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五、發明說明（1) (一）先前技術 傳統可膨脹石墨粉之製作首見於1 9 6 8美國UCAR公司專 利（U S p a t e n t 3，4 0 4，0 6 1 )，利用此種粉末經 8 0 0。0 1 0 0 0 °C之高溫熱處理，可製得蠕虫狀（vermi form)石墨；將此 蠕虫狀石墨經適當軋壓處理，可製得柔性石墨片（板）。上 述粉末典型之製作方法為（US patent 3,494,382 ):取98% 濃硫酸体積份量為9，6 5 %硝酸体積份量為1，將鱗片狀石 墨粉（重量約為濃硫酸1 / 4〜1 / 4 0 0 )先置入硫酸中浸泡並攪 拌均勻，接著倒入硝酸並持續攪拌1 5分鐘至數小時，溫度 控制在室溫至1 0 5 t：間（隨石墨粉粒徑不同而變動），最 後，取出天然石墨粉並予以水洗、烘乾，在8 0 0 °C〜1 0 0 0 °C 高溫環境下1 5秒〜3 0秒製得8 0 c c / g〜3 0 〇 c c / g蠕虫狀石墨。 傳統製程具有如下三項缺點： 1 · 製得蠕虫狀膨脹石墨之膨脹倍率不高，對於應用此粉 末製作柔性石墨板時，機械性質無法提昇。若應用作為除 油材時，其吸除油污之效率較差。 2 ·隨粉末粒徑變化需改變操作時間，最高達數小時之 久，耗時甚久。 3 · 酸液混合物無法重複使用。 、、、ί、* 另於1 98 9年中國大陸專利（CN 1 0 32 3 25'A)、、高倍率膨脹 的鱗片石墨的製造方法// ，利用氣化鐵、作^插入劑，過錳酸 鉀作為氧化劑，在濃硫酸、硝酸混合液;卷':，對浸泡石墨粉 進行氧化及插入化學作用，結果製得可膨脹至V. Description of the invention (1) (1) The production of the traditional expandable graphite powder of the prior art was first seen in U.S. Patent U.S.A. (U.S. patent 3,400,4.01), and the use of this powder was tested by 80 Vermi form graphite can be obtained by high temperature heat treatment at 0.0 1 0 0 ° C; flexible graphite sheet (plate) can be obtained by subjecting this vermicular graphite to appropriate rolling treatment. The typical manufacturing method of the above powder is (US patent 3,494,382): taking 98% concentrated sulfuric acid by volume and 9,65% nitric acid by volume, the flake graphite powder (weight is about 1/4 ~ 1/4) 0 0) Soak in sulfuric acid and stir well, then pour in nitric acid and continue stirring for 15 minutes to several hours, and control the temperature from room temperature to 105 t: between (varies with the particle size of graphite powder), Finally, the natural graphite powder was taken out, washed with water, and dried. In a high-temperature environment at 800 ° C ~ 100 ° C, 15 seconds ~ 30 seconds were used to produce 80 cc / g ~ 3 0 cc / g. Worm-like graphite. The traditional process has the following three disadvantages: 1. The expansion ratio of the worm-like expanded graphite is not high. When applying this powder to make flexible graphite plates, the mechanical properties cannot be improved. If it is used as a degreasing material, its efficiency in sucking and removing oil stains is poor. 2 · The operation time needs to be changed as the powder particle size changes. It can take up to several hours and takes a long time. 3 · The acid mixture cannot be reused. ,,, ί, * Also produced in the Chinese mainland patent (CN 1 0 32 3 25'A) in 1989, a method of manufacturing high-scale expanded flake graphite //, using gasified iron as an insert, Potassium manganate as an oxidant, in a mixed solution of concentrated sulfuric acid and nitric acid; Volume ': Oxidation and chemical insertion of immersed graphite powder, resulting in expansion to
520344 五、發明說明（2) 4 0 0^/^〜6 0 0 〇(：/^之可膨脹石墨粉。此篇專利製程具有如 下四項缺點： 1 · 操作步驟太繁複且耗時甚久（約1 2小時）。 2. 使用到高價之氯化鐵及過錳酸鉀，不利經濟成本且增 加製程之複雜性。 3. 氯化鐵及過錳酸鉀與酸液相混，若未能操作得當，會 引：起爆炸，具工安潛在問題。 4. 酸液混合物無法重複使用。 (二）發明目的 本發明之目的為：建立一種由鱗片狀天然石墨粉製作 可膨脹性石墨粉之製程，其步驟簡易省時且酸液混合物可 重複使用。同時又可製出400cc/g〜500cc/g之螺虫狀石 墨。 (三）技術内容 本發明為一種可膨脹性石墨粉製作方法。以粒徑為2 0 目〜8 0目鱗片狀天然石墨粉為原料，取濃硫酸（9 5 %〜9 8 % )、 硝酸（6 9%〜71%)及水等，將其均勻混合並控制混合酸溶液 溫度在1 5 °C〜3 0 °C，量取適量之2 0目〜8 0' :目：鱗片狀天然石墨 粉，將此石墨粉置入混合酸液中，並以2 Cl·? 5 0 r p m轉速攪拌 1 0分鐘〜6 0分鐘，隨後取出浸酸之天然石.墨'粉，並以< 3 5 °C之冷水予以水洗清除表面餘酸後，再予脫水、烘乾處520344 V. Description of the invention (2) 4 0 0 ^ / ^ ~ 6 0 0 〇 (: / ^ of expandable graphite powder. This patent process has the following four disadvantages: 1 · The operation steps are too complicated and time-consuming (Approximately 12 hours). 2. The use of high-priced ferric chloride and potassium permanganate is unfavorable to economic costs and increases the complexity of the process. 3. Ferric chloride and potassium permanganate are mixed with the acid phase. Proper operation will lead to: explosion, potential safety problems. 4. Acid-liquid mixtures cannot be reused. (2) Purpose of the invention The purpose of the present invention is to establish a flaky graphite powder made from flaky natural graphite powder. The process is simple and time-saving, and the acid mixture can be reused. At the same time, 400cc / g ~ 500cc / g wormworm graphite can be produced. (III) Technical content The present invention is a method for making expandable graphite powder. .Take natural flake graphite powder with particle size of 20 mesh to 80 mesh as raw material, take concentrated sulfuric acid (95% ~ 98%), nitric acid (69% ~ 71%), water, etc. and mix them evenly And control the temperature of the mixed acid solution at 15 ° C ~ 30 ° C, take an appropriate amount of 20 mesh ~ 8 0 ': mesh: scale Natural graphite powder, put this graphite powder into a mixed acid solution, and stir at 2 Cl ·? 50 rpm for 10 minutes to 60 minutes, and then take out the soaked natural stone. Ink 'powder, and < Wash at 3 ° C with cold water to remove residual acid on the surface, and then dewater and dry.
520344 五、發明說明（3) __ 理。即可獲得高膨叮 示。 艮仡牛之可衫脹石墨粉。製程如圖1所 本發明使用水作 ☆ 一 中之N03-1，HS〇 y 硝酸之解離介質，使得混酸液 插入天然石墨之層S〇4 2等離子可大量解離，並氧化、 逸散，造成膨脹倍j結構;^待受熱時可大力撐裂層間結構 墨粉發明技術，未^大之纟而虫狀石墨。先前有關可膨脹石 酸、硝酸及水等先二使作為解離介質；本發明採濃琉 術則將鱗片狀石篇二，此合後再加入石墨粉浸泡，先前技 硝酸並持續攪掉·太，/又心1 §夂中並攪拌均勻，接著倒入 粒徑大小^目時間為1〇分鐘〜歸鐘，無論 赤棧有1 ’抑或是浸酸時間甚長（達12小時以上）；本發明 之I液此0物可重複使用，先前技術則無法重複使用。 例1 ·取3 6 0 cc濃硫酸（98%)、2〇〇〇硝酸（7〇%)及2〇“水等溶 液’將其均勻混合並控制混合酸溶液溫度在2 0 t：，量取1 3 克3 2目〜4 G目之鱗片狀天然石墨粉，將此石墨粉置入混合 酸液中’並以20〜50rpm轉速攪拌20分鐘且溫度維持25。(：左 右’隨後取出浸酸之天然石墨粉，並以< 3 5 t之冷水予以 水洗清除表面餘酸後，再予脫水、烘乾處釋。取製得之可 膨脹性石墨粉，置入95(TC，空氣氣氛£:、&中1 5秒，測得 其膨脹後体積為4 5 0 c c / g。 '，.、 * 例2 :取3 6 0 CC濃硫酸（98%)、20cc硝酸（70%)與20cc水等溶 520344 五、發明說明（4) 液，將其均勻混合並控制混合酸溶液溫度在2 0 °C，稱取4 0 克鱗片狀天然石墨粉（2 0目〜.8 0目），將此石墨粉置入混合 酸液中，並以2 0〜5 0 r p m轉速攪拌3 0分鐘且溫度維持2 5 °C左 右，隨後取出浸酸之天然石墨粉，並以< 3 5 °C之冷水予以 水洗清除表面餘酸後，再予脫水、烘乾處理。取製得之可 膨脹性石墨粉，置t，空氣氣.氛之爐中15秒，測得 其膨脹後体積為4 1 0 。 、'‘Λ、、'、、、、、:·: :'、一 _ ，Ά、、ν 餘者條件如同例2 测得其 例3 :除 了硝酸（70%k^%2cc 膨脹後体積為4 1 5 c c厂g:、 例4 :除了水取1 8 c c，餘者條件如同例2 ，測得其膨脹後 体積為4 0 0 c c / g，以上舉例之膨脹倍率如表1所示。 表1 · 可膨脹性石墨粉之不同條件之膨脹後體積 IPill520344 V. Description of Invention (3) __ Management. You get a high-inflation bite. Gentle yak's swellable graphite powder. The process is shown in Figure 1. The present invention uses water as the dissociation medium of N03-1, HSOy and nitric acid in ☆ No. 1, so that the mixed acid solution can be inserted into the natural graphite layer S042, and the plasma can be dissociated in large quantities, and oxidized and escaped, resulting Expansion times j structure; ^ When heated, it can vigorously support the interlaminar structure toner invention technology, which is not as big as worm-like graphite. Previously, expandable lithic acid, nitric acid, and water were used as dissociation media. In the present invention, the scaly stones are used as the disintegrating medium. After that, graphite powder is added for soaking. ， / 心心 1 § 夂 and stir well, then pour the particle size ^ mesh time is 10 minutes ~ Guizhong, whether the red stack has 1 'or the acid pickling time is very long (up to 12 hours); this The invention I solution can be reused, but the prior art cannot be reused. Example 1 · Take 3 600 cc concentrated sulfuric acid (98%), 2000 nitric acid (70%) and 20 "water and other solutions' to mix them uniformly and control the temperature of the mixed acid solution at 20 t: Take 1 3 grams of 3 2 mesh to 4 G mesh flake-shaped natural graphite powder, put this graphite powder in a mixed acid solution, and stir at 20 to 50 rpm for 20 minutes while maintaining the temperature at 25. (: left and right ', then take out the dip Natural graphite powder with acid, washed with cold water <3 5 t to remove residual acid on the surface, and then release it from dehydration and drying. The expandable graphite powder obtained was placed in 95 (TC, air atmosphere) £ :, & 15 seconds, the volume after expansion was measured to be 450 cc / g. ',., * Example 2: Take 3 600 CC concentrated sulfuric acid (98%), 20cc nitric acid (70%) It is solubilized with 20cc water 520344 V. Description of the invention (4) Liquid, mix it uniformly and control the temperature of the mixed acid solution at 20 ° C. Weigh 40 grams of flake-like natural graphite powder (20 mesh ~ .80 mesh ), Put this graphite powder into a mixed acid solution, and stir at a speed of 20 to 50 rpm for 30 minutes and maintain the temperature at about 25 ° C, and then take out the acid-soaked natural graphite powder, and use < 3 5 ° C cold It was washed with water to remove the residual acid on the surface, and then dehydrated and dried. The obtained expandable graphite powder was placed in a t-air oven for 15 seconds, and its expanded volume was measured to be 4 1 0. , "Λ ,, ',,,,, ::::', _, Ά,, ν The conditions of the rest are the same as those measured in Example 2. Except for nitric acid (70% k ^% 2cc, the volume after expansion is 4 1 5 cc factory g :, Example 4: Except for the water 1 8 cc, the remaining conditions are the same as in Example 2. The volume after expansion is measured to be 4 0 cc / g. The expansion ratios of the above examples are shown in Table 1. Table 1 · Expandable volume of expandable graphite powder under different conditions IPill
例1 例2 例3 .例4 濃硫酸（98%) cc 360 360 360 360 硝’酸(70%) cc 20 20 22 20 水CC 20 20 20 18 天然石墨粉（目） 13g(32〜40) 40g(20〜80) 40g(2Q〜80) 40g(20〜80) 膨脹後體積（cc/g) 450 410 415、 400 ('、 第8頁 520344Example 1 Example 2 Example 3. Example 4 Concentrated sulfuric acid (98%) cc 360 360 360 360 Nitric acid (70%) cc 20 20 22 20 Water CC 20 20 20 18 Natural graphite powder (mesh) 13g (32 ~ 40) 40g (20 ~ 80) 40g (2Q ~ 80) 40g (20 ~ 80) Volume after expansion (cc / g) 450 410 415, 400 (', page 8 520344