鈦材料，以及生成包括硫酸渡 之製程溶液，分離該製程溶液與殘餘固相^錢 濾液於瀝濾隨後瀝濾步驟之殘餘固相，以及生勺)以瀝 酸氧鈦及硫酸鐵之酸性溶液之另一製程溶液成包括石泉 離該製程溶液與殘餘固相；及ω供給分 至第—瀝渡步驟，及/或混合分離所得製程溶液 歷渡步驟之製程溶液供隨後用於還原步驟 π如前述帽糊翻各射任—奴枝， ㈣⑻包括選擇及/或控制瀝滤條件，來避免非 里2過早水解以及避免非期魏量之過早沉搬。 18.如前述申請專利範圍各項中任一項之方法其中當 C之4點⑽®之輯溫度操作時，遞濾步驟(b)之酸 :整個瀝濾步驟須至少為35。克/升硫酸來避免過‘： 19.如前述Μ專利制各射任1之方法，其中當於95 C之碑點範圍之㈣溫度操作時，_步驟(b)結束時之 酸濃度須低於450克/升，以免非期望數量之硫酸氧銳過 22 200538397 早沉殿。 20.如前述申請專利範圍各項中任一項之方法，其中於瀝濾 . 步驟(b)開始時之酸濃度係低於700克/升。 • 21.如前述申請專利範圍各項中任一項之方法，其中步驟(c) 5 由瀝濾液回收二氧化鈦包含下列步驟：⑴由瀝濾液分離 硫酸鐵，（ii)於一步驟⑴之後或之前，由瀝濾液分離硫 酸氧鈦，以及（iii)由硫酸氧鈦回收二氧化鈦。 22.如申請專利範圍第21項之方法，其中步驟(ii)由瀝濾液 B 分離硫酸氧鈦包含由瀝濾液藉溶劑萃取硫酸氧鈦。 10 23.如申請專利範圍第21項之方法，其中步驟(ii)由瀝濾液 分離硫酸氧鈦包含由瀝濾液沉澱硫酸氧鈦。 * 24.如申請專利範圍第1至15項中任一項之方法，其中瀝濾 步驟(b)可根據標準硫酸鹽方法，其包括2段式步驟，第 一階段涉及以濃硫酸固態硫酸化得自步驟(a)之經前處 15 理之含鈦材料；以及第二階段涉及溶解硫酸化產物於水 /稀酸，以及生成硫酸氧鈦及硫酸鐵之酸性溶液。 23200538397 10. Scope of patent application: 1. A method of solid titanium-containing material containing iron, the method includes the following steps: Qin Tieshiguang) manufacturing iridium dioxide osmium under the iron parts of the reducible titanium-containing material, processing The iron-containing titanium-containing material is in contact with the reducing gas of ferrous ions; the conditions include the titanium-containing material and (b) the titanium-containing material after leaching treatment, and the formation of the acid solution of ferric sulfate. Titanium oxysulfate 10 15 20 (C) Recovering dioxin from the leachate. 2 According to the method in the scope of the patent application, ° ferrous ions become titanium-containing material A A⑷ is included in the available titanium-containing material. Under the condition of the main iron form 3. If the scope of application for patent No. 丨 or 2 will lead to the substantial formation of rutile: where step ⑷ is included in the condition that is not in the filtering step 滤 cannot be mastered 4. 如 as above Each term = ⑷ is included in the method under the following conditions, in which the step generates metal ions, or in the 料 2 material, so it is not an ion at this step. ^ Generate a selected relatively small amount of gold 5. The method according to any one of the foregoing patent claims, wherein step (a) contains a titanium-containing material. ^ Planted in first-class chemical bed contact for treatment 6. As described in the aforementioned patent application, the method described in item A, where the reducing gas can be any gas such as chlorine, carbon monoxide, and mixtures thereof. 20 200538397 7. A method as claimed in any one of the foregoing patent claims, wherein the reducing gas is (a) hydrogen and / or carbon monoxide and / or methane and (b) another suitable gas such as an inert gas and / or carbon dioxide mixture. 8. The method according to item 7 of the patent application, wherein the inert gas is nitrogen 5 gas. 9. The method according to any one of the foregoing claims, wherein in the case where the reducing gas contains hydrogen and the inert gas contains nitrogen, the hydrogen system accounts for up to 25% and more preferably 3-25% by volume of the reducing gas. 10. The method according to any one of the scope of the aforementioned patent application, wherein in the case where the reducing gas contains hydrogen, the temperature of the reducing gas is lower than 700 ° C to avoid substantial formation of rutile, and the rutile is subjected to a leaching step ( b) can not be filtered under the conditions. 11. The method according to any one of the foregoing claims, wherein the temperature of the reducing gas is 15 450-550 under the condition that the reducing gas contains hydrogen. . . 12. The method according to any one of the claims 1 to 8, wherein in the case where the reducing gas contains carbon monoxide and the other gas contains carbon dioxide, carbon monoxide accounts for up to 60% and more preferably 30-60% of the reducing gas. Volume ratio. 20 13. The method according to any one of claims 1 to 8 in the scope of patent application, wherein in the case where the reducing gas contains carbon monoxide and the inert gas contains nitrogen, the temperature of the reducing gas is lower than 700 ° C, and more preferably lower than 650. ° C. 14. The method according to any one of claims 1 to 8 in the scope of patent application, wherein in the case where the reducing gas contains carbon monoxide and the inert gas contains nitrogen, the temperature of the gas 21 200538397 is 600 ° C. 15. The method according to any one of the foregoing claims, wherein the average contact phase of the titanium-containing material with the reducing gas is in the step minutes, more preferably 20-120 minutes. XI Yu 12〇16. The method according to any one of the scope of the aforementioned patent application, wherein the step (b) above includes multiple leaching steps, which involves leaching of the 10th and 20th liquid leaching. The titanium-containing material, and a process solution including sulfuric acid, to separate the process solution from the residual solid phase, and to separate the residual solid phase from the leaching followed by the leaching step, and the raw spoon) to titanate and ferric sulfate Another process solution of the acidic solution includes the separation of the stone solution from the process solution and the residual solid phase; and the omega supply is divided into the first-leach step, and / or the process solution of the process solution obtained after the separation step is mixed and separated for subsequent reduction. Step π is the same as the aforementioned cap paste, which includes selecting and / or controlling leaching conditions to avoid premature hydrolysis of Feili 2 and premature sinking of non-expected quantities. 18. The method according to any one of the aforementioned patent application scopes, wherein when the temperature of the 4 o'clock temperature of C is operated, the acid of step (b) is filtered: the entire leaching step must be at least 35. G / L sulfuric acid to avoid over: 19. As described in the above M patent method, each of the methods of shooting 1, in which when operating at the temperature of 95 C of the monument range, the acid concentration at the end of step (b) must be low At 450 g / l, to avoid undesired amounts of oxygen sulphate sharpening 22 200538397 Early sanctuary. 20. A method as claimed in any one of the foregoing patent claims, wherein the acid concentration at the beginning of step (b) is less than 700 g / l. 21. The method according to any one of the preceding claims, wherein step (c) 5 recovering titanium dioxide from the leachate comprises the following steps: (i) separating the iron sulfate from the leachate, (ii) after or before step (i) , Separating titanyl sulfate from the leachate, and (iii) recovering titanium dioxide from titanyl sulfate. 22. The method of claim 21, wherein step (ii) separating the titanyl sulfate from the leachate B comprises extracting the titanyl sulfate with a solvent from the leachate. 10 23. The method of claim 21, wherein step (ii) separating the titanyl sulfate from the leachate comprises precipitating the titanyl sulfate from the leachate. * 24. The method according to any one of claims 1 to 15, wherein the leaching step (b) can be based on a standard sulfate method, which includes a two-stage step, and the first stage involves solid sulfurization with concentrated sulfuric acid. The pre-treated titanium-containing material from step (a); and the second stage involves dissolving the sulfated product in water / dilute acid and generating an acidic solution of titanium oxysulfate and iron sulfate. twenty three