TW297017B - - Google Patents

Description

五、 發明説明（ A 7 B7 經濟部中央橾隼局員工消費合作祍印袈 本發明係關於一種以一種噴霧烺燒方法再生具有加入之 鋅之氣化氫浸酸之方法° 具有高於10克/升之鋅濃度之浸酸之再生已係一項問題 歷時多年，及係一項尚未解決之問題。因此，迄今已作多 项嘗試，試驗以限制於廢浸液中之鋅含量至10克/升，以 使此等浸酸可於一種相對地無困難之方法中再生。缺點係 ，與鋅组合之氫氣酸不能回收及由於製造之氧化鐵之氣化 鋅含量因此製造之氧化鐵未經進一步處理係不能丟棄。此 亦適用於低氣化鋅含量》必須中和具有較高鋅含量之浸酸 ’此招致可觀之費用，及於於泥丢棄及廢水中之嚴重問題 〇 由於高揮發性之氣化鋅，因此於再生具有高鋅含量之浸 酸中具有困難。當煅燒氣化亞鐵時，於燃燒器區中之溫度 係較高於氣化鋅之沸點。此外，氣化鋅係很吸濕的，以使 印’、於V線、旋風器及反應器中冷卻時其造成堵塞及沈殿 ’此嚴重地阻礙操作。 本發明之目的係再生具有加入之鋅之氣化氫廢浸液而無 任何困難。 因此，本發明建議，將一種數量之鎂離子加入廢浸液中 。鋅可係經由將鎂離子加人而複合，因此容許無困擾之去 棄。 :發明之進一步發展之特徵爲_種數量之鎂離子之添加 有=少相等於鋅之數量 '經由如此作，可再生縱然具 有顯考地較高於⑽/升之鋅含量之廢浸液而無 4- (請先聞讀背面之：;i意事項再填艿本頁) .裝. 訂 本紐尺度 (CNS ) A4現格（2丨0:< 297公釐） 經濟部中央樣箪局員工消費合作社印製 297017 at B7五'發明説明（2) ，並且無堵塞或沈澱之危險。 鎮離子可係以氣化缓之形式或如菱鐵礦廢料（諸如細灰或 浮選尾;'查）加入。 由於鐵氧化物之有利之轉化成爲一種Zn0.Mg0.Fe203尖 晶石，因此廢浸液可於任何氫氣酸再生工廠中容易地處理 而無須任何其他輔助設備。 由於將鋅複合，因此不具有氣化鋅之堵塞或沈澱。再生 之氫氣酸實質上係不含鋅。 於迄今使用之方法中，下列反應發生 (1) ZnCl2 + 2 FeC12 + 2 H20+1/2 02--->Fe203+ZnC 12 + 4 HC1 於此種反應中，ZnC丨2不能適當地複合並且由於其之揮 發性因此其造成於管線之較冷部分中之沈澱及不良之堵塞 〇 根據本發明之方法，例如，根據下列式操作； (2) MgC12+ZnC12+2 FeC12+4 H20+1/2 02—>MgZnFe205+8 HC1 過量之氣化亞鐵係於反應器中根據下列式轉化： (3) FeC12+2 H20+1/2 02 —>Fe203+4 HC1 經由將鎂離子加入，例如以如於式（2 )中之氣化鎂之形 式，可複合鋅及再生實質上所有之酸。 本發明現在將係使用其之實施之實際實例、及附隨之圖 而解釋，圖表示其中可應用本發明之一種工廠之一種流程 圖。實例1 : 將8 0升之具有下列組成之溶液 -5 - ---^---------1------1T-------^ (請先閱讀背面之注意事項再填本頁) 本紙伕尺度適用中國國家標準（CNS ) A4堤格（210X29?公釐） 經濟部中央標準局員工消費合作社印製 297017 五、發明説明（3 ) 233.4克/升 FeC12 31.8克/升 ZnC12 23.1克/升 MgC12 173.0克/升 經複合並且不含HC1者 加入一種喷霧懷燒方法中=> 此對應於 15.2克/升 鋅離子及Mg ·· Zn = 1:1之莫耳比 反應之產物係14.0公斤具有下列组成之噴霧烺燒氧化物 84.75% Fe203 9.61% ZnO 5.40% MgO 0.25% 殘餘之氣化物， 以及73升之具有下列組成之再生之氫氣酸 2.04克/升 FeC13 3.55克/升 ZnC 12 1.76克/升 MgC12 190克/升 經複合並且不含HC1者。 實例2 ; 將8 0升之具有下列組成之溶液 23 1.5克/升 FeC12 31.8克/升 ZnC12 32.5克/升 MgC12 178.0克/升 經複合並且不含HC1者 加入一種噴霧烺燒方法中。此對應於 15.2克/升 鋅離子及Mg ·_ Zn= 1.5:1之莫耳: -6- -_- In ! -1 —ί - I I - - ..1 - -- -Is--II 士R——i 1 I I —. -i {(—^ T« - - -. -I - I— I----, -I - • 、v'°-Ϊ·7 f (請先閱讀背V®之注意事項再填"本頁) 本紙張尺度適用中國國家標在（CNS ) A4規格（210X29：1公釐） 五、發明説明（4 A7 B7 反應之產物係14.1公斤具有下列組成之噴霧烺燒氧化物 82.60% 9.48% 7.69% 0.23%V. Description of the invention (A 7 B7 Employee consumption cooperation of the Central Falcon Bureau of the Ministry of Economic Affairs. The present invention relates to a method of regenerating gasified hydrogen leaching acid with added zinc in a spray burn method. The regeneration of leaching acid with a zinc concentration of 1 litre has been a problem for many years and an unsolved problem. Therefore, many attempts have been made so far to limit the zinc content in the waste leaching solution to 10 grams / L, so that these pickled acids can be regenerated in a relatively trouble-free method. The disadvantage is that the hydrogen acid combined with zinc cannot be recovered and the iron oxide produced is not due to the vaporized zinc content of the iron oxide produced. Further treatment cannot be discarded. This also applies to low gasified zinc content, which must neutralize acid pickling with higher zinc content. This incurs considerable costs and serious problems in mud disposal and wastewater. Due to high volatilization Gasified zinc, so it is difficult to regenerate the pickling acid with high zinc content. When calcining gasified ferrous iron, the temperature in the burner zone is higher than the boiling point of gasified zinc. In addition, gasified zinc Department sucks Wet, so as to cause clogging and Shen Dian 'in the V line, cyclone and reactor when cooling, which seriously hinders the operation. The purpose of the present invention is to regenerate the waste leaching solution of gasified hydrogen with added zinc and There is no difficulty. Therefore, the present invention proposes to add a certain amount of magnesium ions to the waste leaching solution. Zinc can be compounded by adding magnesium ions to humans, so that it can be discarded without trouble .: The characteristics of the further development of the invention are: _The addition of a certain amount of magnesium ions = less equal to the amount of zinc 'By doing this, it is possible to regenerate waste leaching solution with a zinc content significantly higher than ⑽ / liter without 4- (please read first The back of the page :; i will fill in this page if you want to.). Packed. The New Zealand Standard (CNS) A4 is now available (2 丨 0: < 297mm) Printed by the Employee Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs 297017 at B7 Five 'Description of the invention (2), and there is no danger of clogging or precipitation. The ballast ions can be added in the form of slow gasification or such as siderite waste (such as fine ash or flotation tail;' check). Due to iron oxidation The beneficial conversion of the material into a Zn0.Mg0.Fe203 spinel, so waste leaching The liquid can be easily handled in any hydrogen acid regeneration plant without any other auxiliary equipment. Since zinc is compounded, there is no clogging or precipitation of vaporized zinc. The regenerated hydrogen acid is essentially free of zinc. It has been used so far In the method, the following reactions occur: (1) ZnCl2 + 2 FeC12 + 2 H20 + 1/2 02 ---> Fe203 + ZnC 12 + 4 HC1 In this reaction, ZnC 丨 2 cannot be properly combined and due to its Volatility is therefore caused by precipitation in the colder parts of the pipeline and poor blockage. According to the method of the present invention, for example, according to the following formula; (2) MgC12 + ZnC12 + 2 FeC12 + 4 H20 + 1/2 02— > MgZnFe205 + 8 HC1 excess ferrous gas is converted in the reactor according to the following formula: (3) FeC12 + 2 H20 + 1/2 02 —> Fe203 + 4 HC1 is added by adding magnesium ions, for example In the form of vaporized magnesium in formula (2), zinc can be compounded and substantially all acids can be regenerated. The present invention will now be explained using practical examples of its implementation and accompanying drawings, which show a flow chart of a plant in which the present invention can be applied. Example 1: 80 litres of solution with the following composition -5---- ^ --------- 1 ------ 1T ------- ^ (please read the back Please pay attention to this page and then fill out this page.) This paper is applicable to China National Standard (CNS) A4 Dike (210X29? Mm). Printed 297017 by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) 233.4g / L FeC12 31.8 g / l ZnC12 23.1 g / l MgC12 173.0 g / l compounded without HC1 is added to a spray calcination method => this corresponds to 15.2 g / l zinc ion and Mg · Zn = 1: 1 The product of the molar ratio is 14.0 kg of sprayed oxide with the following composition: 84.75% Fe203 9.61% ZnO 5.40% MgO 0.25% residual gasification, and 73 liters of regenerated hydrogen acid with the following composition 2.04 g / L FeC13 3.55 g / l ZnC 12 1.76 g / l MgC12 190 g / l compounded without HC1. Example 2; 80 liters of a solution having the following composition 23 1.5 g / L FeC12 31.8 g / L ZnC12 32.5 g / L MgC12 178.0 g / L Compounded and free of HC1 was added to a spray burn method. This corresponds to 15.2 g / l zinc ion and Mg · Zn = 1.5: 1 mole: -6- -_-- In! -1 —ί-II--..1---Is--II taxi R——i 1 II —. -I {(— ^ T «---. -I-I— I ----, -I-•, v '° -Ϊ · 7 f (Please read back V first ®Precautions for "Fill in" this page) This paper size is applicable to the Chinese national standard (CNS) A4 specifications (210X29: 1 mm) 5. Description of the invention (4 A7 B7 The reaction product is 14.1 kg of spray with the following composition Burning oxide 82.60% 9.48% 7.69% 0.23%

Fe203 ZnO MgO 殘餘之氣化物 以及72升之具有下列組成之再生之氫氣酸 2.62克/升 2.93克/升 2.51克/升 196.8克/升 實例3 ;Fe203 ZnO MgO residual gasification and 72 liters of regenerated hydrogen acid with the following composition 2.62 g / L 2.93 g / L 2.51 g / L 196.8 g / L Example 3;

FeC13 ZnC12 MgC12 經複合並且不含HC1者 將8 0升之具有下列组成之溶液 220.2克/升 58.5克/升 43.9克/升 208.0克/升 經濟部中央標準局員工消费合作社印裝FeC13 ZnC12 MgC12 compounded and not containing HC1 Print 80 liters of a solution with the following composition 220.2 g / L 58.5 g / L 43.9 g / L 208.0 g / L

FeC12 ZnC12 MgC12 經複合並且不含HC1者。 加入一種噴霧愤燒方法中。此對應於 28.0克/升 鋅離子及Mg : Zn=l: 1之莫耳比。 此反應之產物係15.2公斤具有下列组成之噴霧烺燒氧化物 72.91%克 / 升 Fe203 17.16% ZnO 9.61% MgO 0.3 1% 殘餘之氣化物， 以及84升之具有下列組成之再生之氫氣酸 -7- 本紙伕尺度適用中國國家標準（C\S ) A4規格（210X297公釐） ---；---------裝-------訂------線 (請先"讀背面之注意事項再填寫大*頁) B7 五、發明説明（5 2.62克/升 3.32克/升 3.53克/升 197克/升 實例4 ;FeC12 ZnC12 MgC12 is compounded and does not contain HC1. Add a spray anger method. This corresponds to a molar ratio of 28.0 g / L of zinc ions and Mg: Zn = l: 1. The product of this reaction is 15.2 kg of spray burned oxide with the following composition 72.91% g / l Fe203 17.16% ZnO 9.61% MgO 0.3 1% residual gasification, and 84 liters of regenerated hydrogen acid-7 with the following composition -The size of this paper is applicable to the Chinese National Standard (C \ S) A4 specification (210X297mm) ---; --------- installed ------- order ------ line ( Please read the "Notes on the back first and then fill in the large * page) B7 5. Description of the invention (5 2.62 g / l 3.32 g / l 3.53 g / l 197 g / l Example 4;

FeC13 ZnC12 MgC12 經複合並且不含HC1者 將8 0升之具有下列组成之溶液 226.8克/升 9.6克/升 6.7克/升 171.0克/升FeC13 ZnC12 MgC12 compounded without HC1 80 liters of a solution with the following composition 226.8 g / l 9.6 g / l 6.7 g / l 171.0 g / l

FeC12 ZnC12 MgC12 經複合並且不含HC1者 加入一種噴霧煅燒方法中。 此反應之產物係12公斤具有下列组成之噴霧烺燒氧化物 94.38% 3.65% 1.85% 0.10%FeC12 ZnC12 MgC12 compounded without HC1 is added to a spray calcination method. The product of this reaction is 12 kg of spray burned oxide with the following composition 94.38% 3.65% 1.85% 0.10%

Fe203 ZnO MgO 殘餘之氣化物 以及69升之具有下列組成之再生氫氣酸 ---：---------裝-------訂------咸 (請先兒讀背面之注意事項再填寫太頁) 經濟部中央標準局員工消費合作社印裝 2.3克/升 0.4克/升 0.3克/升 193克/升Fe203 ZnO MgO residual gasification and 69 liters of regenerated hydrogen acid with the following composition ---: --------- installation ------- order ------ salty (please first (Please read the notes on the back and fill in the page.) Printed and printed by the Staff and Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2.3g / liter 0.4g / liter 0.3g / liter 193g / liter

FeC13 ZnC12 MgC12 經複合並且不含HC1者。 圖解顯示浸酸再生工廠之一種流程圖，其中將包含鋅之 種廢浸液1置於一種混合槽2中，將一種數量之鎂離子 (例如以氣化鎂、氧化鎂或碳酸鎂之形式）加入其中及使 -8- 本紙張尺度適用中國國家標準（（：>；5)六4規格（210<29，公釐） A7 A7 經濟部中央糅準局員工消費合作杜印褽 —____B7 五、發明説明（6 ) ~ ~ - 用一種混合機4共同混合。將此種複合物進料至—種細腰 洗滌器（venturi washer) 5及部分之混合物9自此哈 '-貝務入反 應器6中。使用過之浸酸係經由將燃氣7及空氣8加入而 於約700-7 5(TC之溫度烺燒，即氡化。來自爐1〇之^化物 係經由一種風扇12而輸送至一個槽丨丨及氧化鐵丨3係自此處 抽出以進一步處理或銷售，來自反應器6之排出空氣係進 料通過一種旋風器14,其中移除殘餘之旋風器氧化物15, 然後循環至反應器6。使用過之浸酸之酸部份16係自細腰 洗滌器進料至一種吸收器17。自吸收器17之排出氣體通過 一種洗滌器18，及係經由一種風扇19而自此處排入大氣2〇 中。再生之酸2 1係自吸收器抽出及返回至浸潰方法3 本發明不受限於在圖及實例中提及之設計。相反地，倘 若廢浸酸具有相對地低之鋅含量（例如低於5克/升），則亦 可使用本發明以獲益，如此顯著地減少迄今遭遇之丢棄問 題。再生工廠之設計亦可不同於所表示者。 圖式簡單説明 圖1顯示浸酸再生工廠之流程圖，其中 1. 代表廢浸液， 2. 代表混合槽， 3. 代表錢離子， 4. 代表混合機， 5. 代表細腰洗滌器， 6-代表反應器， 7·代表燃氣， -9- 本紙張尺度料（CNS ) A4規格（公一 --- ---:----------裝-------^訂-------咸 ~一 (讀先閱讀背面之：;i意事項、再填寫未頁) B7五、發明説明（7) 8. 代表空氣， 9. 代表混合物， 10. 代表爐， 11. 代表槽， 12. 代表風扇， 13. 代表氧化鐵， 14. 代表旋風器， 15. 代表旋風器氧化物， 16. 代表酸部份， 17. 代表吸收器， 18. 代表洗滌器， 19. 代表風扇， 20. 代表大氣， 21. 代表再生酸。 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 本紙伕尺度適用中國國家標準（CNS ) A4規格（2丨OX29：7公釐）FeC13 ZnC12 MgC12 is compounded and does not contain HC1. The diagram shows a flow chart of an acid leaching regeneration plant, in which a waste leaching solution 1 containing zinc is placed in a mixing tank 2 and a quantity of magnesium ions (for example in the form of vaporized magnesium, magnesium oxide or magnesium carbonate) Add to it and make -8- This paper standard is applicable to Chinese national standards ((: >; 5) Six 4 specifications (210 < 29, mm) A7 A7 Employee Consumption Cooperation of the Ministry of Economic Affairs, Ministry of Economic Affairs, Du Yinju —____ B7 Five , Description of the invention (6) ~ ~-Mix together with a mixer 4. Feed this compound to a kind of thin waist washer (venturi washer) 5 and part of the mixture 9 from now on Ha'-bei into the reaction 6. The used leaching acid is burned at a temperature of about 700-7 5 (TC) by adding fuel gas 7 and air 8, ie radonization. The chemical compound from furnace 10 is passed through a fan 12 It is transported to a tank and the iron oxide is extracted from here for further processing or sale. The exhaust air from the reactor 6 is fed through a cyclone 14 in which residual cyclone oxide 15 is removed, and then Circulate to the reactor 6. The used acid portion 16 of the pickled acid is washed from the waist The scrubber is fed to an absorber 17. The exhaust gas from the absorber 17 passes through a scrubber 18 and is discharged into the atmosphere 20 from here via a fan 19. The regenerated acid 21 is withdrawn from the absorber And return to the dipping method 3 The present invention is not limited to the designs mentioned in the figures and examples. On the contrary, if the waste dipping acid has a relatively low zinc content (eg less than 5 g / L), it can Using the present invention to benefit, so significantly reduce the discard problem encountered so far. The design of the recycling plant can also be different from the one shown. The schematic diagram illustrates the flow chart of the acid leaching recycling plant shown in Figure 1, where 1. represents waste Immersion liquid, 2. stands for mixing tank, 3. stands for money ion, 4. stands for mixer, 5. stands for thin waist washer, 6- stands for reactor, 7 · stands for gas, -9- this paper standard material (CNS ) A4 specifications (public one --- ---: ---------- installed ------- ^ order ------- salty ~ one (read first to read the back: ; i meanings, fill in the rest pages) B7 V. Description of the invention (7) 8. Represents air, 9. Represents mixture, 10. Represents furnace, 11. Represents trough, 12. Represents fan, 13 . Stands for iron oxide, 14. stands for cyclone, 15. stands for cyclone oxide, 16. stands for acid part, 17. stands for absorber, 18. stands for scrubber, 19. stands for fan, 20. stands for atmosphere, 21. It stands for regenerated acid. (Please read the precautions on the back before filling in this page) The size of the paper printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 (2 丨 OX29: 7mm)

Claims (1)

ABCD π、申請專利範圍 1. —種以一種噴霧烺燒方法再生具有加入之鋅之氣化氩 (Η⑶浸酸之方法’其特徵係將一種數量之鎂離子加入 廢浸液中。 2. 根據中請專利範圍第}項之方法，其特徵係鎂離子之數 量係至少等於存在之鋅之數量。 3. 根據申請專利範圍第χ或2項之方法，其特徵係鎂離子 之數量係以氣化鎂之形式加入。 4. 根據申請專利範圍第}或2項之方法，其特徵係鎂離子 之數量係以愛鐵礦廢料（例如細灰或浮選尾杳）之形式 力口入。 1根據申請專利範圍第1項之方法，其特徵係鐵氧化物係 轉化成爲一種ZnO.MgO.Fe2〇3尖晶石。 6.根據申請專利範圍第1項之方法’其特徵係製造之旋風 器氧化物係循環至噴霧烺燒反應器。 — II----,·---— 裝-------- I-----線 (請先閔讀背面之注意事項再填寫表頁) 經濟部中央標準局員工消費合作社印製 11 - 各紙浪尺度適用中國國家樣隼（CXS ) A4規.格（210X297公釐）ABCD π, patent application 1. A method of regenerating vaporized argon with added zinc in a spray sintering method (HCD leaching acid method) is characterized by adding a quantity of magnesium ions to the waste leaching solution. 2. According to The method of item} in the patent application scope is characterized in that the amount of magnesium ions is at least equal to the amount of zinc present. 3. According to the method of item χ or 2 in the patent application scope, the method is characterized in that the amount of magnesium ions is based on gas In the form of magnesium oxide. 4. According to the method of item} or 2 of the patent application, the characteristic is that the amount of magnesium ions is imported in the form of iron ore waste (such as fine ash or flotation tail). 1 According to the method of item 1 of the patent application, its characteristic is that the iron oxide system is transformed into a ZnO.MgO.Fe2〇3 spinel. 6. According to the method of item 1 of the patent application, its characteristic is the cyclone manufactured The oxides are recycled to the spray reactor. — II ----, · ---— Pack -------- I ----- line (please read the notes on the back before filling in Sheet) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 11 Use the Chinese National Falcon (CXS) A4 gauge (210X297mm)