TW497980B - Method for extracting useful material from waste acid liquid and device therefor - Google Patents

Abstract

The present invention relates to a method for extracting useful material from waste acid liquid and a device therefor. The method mainly comprises using a sulfuric acid replacement method to react ferrous chloride in the waste acid liquid into ferrous sulfate and hydrochloric acid. Not only hydrochloric acid can be recycled by this method, but also ferrous sulfate can be introduced with ozone to be oxidized into ferric sulphate. This method can decompose a large amount of waste acid liquid into products with economic values. The waste hydrochloric acid can be concentrated into a useful hydrochloric acid to be used for cleaning steel in industry. The ferric sulphate and ferrous sulfate can be used in the dyeing industry, the leather industry, and waste water treatment, as a solid polymerization water purifier, and a sewage treatment agent, thereby reducing the investment on the equipment cost by the product with high economic value.

Description

49798U 曰 皇號901_ι 五、發明說明（1) 本發明係有關於 方法及裝置，其係使 亞鐵轉化形成硫酸亞 酸，而硫酸亞鐵再通 鋼鐵置於空氣中 之生鏽，而於鋼鐵之 酉文來清洗氧化之鋼鐵 大量使用於此領域中 成為Ϊ衣保—環^中之^最 之廢酸液約33萬噸， 、直接加氣氧化法、 法等數種方法·，詳述 1 ·喷霧燒培法：其採 適用於較大的廢酸 嘲/月，才可能具 化鐵的價位高，所 在進行噴霧燒培技 鍵技術難以突破， 2 ·直接加氯氧化法： 全問題，所產生之 於國内已經是供過 並無法回收其效益 3 ·樹脂吸附法及擴散 而已，而剩下的廢 決廢酸液的問題。 修正 一種自廢酸液中提取有用 用硫酸與廢酸液進行反應 鐵，並會產生濃度高於廢 入臭氧以氧化生成硫酸鐵 無可避免會發生氧化反應 表面生成氧化鐵。工業上 表面，因為鹽酸費用較便 ，但其·伴而產生之大量廢 大問題，目前國内鋼鐵業 其中廢酸液之處理方式有 樹脂吸附法、真空蒸顧法 如下： 用流體化燒培法設備投資 處理規模，處理廢酸量需 有投資可行性；因產生資 以投資可行性也可能相對 術時，則另需考慮喷嘴問 且製造成本甚高。 技術上需注意加氯反應單 氣化鐵則需考慮銷售問題 於求的情形，所以使用本 〇 透析法：僅可以自廢酸液 酸液則無法再使用，所以 物質之製造 ，以將氯化 酸液中之鹽 〇 即一般所說 一般使用鹽 宜，所以被 酸液處理即 每年所產生 喷霧燒培法 與硫酸置換 成本1¾，較 大於1，000 源化產品氧 面；但其中 題，不僅關 元之工業安 ，因氯化鐵 法在產業上 中回收鹽酸 無法真正解49798U King No. 901_ι 5. Description of the invention (1) The present invention relates to a method and a device which convert ferrous iron to form sulfuric acid, and ferrous sulfate is then rusted by placing steel in the air and rusting it. The text used to clean and oxidize steel is widely used in this field to become the most expensive waste acid solution in the clothing industry. It is about 330,000 tons, and several methods such as direct aeration oxidation method, method, etc., detailed 1 · Spray firing method: It is suitable for large waste acid / month, it is possible to have high price of chemical iron, it is difficult to break through the technology of spray firing, 2 · Direct chlorination oxidation method: Full The problem arises from the fact that it has been supplied in the country and cannot be recovered. 3. Resin adsorption method and diffusion, and the remaining waste is the problem of waste acid solution. Correction A kind of useful extraction from waste acid solution. Sulfuric acid reacts with waste acid solution to produce iron, and the concentration will be higher than waste. Ozone will be oxidized to form iron sulfate. Oxidation reaction will inevitably occur, and iron oxide is formed on the surface. On the industrial surface, due to the relatively low cost of hydrochloric acid, it has a large amount of waste problems. At present, the domestic steel industry has the following methods to treat waste acid liquid: resin adsorption method and vacuum evaporation method as follows: The scale of equipment investment and processing requires investment feasibility to deal with the amount of waste acid. Because the investment feasibility of generating resources may also be relative to the time of surgery, the nozzle needs to be considered and the manufacturing cost is very high. It is technically necessary to pay attention to the fact that the monogasification of iron in the chlorination reaction needs to consider the situation of sales. Therefore, this dialysis method is used: only the self-spent acid solution can not be used, so the manufacture of substances to chlorinate The salt in the acid solution, that is, generally speaking, is generally suitable for salt, so being treated by the acid solution means that the annual cost of spray roasting and sulfuric acid replacement is 1¾, which is greater than the oxygen surface of the 1,000 source products; Not only Guan Yuan's industrial safety, but because of the industrial recovery of hydrochloric acid by the ferric chloride method, there is no real solution.

第4頁 497980 案號 90100420 、發明説明（2)Page 4 497980 Case No. 90100420, Description of Invention (2)

修正 4•真空蒸德法·處理其廢酸液問題時，可產生鹽酸及氯化 亞鐵，但$反應溫度太高，係造成設備成本增加，且氯 化亞鐵目則只使用在廢水上，故使用領域上並不廣泛。 因此如何針對上述問題而提出一種新穎之自廢酸液 中提取有用物質’不僅可以解決大量廢酸液的問題，又可 以產生高經濟價值之副產物，且其設備投資成本可以比較 低，又可回收鹽酸供給再使用，長久以來一直是使用者殷 切盼望及本發明人念茲在茲者’而本發明人基於多年從事 於化工相關產品之研究、開發、及銷售實務經驗，乃思及 改良之忌念’窮其個人之專業知識，經多方研究設計、專Amendment 4 • Vacuum distillation method · When treating its waste acid solution, hydrochloric acid and ferrous chloride can be generated, but the $ reaction temperature is too high, which causes increased equipment costs, and the ferrous chloride is only used in wastewater , So it is not widely used in the field. Therefore, how to propose a novel extraction of useful substances from waste acid solution to the above problems can not only solve the problem of a large amount of waste acid solution, but also generate high economic value by-products, and the equipment investment cost can be relatively low, and Recovered hydrochloric acid is supplied and reused for a long time. The user has long been eagerly looking forward to the inventor ’s intentions. The inventor is based on many years of practical experience in research, development, and sales of chemical-related products. Don't miss the poor personal expertise, researched and designed by many parties,

題探討’終於研究出一種自廢酸液中產生硫酸鐵之製造方 法，可解決上述之問題。爰是 本發明之主要目的’在於提供一種自自廢酸液中提取 有用物質之製造方法及裝置，在於可產生高經濟值之硫酸 鐵及硫酸亞鐵’並可以回收廢酸液之鹽酸。 本發明之次要目的’在於提供一種自廢酸液中提取有 用物質之製造方法及裝置’其因為產生高經濟價值的三樣 產物，將可以快速回收投資之設備成本。Question Discussion ’Finally, a manufacturing method to produce iron sulfate from waste acid solution was developed to solve the above problems. The main purpose of the present invention is to provide a manufacturing method and device for extracting useful substances from waste acid liquid, which can produce high-economic-value iron sulfate and ferrous sulfate 'and can recover hydrochloric acid of waste acid liquid. A secondary object of the present invention is to provide a manufacturing method and device for extracting useful substances from waste acid liquid, which can quickly recover investment equipment costs because it produces three products with high economic value.

本發明之又一目的，在於提供一種自廢酸液中提取有 用物質之製造方法及裝置’在於解決清洗鋼鐵時所產生之 廢酸液。 茲為使貴審查委員對本發明之結構特徵及所遠成之 功效有更進一步之瞭解與認識，謹佐以較佳之實施例圖及 配合詳細之說明，說明如後：Another object of the present invention is to provide a manufacturing method and apparatus for extracting useful substances from waste acid liquid, which is to solve the waste acid liquid generated when cleaning steel. In order to make your reviewing members have a better understanding and understanding of the structural features and far-reaching effects of the present invention, I would like to accompany the drawings of the preferred embodiment and the detailed description, as explained below:

497980 案號 90100420 月 曰 修正 五、發明說明（3) 結構示意圖；如圖所示，首先係將含有濃度可為 %與氣化亞鐵11%之廢酸液與濃度為70%〜90% 反應器槽1 〇中，在操作溫度為8 〇〜9 0 °c之情形下 鐵與琉酸將產生反應而生成硫酸亞鐵及鹽酸，此 之鹽酸與廢酸液中之5 %鹽酸混合，藉以提高整 濃度。 由於氣化亞鐵與硫酸反應生成產物之一的鹽 氣其為氣態存在，以吹風器60帶動氣流經一管線 吸收塔70，其產生濃度為21 %的鹽酸集中於稀酸 於反應器10與吸收塔70之間有一除霧器50，其係 之鐵予以分離去除，藉以提高鹽酸之純度，而至 之較高濃度後之2 1 %鹽酸將可以回收再使用於一 等清洗產業中，以清洗鋼鐵表面之氧化鐵。 另一方面，氯化亞鐵與硫酸反應生成產物之 鐵將被導引至沉澱槽2 〇中，並藉由一水洗裝置（ 進行水洗動作，因為其含有一些酸性，所以須經 序並將殘餘的酸液除去。在本發明中水洗後的酸 一管線重新回到反應器1 〇中以進行再回收程序， 洗處理過之硫酸亞鐵將再經除水器3 0與水進行分 如此將可得硫酸亞鐵之粉末，即可成為本發明需 一。而濕餅狀之硫酸亞鐵，也可以再加入水並通 臭氧反應器4 0中以進行氧化反應，使其硫酸亞鐵 酸鐵，即可得產物硫酸鐵溶液。 廢鹽酸5 硫酸加入 ’氯化亞 時新產生 體鹽酸之 酸與水蒸 而連線至 槽80，而 將氣態中 此所產生 般鋼鐵業 一硫酸亞 未顯示） 水清洗程 液可再經 而已經水 離步驟， 得產品之 入臭氧於 氧化成硫 用於染整 而本發明所產生之硫酸亞鐵之用途廣泛，適 業、皮革業與廢水處理；而硫酸亞鐵於氧化後之 硫酸鐵可497980 Case No. 90100420 Rev. V. Description of the Invention (3) Schematic diagram of the structure; as shown in the figure, firstly, a waste acid solution containing a concentration of 11% and gasified iron 11% is reacted with a concentration of 70% to 90% In the tank 10, iron and sulphuric acid will react to produce ferrous sulfate and hydrochloric acid at an operating temperature of 80 to 90 ° C. This hydrochloric acid is mixed with 5% hydrochloric acid in the waste acid solution, whereby Increase the whole concentration. As the salt gas, one of the products formed by the reaction between gasification of ferrous iron and sulfuric acid, exists in a gaseous state, a blower 60 is used to drive the gas stream through a line absorption tower 70, and the hydrochloric acid with a concentration of 21% is concentrated in the dilute acid in the reactor 10 and There is a demister 50 between the absorption tower 70, and the iron of the system is separated and removed to improve the purity of hydrochloric acid. The higher concentration of 21% hydrochloric acid can be recovered and reused in the first-class cleaning industry. Cleaning iron oxide on steel surface. On the other hand, the iron produced by the reaction between ferrous chloride and sulfuric acid will be guided to the precipitation tank 20, and will be washed by a water washing device (because it contains some acidity, it must be sequenced and the residual In the present invention, the acid-line after water washing is returned to the reactor 10 to perform a recovery process, and the washed ferrous sulfate will be separated from the water through the water remover 30 so that The powder of ferrous sulfate can be obtained, which can become one of the requirements of the present invention. The ferrous sulfate in the form of wet cake can also be added to water and passed through the ozone reactor 40 to carry out the oxidation reaction to make it ferrous sulfate. The product ferric sulfate solution can be obtained. Waste hydrochloric acid 5 Sulfuric acid is added to the acid of the newly produced hydrochloric acid and water when steaming and connected to the tank 80, and the general production of iron and steel in the gaseous state is not shown. ) The water cleaning process liquid can be passed through the water separation step again. The product can be oxidized into ozone and oxidized to sulfur for dyeing and finishing. The ferrous sulfate produced by the present invention has a wide range of applications, suitable for industry, leather industry and wastewater treatment; and Ferrous sulfate and oxygen After the iron sulfate may

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以使用在 系宗上 物質之製 ，以將氯 酸液中之 。故本發 ，應符合 提出發明 惟以 非用來限 ’舉凡依 精神所為 利範圍内 固體聚 所述， 造方法 化亞鐵 鹽酸， 明實為 我國專 專利申 上所述 定本發 本發明 之均等 合淨水劑與 本發明係有 及裝置，其 轉化形成硫 而硫酸亞鐵 一具有新穎 利法所規定 請，祈 鈞 者，僅為本 明實施之範 申請專利範 變化與修錦 污水處 關於一 係使用 酸亞鐵 再通入 性、進 之專利 .局早曰 發明之 圍， 圍所述 ，均應 理劑。 種自廢酸液中提取有用 硫酸與廢酸液進行反應 ’並會產生濃度高於廢 臭氧以氧化生成硫酸鐵 步性及可供產業利用者 申請要件無疑，爰依法 賜准專利，至感為禱。 一較佳實施例而已，並 之形狀、構造、特徵及 包括於本發明之申請專 圖號簡單說明： 10反應器 2 0 沉澱槽 3 0除水器 40臭氧反應器 50除霧器 6 〇吹風器 70 吸收塔 80稀酸槽Based on the material used in the lineage, the chloric acid solution is used. Therefore, the present invention should meet the requirements of the invention, but not for the purpose of limiting the use of solid materials within the scope of the benefits of the spirit, and the method of ferrous hydrochloric acid, which is clearly stated in the patent application of our country. The combined water purification agent and the present invention are equipped with a device, which transforms to form sulfur and ferrous sulfate has the provisions of a novel interest law. Those who pray, apply for patent changes only for the implementation of this application and the Sewage Treatment Department. A series of patents that use ferrous acid to re-enter and enter. The bureau said earlier that the scope of inventions should be treated as described. This kind of self-extracting useful sulfuric acid from waste acid solution reacts with waste acid solution 'and will produce a concentration higher than waste ozone to oxidize to generate iron sulfate. The steps are no doubt applicable to industrial users, and the patent is granted according to law. prayer. It is only a preferred embodiment, and its shape, structure, features and application drawing numbers included in the present invention are simply explained: 10 reactors 2 0 sedimentation tanks 3 0 water separators 40 ozone reactors 50 demisters 6 air blowing Device 70 Absorption tower 80 Dilute acid tank

497980 _案號90100420_年月日_修正 圖式簡單說明 第1圖：本發明之一較佳實施例示意圖。497980 _Case No. 90100420_Year Month Day_Amendment Brief Description of Drawings Figure 1: A schematic diagram of a preferred embodiment of the present invention.

Claims (1)

一種自廢酸液中提取有用物質之製造裝置，其主要結 構包括有： 反應器’其主要係用以裝載廢酸液與硫酸，且在此 反應器中進行廢酸液與硫酸之反應； 一吸收塔，可藉由一管線連接於該反應器之另一側， 可吸收並收集廢酸液與硫酸進行反應後所產生之鹽 酸； 一沈殿槽，可藉由一管線連接於反應器之另一側，可 收集廢酸液與硫酸進行反應後所生成之硫酸亞鐵， 該裝置可將硫酸亞鐵内所含有之酸物質去除； 一除水器，連接於該沈澱槽，係將硫酸亞鐵中所含之 水分子去除而可得至少一硫酸亞鐵粉末；及 一臭氧反應器，連接於該沈澱槽，並可輸入至少一臭 氧，而可將硫酸亞鐵中氧化以反應生成硫酸鐵。、 如申請專利範圍第1項所述之製造裝置，尚可包括有 一吹風器以連接於反應器，其可帶動鹽酸氣體至吸收 塔中。 2申請專利範圍第1項所述之製造裝置，尚可包括除 霧器以連接於反應器與吸收塔間，可用以係將鐵離子 予以去除者。 如申請專利範圍第1項所述之製造裝置，其中該沈澱 槽中係可藉由一水洗裝置沖洗硫酸亞鐵以去除其内含 之水分者。 一種自廢酸液中提取有用物質製造裝置之方法，其主A manufacturing device for extracting useful substances from waste acid liquid, the main structure includes: a reactor 'which is mainly used for loading waste acid liquid and sulfuric acid, and the reaction of waste acid liquid and sulfuric acid is performed in this reactor; An absorption tower can be connected to the other side of the reactor through a pipeline, which can absorb and collect the hydrochloric acid produced by the reaction of the waste acid liquid and sulfuric acid; a Shendian tank can be connected to the other of the reactor through a pipeline On one side, ferrous sulfate produced by the reaction of waste acid solution and sulfuric acid can be collected. This device can remove the acid substances contained in ferrous sulfate; a water remover connected to the precipitation tank, which will At least one ferrous sulfate powder can be obtained by removing water molecules contained in iron; and an ozone reactor connected to the precipitation tank, and at least one ozone can be input, and the ferrous sulfate can be oxidized to react to generate iron sulfate . The manufacturing device described in item 1 of the scope of the patent application may further include a blower to be connected to the reactor, which can drive hydrochloric acid gas to the absorption tower. 2 The manufacturing device described in item 1 of the scope of patent application may further include a demister to connect between the reactor and the absorption tower, which can be used to remove iron ions. The manufacturing device according to item 1 of the scope of the patent application, wherein the precipitation tank is a device capable of rinsing ferrous sulfate by a water washing device to remove the moisture contained therein. Method for producing useful substance from waste acid solution 497980 修正 多號 90100420 六、申請專利範圍 要步驟係包括有： 將廢酸液與硫酸置入_反應器中，使硫酸與廢酸液中 之氯化亞鐵反應，以生成硫酸亞鐵； 將硫酸亞鐵殘餘之酸藉由一水洗裝置除去，並藉由一 除水器將部分之硫酸亞鐵内所含有之水分移除，以 遂得硫酸亞鐵粉末；及 再將部分之硫酸亞鐵進行氧化反應以得到硫酸鐵溶液 b ·如申請專利範圍第5項所述之方法，其中該廢酸液中 廢鹽酸濃度為5 %。 7 ·如申請專利範圍第$項所述之方法，其中該廢酸液加 入硫酸時，所提高之鹽酸濃度為21 %。 8 ·如申請專科範圍第5項所述之方法，其中該廢酸液中 所含之氣化亞鐵為11 %。 9 ·如申請專利範圍第5項所述之方法，其中該輸入反應 器中與廢酸液反應之硫酸濃度為70%〜93%。 I 0 ·如申請專利範圍第5項所述之方法，其中該廢酸液與 硫酸之反應時，係以一吹風器產生之氣體以帶動氣態 狀之產物位移。 II ·如申請專利範圍第1 0項所述之方法，其中該氣態狀之 產物係為鹽酸與水蒸氣與鐵。 1 2 ·如申請專利範圍第1 0項所述之方法，其中係可藉由一 除霧器將氣態狀之鹽酸與水蒸氣中之鐵予已去除。 13 ·如申請專利範圍第5項所述之方法，其中該廢酸浪與497980 Amendment No. 90100420 Sixth, the steps for applying for a patent include the steps of: placing a waste acid solution and sulfuric acid into a reactor, and reacting sulfuric acid with ferrous chloride in the waste acid solution to form ferrous sulfate; The residual acid of ferrous sulfate is removed by a water washing device, and a part of the water contained in the ferrous sulfate is removed by a water remover to obtain a ferrous sulfate powder; and a part of the ferrous sulfate is obtained; An oxidation reaction is performed to obtain a ferric sulfate solution b. The method as described in item 5 of the scope of the patent application, wherein the concentration of waste hydrochloric acid in the waste acid solution is 5%. 7. The method according to item $ in the scope of patent application, wherein when the waste acid solution is added with sulfuric acid, the hydrochloric acid concentration is increased by 21%. 8. The method as described in item 5 of the scope of the application, wherein the waste acid liquid contains 11% of the ferrous gas. 9. The method according to item 5 of the scope of patent application, wherein the sulfuric acid concentration in the input reactor to be reacted with the waste acid solution is 70% to 93%. I 0 · The method as described in item 5 of the scope of the patent application, wherein the reaction of the waste acid liquid with sulfuric acid is carried out by a gas generated by a blower to move the gaseous product. II. The method as described in item 10 of the scope of the patent application, wherein the gaseous products are hydrochloric acid and water vapor and iron. 1 2 · The method according to item 10 of the scope of patent application, wherein the gaseous hydrochloric acid and iron in water vapor can be removed by a demister. 13 · The method as described in item 5 of the scope of patent application, wherein the waste acid wave and 第10頁 497980 _案號90100420_年月日__ 六、申請專利範圍 硫酸之工作反應溫度為7 2〜9 2 °C。 1 4 ·如申請專利範圍第5項所述之方法，其中該硫酸亞鐵 清洗後之酸液，則迴流至廢酸液與硫酸之反應槽内。 1 5 ·如申請專利範圍第5項所述之製造方法，其中硫酸亞 鐵之氧化反應係加入臭氧。Page 10 497980 _Case No. 90100420_Year_Month__ Sixth, the scope of patent application The working reaction temperature of sulfuric acid is 7 2 ~ 9 2 ° C. 14 · The method according to item 5 of the scope of the patent application, wherein the acid solution after the ferrous sulfate washing is refluxed into the reaction tank of the waste acid solution and the sulfuric acid. 15 · The manufacturing method as described in item 5 of the scope of patent application, wherein the oxidation reaction of ferrous sulfate is adding ozone. 第11頁Page 11