487681 A7 ------B7 五、發明說明（） 發明的背景和動機 鎂化學品爲重要之工業原料，由於其具有多項優越特 性而被廣泛運用，因而許多國家均致力於鎂化學品之生 產。海水中富含鎂及其化合物，且取之不盡，而製造氯化 鈉食鹽之廢液（滷水）及海水淡化廠所產生之高鹽廢水（滷 水），更是最適合之原料。高純度之鹼式碳酸鎂不僅是化妝 品、藥物及顏料等之原料外，更是製造高純度氧化鎂之先 驅物（precursor)。在台灣四面環海，礦產資源匱乏的環境， 及近年來國內在精密工業的需求下，必須使工業原料更高 純度化及細化，利用海水或滷水來提煉高純度之鹼式碳酸 鎂無疑已成爲重要之硏發目標。 發明的基本目的 本發明之主要目的在於應用海（滷）水來生產高純度 鹼式碳酸鎂，其可作爲製造電子級氧化鎂之先驅物 (precursor)。爲達到所謂電子級氧化鎂粉末材料之嚴格要 求，目前世界上利用礦石來生產鎂之製程均無法達到，本 發明運用不同之處理程序，將海水中之鎂離子分離純化， 製備碳酸鎂，再精製成高純度鹼式碳酸鎂。 所謂電子級氧化鎂，亦即用於微電子零件之材料’需 求爲微細且粒徑分佈均勻之輕燒、重質（總密度（bulk density)〉0.2g/cm3)高純度之氧化鎂粉體。高純度微細且粒 徑分佈均勻才能製做精密而穩定之元件；輕燒才能使氧化 鎂粉體擁有高度結晶能力；重質才能使粉體燒結成品’體 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) tT: -線· 經濟部智慧財產局員工消費合作社印製 487681 A7 ____B7__ 五、發明說明（2 ) 積不至大幅縮減及避免幾何形狀扭曲。電子級氧化鎂之用 途爲用做半導體零件之封裝、電容器、基板、硏磨劑。目 前市面上使用之電子級氧化鎂以IWATANI公司之產品 (MJ-30)爲例，其純度超過99.9%，比表面積達28.0(m2/g)， 平均粒徑爲0.32// m。本發明之目標即以鹵水爲原料做出 與上述產品同級之氧化鎂：純度大於99.9%，比表面積大於 25.0(m2/g)，平均粒徑小於 0.5// m，總密度（bulk density) > 0.2g/cm3 〇 文獻回顧 由海水（滷水）純化鎂離子（鎂化合物）之方法主要有： 碳氨法、共浮法、溶劑萃取法等，相關專利及文獻略述如 下： 碳氨法： 藉由調整海水之酸鹼度先除去重金屬離子，接著一般 均加入硫酸鎂之水合物來沉澱鈣，過濾後加入碳酸鈉或碳 氨等含碳酸根鹽類，以形成碳酸鎂沉澱，再經由水洗洗去 可溶性之鈉鹽及鉀鹽。此程序之優點爲製程簡單。但因除 鈣過程中，鈉、鉀及氯離子含量過高造成硫酸鈣沉澱不完 全，無法達到高純度碳酸鎂之要求。且若欲大符降低鈉、 鉀離子含量則又需反覆沖洗，消耗大量用水，且提高了產 品之損失率。爲此製程之缺點。（CN1076426A、US3980753) 共浮法（Coflotation): 此法乃是將油酸鈉（Sodium Oleate)加入海水中以形 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： -線· 經濟部智慧財產局員工消費合作社印製 487681 A7 B7 五、發明說明（3 ) 成油酸鎂及油酸鈣之沉澱物，藉此優先將鈉、鉀離子除去， 接著再以硝酸及甲醇之混合溶液將該沉澱物溶解，並加入 硫酸鎂以沉澱硫酸鈣，達到鈣離子去除之目的，而得到純 的鎂離子溶液。此製程之優點爲優先去除鈉、鉀離子，造 成硫酸鈣沉澱較完全，含鈣雜質去除效果較好。然而添加 之藥劑成本較高爲其缺點。（M· A· Kabil，et· al. Separation Science and Technology, 30(20), pp3787-3799, 1995) 溶劑萃取法： 將海水調整酸鹼度後以有機溶劑（e.g. HEP/Kerosene) 進行萃取，並反覆以純鎂溶液淸洗有機相，再針對有機相 進行反萃，得到純鎂溶液，並進行有機相之再生及再利用。 此方法之優點爲同時去除海水中鈉、鉀及鈣等雜質，但操 作繁複則爲其缺點。（US542 1 386) 解決問題之主要技術手段 由於高純度鹼式碳酸鎂在純度上須達99.9%以上，本發 明方法主要利用下列步驟：以電解透析法（Electrodiolysis) 電解透析海水或滷水，而移除其中小粒徑單價陽離子及氯 離子；經由沉殿過濾法（Precipitation-Filtration)主要以無水 硫酸鈣（CaS04)沉澱形式來達到移除鈣離子的目的；加入一 水可溶性碳酸鹽使鎂離子以碳酸鎂型式析出；再以通入 C02的手段使析出的碳酸鎂沉澱與水的混合物轉化爲鹼式 碳酸鎂沉澱。 鈣的硫酸鹽有多種型式如CaS04_H20、CaS04_2H2〇（石 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 487681 A7 B7 五、發明說明（4 ) 膏）及無水硫酸鈣（CaS04)，其中以後者在水中具最低的溶 解度，因此對於鈣離子的去除是否完全，鈣的硫酸鹽的型 式具關鍵的地位。本案發明人發現氯離子濃度低的條件下 不僅會形成想要的無水硫酸鈣，而且無水硫酸鈣在水中的 溶解度亦隨著氯離子濃度降低而降低。所以在本發明中首 先利用電解透析法來移除氯離子，以利於後續鈣離子的去 除，同時達成小粒徑單價陽離子的移除。 另外溫度對於鈣的硫酸鹽的形成型式亦有影響，在大 於40°C時會形成想要的無水硫酸鈣，因此經由沉澱過濾法 (Precipitation-Filtration)以無水硫酸鈣（CaS04)沉殿形式來 移除鈣離子的步驟較佳的係在大於40°C的溫度進行。 較佳具體實施例之詳細說明 本發明之一較佳具體實施例的流程可分爲兩部份：純 化及製取，茲分述如下： I .純化 I .1電透析 電透析是使用帶電荷的離子交換膜，在電位差爲驅動 力的作用下，將液體中之荷電成份予以分離，如採用不同 孔隙之薄膜，亦可進一步將不同粒徑之荷電分子分離。海 水中最主要之成份爲鈉、鉀之鹽類，在將鹵水濾去成份較 不穩定的不溶物雜質後，濾液以電透析方式除去此小粒徑 單價陽離子，其去除率可高達75%以上。 表1電透析效果分析 -7· 玉紙張尺度適財關家標準（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· -線 487681 A7 B7 五、發明說明（5 ) 金屬離子 處理前濃度（ppm) 處理後濃度（ppm) 去除率（％) Na + 40000 10000 75 K + 35000 5000 85 Ca2+ 20000 10000 50 Mg2 + 35000 30000 15 I .2沉澱過濾 由於電解透析中尙含有大量之鈣離子，故須以其他方 法去除。一般除鈣方法，係以二水硫酸鈣（石膏）沉澱去除， 其操作條件對去除效果有不良影響。本發明係在有利於無 水硫酸鈣沉澱形成的條件下進行（先去除氯離子及50°C)， 故可達較佳的去除效果。將硫酸鎂（MgSCV7H2〇 172.53g)， 以對液中鈣濃度成比例的方式加入，使其轉換爲硫酸鈣沉 澱後再去除。其結果如下z ------------_裝--- (請先閱讀背面之注意事項再填寫本頁) 訂· 經濟部智慧財產局員工消費合作社印製 表2鈣離子去除效果分析 MgS04/CaCl2 莫耳比 金屬離子 處理前濃度 (ppm) 處理後濃度 (ppm) 去除率 (%) Ca 25000 1500 94 1.2 Mg 45000 40000 10 Ca 25000 500 98 1.6 Mg 45000 45000 0 由表2可知加入硫酸根有明顯達到去除鈣離子的效 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ^7681 A7487681 A7 ------ B7 V. Description of the invention () Background and motive of the invention Magnesium chemical is an important industrial raw material. Because it has many superior characteristics and is widely used, many countries are committed to the development of magnesium chemicals. produce. Seawater is rich in magnesium and its compounds, and it is inexhaustible. Wastewater (brine) for making sodium chloride table salt and high-salt wastewater (brine) produced by desalination plants are the most suitable raw materials. High-purity basic magnesium carbonate is not only a raw material for cosmetics, pharmaceuticals, and pigments, but also a precursor for producing high-purity magnesium oxide. Surrounded by the sea on Taiwan, the environment of scarce mineral resources, and the domestic demand for precision industries in recent years, it is necessary to make industrial raw materials more purified and refined. The use of seawater or brine to refine high-purity basic magnesium carbonate has undoubtedly become Important goals. Basic object of the invention The main object of the present invention is to use sea (brine) water to produce high-purity basic magnesium carbonate, which can be used as a precursor for the manufacture of electronic-grade magnesium oxide. In order to meet the strict requirements of the so-called electronic grade magnesium oxide powder materials, the current process of producing magnesium from ore in the world cannot be achieved. The present invention uses different processing procedures to separate and purify magnesium ions in seawater, prepare magnesium carbonate, and then refine Into high purity basic magnesium carbonate. The so-called electronic magnesia, which is the material used for microelectronic parts, requires light-burned, heavy (bulk density> 0.2g / cm3) high-purity magnesia powder with fine and uniform particle size distribution. . High purity, fine and uniform particle size distribution can be used to make precise and stable components; light burning can make the magnesium oxide powder have a high crystallization ability; heavy weight can make the powder sintered product. The size of this paper applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) tT: -Line · Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 487681 A7 ____B7__ 5. Description of the invention (2) Dramatically reduce and avoid distortion of geometry. Electronic grade magnesium oxide is used for packaging, capacitors, substrates, and abrasives of semiconductor parts. The electronic grade magnesium oxide currently used in the market is the product of IWATANI (MJ-30), which has a purity of more than 99.9%, a specific surface area of 28.0 (m2 / g), and an average particle size of 0.32 // m. The objective of the present invention is to use the brine as a raw material to make magnesium oxide of the same grade as the above products: purity is greater than 99.9%, specific surface area is greater than 25.0 (m2 / g), average particle size is less than 0.5 // m, total density (bulk density) & gt 0.2g / cm3 〇 Literature review The methods for purifying magnesium ions (magnesium compounds) from seawater (brine) are: carbon-ammonia method, co-float method, solvent extraction method, etc. The relevant patents and literatures are briefly described as follows: Carbon ammonia method: By adjusting the pH of seawater, heavy metal ions are removed first, and then magnesium sulfate hydrate is generally added to precipitate calcium. After filtration, carbonate salts such as sodium carbonate or ammonia are added to form magnesium carbonate precipitates, which are then washed and washed away. Soluble sodium and potassium salts. The advantage of this procedure is the simple process. However, due to the excessive content of sodium, potassium, and chloride ions during the calcium removal process, the precipitation of calcium sulfate was incomplete, and it could not meet the requirements of high-purity magnesium carbonate. And if you want to greatly reduce the content of sodium and potassium ions, you need to repeatedly wash, consume a lot of water, and increase the loss rate of the product. The disadvantage of this process. (CN1076426A, US3980753) Coflotation: This method is to add sodium oleate to seawater to shape the paper size to apply Chinese National Standard (CNS) A4 (210 X 297 mm) (please (Please read the notes on the back before filling this page) Order:-Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 487681 A7 B7 V. Description of the invention (3) Precipitates of magnesium oleate and calcium oleate The sodium and potassium ions are preferentially removed, and then the precipitate is dissolved with a mixed solution of nitric acid and methanol, and magnesium sulfate is added to precipitate calcium sulfate to achieve the purpose of removing calcium ions, and a pure magnesium ion solution is obtained. The advantages of this process are the preferential removal of sodium and potassium ions, resulting in complete precipitation of calcium sulfate and better removal of calcium-containing impurities. However, the higher cost of added chemicals is a disadvantage. (M · A · Kabil, et · al. Separation Science and Technology, 30 (20), pp3787-3799, 1995) Solvent extraction method: After adjusting the pH of seawater, it is extracted with an organic solvent (eg HEP / Kerosene) and repeated The organic phase is washed with a pure magnesium solution, and then the organic phase is back-extracted to obtain a pure magnesium solution, and the organic phase is regenerated and reused. The advantage of this method is the simultaneous removal of sodium, potassium, and calcium impurities in seawater, but complicated operation is its disadvantage. (US542 1 386) The main technical solution to the problem Because the purity of high-purity basic magnesium carbonate must be above 99.9%, the method of the present invention mainly uses the following steps: Electrolytic dialysis (Electrodiolysis) to electrolyze seawater or brine, and remove Remove small-sized monovalent cations and chloride ions; Precipitation-Filtration mainly uses calcium sulfate (CaS04) precipitation to achieve the purpose of removing calcium ions; adding water-soluble carbonate to make magnesium ions to Precipitation of magnesium carbonate type; the mixture of precipitated magnesium carbonate and water was converted into basic magnesium carbonate precipitation by means of introducing CO 2. There are many types of calcium sulfate such as CaS04_H20, CaS04_2H2〇 (The size of the stone paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)) -------------- installation --- (Please read the precautions on the back before filling out this page). Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Employees' Cooperatives of the Ministry of Economic Affairs and printed by the Consumers' Cooperatives of the Ministry of Economic Affairs. Calcium (CaS04), the latter of which has the lowest solubility in water, so for the complete removal of calcium ions, the type of calcium sulfate plays a key role. The inventors of the present invention found that under conditions where the chloride ion concentration is low, not only the desired anhydrous calcium sulfate is formed, but also the solubility of the anhydrous calcium sulfate in water decreases as the chloride ion concentration decreases. Therefore, in the present invention, electrolytic dialysis is first used to remove chloride ions to facilitate the subsequent removal of calcium ions, and at the same time to achieve the removal of monovalent cations with small particle sizes. In addition, the temperature also affects the formation of calcium sulfate, and the desired anhydrous calcium sulfate will be formed when the temperature is higher than 40 ° C. Therefore, the calcium sulfate (CaS04) is used as the sink through precipitation-filtration method. The step of removing calcium ions is preferably performed at a temperature greater than 40 ° C. Detailed description of a preferred embodiment The process of a preferred embodiment of the present invention can be divided into two parts: purification and preparation, which are described as follows: I. Purification I.1 Electrodialysis Electrodialysis uses charged Under the action of the potential difference as the driving force, the ion exchange membrane of the ion exchange membrane can separate the charged components in the liquid. If different membranes are used, the charged molecules with different particle diameters can be further separated. The most important ingredients in seawater are sodium and potassium salts. After the brine is filtered to remove the unstable insoluble impurities, the filtrate is used to remove this small particle size monovalent cation by electrodialysis, and the removal rate can be as high as 75% or more. . Table 1 Analysis of the effects of electrodialysis 487681 A7 B7 V. Description of the invention (5) Concentration before metal ion treatment (ppm) Concentration after treatment (ppm) Removal rate (%) Na + 40000 10000 75 K + 35000 5000 85 Ca2 + 20000 10000 50 Mg2 + 35000 30000 15 I. 2 Precipitation and filtration Because the radon contains a large amount of calcium ions in electrolytic dialysis, it must be removed by other methods. The general calcium removal method uses calcium sulfate dihydrate (gypsum) precipitation to remove, and its operating conditions have an adverse effect on the removal effect. The present invention is carried out under conditions favorable for the formation of anhydrous calcium sulfate precipitation (removal of chloride ions and 50 ° C first), so a better removal effect can be achieved. Magnesium sulfate (MgSCV7H20, 172.53g) was added in a proportion proportional to the calcium concentration in the liquid, and it was converted to calcium sulfate precipitation and then removed. The results are as follows: ------------_ Installation --- (Please read the precautions on the back before filling out this page) Order Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economy Removal effect analysis MgS04 / CaCl2 Mole ratio metal ion concentration before treatment (ppm) concentration after treatment (ppm) removal rate (%) Ca 25000 1500 94 1.2 Mg 45000 40000 10 Ca 25000 500 98 1.6 Mg 45000 45000 0 The effect of adding calcium sulfate is obvious to remove calcium ions. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ^ 7681 A7
1、發明說明（6 ) 經濟部智慧財產局員工消費合作社印製 果，在硫酸鎂對氯化鈣過量的情況下效果更好，因硫酸鈣 在水中的溶解度之故，釣離子去除極限爲200ppm。硫酸鎂 如果過量，會造成多餘的硫酸根殘留於溶液中，硫酸鎂須 在1100°C以上才會熱裂解，增加後續製造電子級氧化鎂的 困擾。因此，建議加入硫酸鎂的量不大於當量比，多餘的 鈣離子利用鈣、鎂化合物的水中溶解度差異，再以濃縮或 加入碳酸根的方式與鎂離子分離。 Π .製取 ' Π . 1碳酸鎂製取 爲提取液體中之鎂離子，本發明係以碳酸鎂型式析出 獲得。其作法是先加入去離子水調整液中鎂離子濃度至 0.5M，再添加碳酸鈉，提供碳酸根與鎂離子結合，以形成 低溶解性碳酸鎂（MgC03_3H20)沉澱，在室溫下靜置稍許 後，以濾紙將不溶性碳酸鎂與濾液分離開，以去離子水淸 洗除去鈉、鉀、鈣等雜質，即可穫得碳酸鎂，由於純度僅 達99%，故二次純化將碳酸鎂轉換成鹼式碳酸鎂乃必要之 手段。 Π .2二次純化 將上述碳酸鎂與去離子水混合，該混合物呈現鹼性範 圍，加溫至40°C，並通入二氧化碳氣體，調整酸鹼値至9.5， 靜置24小時，生成鹼式碳酸鎂（4MgC(VMg(OH)2*4H2〇）沉 澱，過濾之後產物再以去離子水淸洗數次，即穫得高純度 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) !#裝 '—訂· 4 487681 A7 B7_ 五、發明說明（7 ) 鹼式碳酸鎂，純度可提升至99.9%以上。 表3二次純化之效果 金屬離子，ppm 碳酸鎂 驗式碳酸鎂 Na + 500 <100 K + 500 <100 Ca2+ 200 <100 其他 1000 <500 --------------裝--- (請先閱讀背面之注意事項再填寫本頁) -1訂· --線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）1. Description of the invention (6) The printed fruit produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is more effective in the case of magnesium sulfate over calcium chloride. Due to the solubility of calcium sulfate in water, the removal limit of fishing ions is 200 ppm . Excessive magnesium sulfate will cause excess sulfate to remain in the solution. Magnesium sulfate must be thermally decomposed above 1100 ° C, increasing the trouble of subsequent manufacture of electronic grade magnesium oxide. Therefore, it is recommended that the amount of magnesium sulfate is not greater than the equivalent ratio. Excess calcium ions use the difference in solubility of calcium and magnesium compounds in water, and then are separated from magnesium ions by concentration or carbonate. Preparation Π. 1 Preparation of magnesium carbonate In order to extract magnesium ions in the liquid, the present invention is obtained by precipitation of magnesium carbonate. The method is to first add deionized water to adjust the concentration of magnesium ions in the solution to 0.5M, and then add sodium carbonate to provide the combination of carbonate and magnesium ions to form a low-solubility magnesium carbonate (MgC03_3H20) precipitate. After that, the insoluble magnesium carbonate is separated from the filtrate by a filter paper, and the impurities such as sodium, potassium and calcium are washed with deionized water to obtain magnesium carbonate. Since the purity is only 99%, the secondary purification converts magnesium carbonate into Basic magnesium carbonate is a necessary means. Π.2 Secondary purification: The above magnesium carbonate is mixed with deionized water. The mixture is alkaline, heated to 40 ° C, and passed through carbon dioxide gas, adjusted to pH 9.5, and left to stand for 24 hours to generate alkali. Magnesium carbonate (4MgC (VMg (OH) 2 * 4H2〇) precipitated. After filtration, the product was washed with deionized water several times to obtain high purity. This paper is in accordance with China National Standard (CNS) A4 (210 X 297) (Mm) (Please read the note on the back? Matters before filling out this page)! # 装 '— 订 · 4 487681 A7 B7_ 5. Description of the invention (7) Basic magnesium carbonate, the purity can be increased to more than 99.9%. Table 3 secondary purification effect metal ion, ppm magnesium carbonate magnesium carbonate Na + 500 < 100 K + 500 < 100 Ca2 + 200 < 100 other 1000 < 500 ------------ --Install --- (Please read the precautions on the back before filling out this page) -1 Orders--Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm)