201114684 - 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種製造方法，特別是指一種以未燃 碳製成具有石墨性能之粉末材料與多孔性材料的方法。 【先前技術】 工業技術的進步使人們生活愈來愈便利，相對產生的 各種工業廢棄物或污染物也愈來愈多’近年來，環保意識 曰漸抬頭，世界各國無不對各種工業廢棄物或污染物採取 • 更為嚴格的管制措施。 工業廢棄物或污染物雖然會造成環境的汙染，但許多 的工業廢棄物或污染物也潛藏著許多可以回收再利用的物 ' 質’最為常見的當屬電路板上的銅金屬甚至是貴金屬（金、 銀），所以，先進國家除了對各種工業廢棄物或污染物採取 更為嚴格的管制措施外，更積極的回收各種工業廢棄物或 污染物中的可用資源。 相關研究指出’由於燃燒後的飛灰中含有大量的未燃 鲁 碳粒以及由釩、鎳…等金屬元素所構成的少量化合物，因此 右將燃燒後的飛灰直接排入大氣中，除了污染空氣外，若 為人體所吸入將有害健康，因此，各國都會將燃燒後的飛 灰加以收集處理，避免危害人體健康。 近年來’中、美、日、韓…等國除了收集燃燒後的飛灰 外’更積極研發從燃燒後的飛灰中提煉出有價金屬的方法 ’將飛灰中的釩、鎳…等金屬元素與未燃碳分離，最後將有 價金屬用以生產相關的金屬製品，而殘留的未燃碳粒則當 201114684 成事業廢棄物加以掩埋。 【發明内容】 因此，本發明之目的，即在提供一種以未燃碳製成具 有石墨性能之粉末材料的方法。 本發明之另-目的，即在提供一種以未燃碳製成具有 石墨性能之多孔性材料的方法。 於疋，本發明以未燃碳製成具有石墨性能之粉末材料 的方法，依序包含一收集步驟、一純化步驟、一研磨步驟 ’及—石墨化步驟。 该收集步驟是收集含多孔質未燃碳的含碳飛灰；該純 化步驟疋去除多孔質未燃碳中所含雜質；該研磨步驟是研 磨經純化步驟之多孔質未燃碳至平均粒徑5〇μιη以下。 該石墨化步驟是將平均粒徑50μιη以下的多孔質未燃碳 於惰性氣體的環境下加熱至1600°C〜2700°C並維持一設定時 間再冷卻至室溫，將多孔質未燃碳製作成具有石墨性能之 粉末材料。 而本發明以未燃碳製成具有石墨性能之多孔性材料的 方去’包含一收集步驟、一純化步驟、一混合步驟、一成 型步驟、一燒結步驟，及一二次加工步驟。 s亥收集步驟是收集含多孔質未燃碳的含碳飛灰；該純 化步驟是去除多孔質未燃碳中所含雜質；該混合步驟是將 黏著劑、添加物與經純化步驟的多孔質未燃碳相互混合， 而獲得一成型原料。 該成型步驟是利用1 〇〇kg/cm2以上的壓力壓結該成逛原 201114684 • 料成為一毛胚；該燒結步驟是於惰性氣體的環境下將該毛 胚加熱至900。(：以上並維持一設定時間再冷卻至室溫。 該二次加工步驟是利用機械加工法加工經該燒結步驟 的毛胚獲得一具有石墨性能之多孔性材料。 本發明之功效在於：利用回收含多孔質未燃碳的含碳 飛灰’經由收集步驟、純化步驟、研磨步驟，及石墨化步 驟’將多孔質未燃碳製作成具有石墨性能之粉末材料與多 孔性材料，以分別應用於鋰電池的負極材料與 # …中，藉此充分利用再生資源，有效減少工業廢：物 或污染物。 【實施方式】 ' 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圖式之一個較佳實施例的詳細說明中，將可 清楚的呈現。 參閱圖卜本發明以未燃碳製成具有石墨性能之粉末材 料的方法之較佳實施例，包含一收集步驟11、一純化步驟 12、一研磨步驟13，及一石墨化步驟14。 該收集步驟11是收集含多孔質未燃碳的含碳飛灰，於 本較佳實施例中的含碳飛灰是以靜電集塵方式所收集燃煤 飛灰，當然在實際的應用上也可以是燃油飛灰或其他含有 多孔質未燃碳的含碳飛灰，而收集的方式除了靜電集塵方 式外也可以是利用旋風集塵方式收集，並不應為本實施例 的揭露所囿限。 該純化步驟12是利用酸洗純化、鹼洗純化或高溫純化 201114684 方式，去除多孔質未燃碳中所含雜質。該純化步驟12是利 用硫酸酸洗純化後再採用高溫純化方式去除多孔質未燃碳 中所含雜質，所述咼溫純化方式是以9〇〇。匸〜27〇〇£>c加熱多 孔質未燃碳3G分鐘以上以去除多孔質未燃破中所含雜質。 於本較佳實苑例中’是以丨8〇〇。匸加熱多孔質未燃碳3〇分鐘 〇 該研磨步驟13是將經純化步驟丨2之多孔質未燃碳研 磨至平均粒徑50μηι以下，藉由粒徑的限制，以提供應用於 二次鋰電池的負極材料的最佳運用狀態。 該石墨化步驟14是將平均粒徑5〇μηι以下的多孔質未 燃奴置於一加熱爐中且將該加熱爐抽真空後通入體積百分 率99%以上的惰性氣體，將平均粒徑5〇μιη以下的多孔質 未燃碳置於惰性氣體的環境下加熱至i 〜27〇〇(>c並維持 -設定時間再冷卻至室溫，❹孔質未燃碳製作成石墨材 料粉末。其中，本較佳實施例所選用的惰性氣體是可以是 氦、氖、氬、氪、氙、氡、氮的其中之一，或其中兩者以 上的組合·’而所設定的加熱時間是在1〇分鐘以上，再以風 力冷卻、或低溫惰性氣體冷卻、或流體冷卻，或自然冷卻 方式（於加熱爐中冷卻）將經加熱的多孔質未燃碳冷卻到室溫 〇 在考慮價格與取得的方便性，於本較佳實施例中，是 以體積百分率99%的氮來隔絕氧的作用，並將加熱爐中的 多孔質未燃碳於2300t下加熱1〇分鐘，使多孔質未燃碳石 墨化，再以自然冷卻方式將加熱後的多孔質未燃碳於加熱 201114684 " 爐中冷卻2至6小時以冷卻至室溫，而獲得具有石墨性能 之粉末材料。 參閱表1，利用本發明之方法將未燃碳製成具有石墨性 忐之粉末材料（實驗1、2 )具有平均292mAh/g的可逆電 容與穩定的電性迴圈維持率（1〇〇cycle達97%以上），可應用 在二次鐘電池的負極材料。 實驗1 實驗2 充電電容量（mAh/g) 340.78 345.48 放電電容量（mAh/g) 289.22 295.29 不可逆電容量（mAh/g) 51.56 50.19 可逆電容量（mAh/g) 285.41 286.43 電性迴圈維持率（％) 98.68 97.00 參閱圖2’本發明以未燃碳製成具有石墨性能之多孔性 材料的方法，包含-收集㈣21、一純化步驟22、一研磨 步驟23、一混合步驟24、一成型步驟乃、一燒結步驟％ ，及一二次加工步驟27 。 該收集步驟21 {收集含多孔質未燃碳的含碳飛灰，於 本較佳實施財的含碳飛灰是以靜f錢方式所收集燃煤 飛灰，當,然在實際的應用上也可以是燃油飛灰或其他含有 多孔質未燃碳的含碳驗，而收集的方式除了靜電集塵方 式外也可以是利用旋風集塵方式收集，並不應為本實施例 的揭露所囿限。 201114684 該純化步驟22疋利用1洗純化、驗洗純化或高溫純化 方式’去除多孔質未燃碳中所含雜質。該純化步驟22方式 是利用硫酸酸洗純化後再採用高溫純化方式去除多孔質未 燃碳中所含雜質，所述高溫純化方式是以900°C〜2700°C加 熱多孔質未燃碳30分鐘以上以去除多孔質未燃碳中所含雜 質。於本較佳實施例中，是以18〇〇°C加熱多孔質未燃碳3〇 分鐘。 該研磨步驟23是將經純化步驟22之多孔質未燃碳研 磨至至平均粒徑50μιη以下，藉由粒徑的限制，以提供應用 於散熱材料的最佳運用狀態。 該混合步驟24是將黏著劑、添加物與經純化步驟22 的多孔質未燃碳相互混合，而獲得一成型原料，其中的黏 著劑是選自樹酯或瀝青其中之一；而其中的添加物選自：鋁 、鐵、銅、高填土、氧化石夕、氧化紹、氮化在呂、氮化石夕、 氧化鈦或矽鋁酸鹽，及其任兩種以上的組合，於本較佳 實施例中的黏著劑是樹酯，該添加物是氧化鋁。 ，該成型步驟25是利用i〇0kg/cm2以上的壓力壓結該成 型原料成為—毛胚，其中，該成型步驟25採冷壓法或熱壓 法其中之一方式麼結該成型原料’於本較佳實施例十是以 冷塵法以刚kg/cm2以上的麼力壓結該成型原料成為一毛胚 抽直2結㈣Μ是將毛胚置於—加熱射且將該加熱爐 1在通入體積百㈣鴨以上的惰性氣體，且使該毛 ““體的環境下加熱至赋並維持-設定時間後再 201114684 冷部至室溫，使黏著劑充分地與多孔質未燃碳相互結合， 進而使該毛胚固化，其中，惰性氣體是可以是氦、氖、氬 、氪、氙、氡、氮的其中之一，或其中兩者以上的組合； 而所設定的加熱時間是在3〇分鐘以上，再以風力冷卻:或 低溫惰性氣體冷卻、或流體冷卻，或自然冷卻（於加熱爐中 冷卻）將經加熱的多孔質未燃碳冷卻到室溫。 在考慮價格與取得的方便性，於本較佳實施例中是BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a manufacturing method, and more particularly to a method of producing a powder material having a graphite property and a porous material from unburned carbon. [Prior Art] Advances in industrial technology have made people's lives more and more convenient, and more and more industrial wastes or pollutants have been produced. In recent years, environmental awareness has gradually risen, and all countries in the world have all kinds of industrial waste or Contaminants are taken • More stringent control measures. Although industrial waste or pollutants cause environmental pollution, many industrial wastes or pollutants also have many substances that can be recycled. The most common one is copper metal or even precious metals on the circuit board. Gold, silver), therefore, in addition to more stringent control measures for various industrial wastes or pollutants, advanced countries are more active in recovering available resources from various industrial wastes or pollutants. Related research pointed out that 'the fly ash after combustion contains a large amount of unburned Lu carbon particles and a small amount of compounds composed of metal elements such as vanadium, nickel, etc., so the fly ash after combustion is directly discharged into the atmosphere, except for pollution. Outside the air, if it is inhaled by the human body, it will be harmful to health. Therefore, all countries will collect and treat the burnt fly ash to avoid harming human health. In recent years, in addition to the collection of burnt fly ash, countries such as China, the United States, Japan, and Korea have been more active in researching and extracting valuable metals from burnt fly ash, such as vanadium, nickel, etc. in fly ash. The elements are separated from the unburned carbon, and finally the valuable metals are used to produce the relevant metal products, and the remaining unburned carbon particles are buried as 201111684 commercial waste. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method of producing a powder material having graphite properties from unburned carbon. Another object of the present invention is to provide a method of making a porous material having graphite properties from unburned carbon. In the present invention, the present invention comprises a method of preparing a powder material having graphite properties from unburned carbon, and sequentially comprises a collecting step, a purifying step, a grinding step and a graphitization step. The collecting step is to collect carbonaceous fly ash containing porous unburned carbon; the purifying step is to remove impurities contained in the porous unburned carbon; the grinding step is to grind the porous unburned carbon to the average particle diameter in the purification step 5〇μιη below. In the graphitization step, porous unburned carbon having an average particle diameter of 50 μm or less is heated to 1600 ° C to 2700 ° C in an inert gas atmosphere, and maintained for a set period of time and then cooled to room temperature to prepare porous unburned carbon. It is a powder material with graphite properties. The present invention comprises the steps of: a collecting step, a purifying step, a mixing step, a forming step, a sintering step, and a secondary processing step of forming a porous material having graphite properties from unburned carbon. The shai collecting step is to collect carbonaceous fly ash containing porous unburned carbon; the purifying step is to remove impurities contained in the porous unburned carbon; the mixing step is to apply the adhesive, the additive and the porous material in the purification step. Unburned carbon is mixed with each other to obtain a molding material. The molding step is to use a pressure of 1 〇〇kg/cm2 or more to press the original 201114684. The material is a blank; the sintering step is to heat the blank to 900 in an inert gas atmosphere. (: The above and maintaining a set time and then cooling to room temperature. The secondary processing step is to use a machining process to process the blank of the sintering step to obtain a porous material having graphite properties. The effect of the present invention is: recycling The carbonaceous fly ash containing porous unburned carbon is formed into a powder material having a graphite property and a porous material through a collecting step, a purifying step, a grinding step, and a graphitization step to respectively apply The negative electrode material of the lithium battery and the ..., thereby fully utilizing the renewable resources, and effectively reducing industrial waste: substances or contaminants. [Embodiment] The foregoing and other technical contents, features and effects of the present invention are referred to the following. A detailed description of a preferred embodiment of the drawings will be apparent. Referring to the drawings, a preferred embodiment of the method for producing a powder material having graphite properties from unburned carbon, comprising a collecting step 11, a purification step 12, a grinding step 13, and a graphitization step 14. The collecting step 11 is to collect carbonaceous fly ash containing porous unburned carbon. The carbon-containing fly ash in the preferred embodiment is a coal-fired fly ash collected by electrostatic dust collection. Of course, in practical applications, it may be a fuel fly ash or other carbon-containing fly containing porous unburned carbon. In addition to the electrostatic dust collection method, the collection method may be collected by cyclone dust collection, and should not be limited to the disclosure of the embodiment. The purification step 12 is performed by pickling purification, alkali washing purification or high temperature. Purifying the impurities contained in the porous unburned carbon by purifying the method of 201114684. The purification step 12 is to purify the impurities contained in the porous unburned carbon by high-temperature purification after purification by sulfuric acid pickling, and the purification method is 9〇〇.匸~27〇〇£>cheat porous unburned carbon for 3G minutes or more to remove impurities contained in the porous unburned.匸 heating the porous unburned carbon for 3 minutes. The grinding step 13 is to grind the porous unburned carbon of the purification step 丨2 to an average particle diameter of 50 μm or less, and to provide a secondary lithium battery by limiting the particle size. The best anode material for the pool The graphitization step 14 is to place a porous unburned slave having an average particle diameter of 5 〇μη or less in a heating furnace and evacuate the furnace to an inert gas having a volume percentage of 99% or more. The porous unburned carbon having a particle diameter of 5 〇μηη or less is heated to i ～27 〇〇 (>c and maintained for a set time and then cooled to room temperature in an inert gas atmosphere, and the unburned carbon is made into graphite. a material powder, wherein the inert gas selected in the preferred embodiment is one of 氦, 氖, argon, krypton, xenon, krypton, nitrogen, or a combination of two or more The time is more than 1 minute, and then the cooled porous unburned carbon is cooled to room temperature by wind cooling, low temperature inert gas cooling, or fluid cooling, or natural cooling (cooling in a heating furnace). The price and the convenience obtained, in the preferred embodiment, the effect of isolating oxygen by 99% by volume of nitrogen, and heating the porous unburned carbon in the heating furnace at 2300t for 1 minute to make the porous Graphitization of unburned carbon And then to natural cooling after heating a porous carbon unburned heated 201114684 " furnace cooled to 2-6 hours cooled to room temperature, to obtain a powder material having the properties of graphite. Referring to Table 1, the unburned carbon was made into a powdery material having graphite crucible by using the method of the present invention (Experiments 1, 2) having an average reversible capacitance of 292 mAh/g and a stable electrical loop maintenance ratio (1〇〇cycle) Up to 97%), can be applied to the negative electrode material of the secondary clock battery. Experiment 1 Experiment 2 Charging capacity (mAh/g) 340.78 345.48 Discharge capacity (mAh/g) 289.22 295.29 Irreversible capacity (mAh/g) 51.56 50.19 Reversible capacity (mAh/g) 285.41 286.43 Electrical loop retention (%) 98.68 97.00 Referring to Figure 2, a method of making a porous material having graphite properties from unburned carbon, comprising - collecting (four) 21, a purification step 22, a grinding step 23, a mixing step 24, and a molding step That is, a sintering step %, and a second processing step 27 . The collecting step 21 {collects the carbonaceous fly ash containing porous unburned carbon, and the carbonaceous fly ash in the preferred implementation method collects the coal fly ash in a static way, when, in practical application, It may also be a fuel fly ash or other carbon-containing test containing porous unburned carbon, and the collection method may be collected by a cyclone dust collection method other than the electrostatic dust collection method, and should not be disclosed in the embodiment. limit. 201114684 This purification step 22 utilizes 1 wash purification, wash purification or high temperature purification to remove impurities contained in the porous unburned carbon. The purification step 22 is to remove impurities contained in the porous unburned carbon by high-purity purification by acid washing with sulfuric acid, and the high-temperature purification method is to heat the porous unburned carbon at 900 ° C to 2700 ° C for 30 minutes. The above is to remove impurities contained in the porous unburned carbon. In the preferred embodiment, the porous unburned carbon is heated at 18 ° C for 3 minutes. This grinding step 23 is to grind the porous unburned carbon of the purification step 22 to an average particle diameter of 50 μm or less, which is limited by the particle diameter to provide an optimum use state for the heat dissipating material. The mixing step 24 is to mix the adhesive, the additive and the porous unburned carbon of the purification step 22 to obtain a molding material, wherein the adhesive is one selected from the group consisting of a resin or a pitch; and the addition thereof The material is selected from the group consisting of aluminum, iron, copper, high-filled earth, oxidized stone, oxidized, nitrided, lanthanum, titanium oxide or strontium aluminate, and a combination of two or more thereof. The adhesive in the preferred embodiment is a resin and the additive is alumina. The molding step 25 is to pressurize the molding material into a blank by using a pressure of i 〇 0 kg/cm 2 or more, wherein the molding step 25 adopts one of cold pressing method or hot pressing method to bond the molding material to In the preferred embodiment, the forming material is pressed by the cold dust method with a force of just above kg/cm2 to become a blank, and the knot is straightened. 2 (4) The blank is placed in a heat-emitting manner and the heating furnace 1 is placed at Passing an inert gas of more than one hundred (four) ducks, and heating the hair to "enhance and maintain" - after setting time, then 201114684 cold part to room temperature, so that the adhesive is fully interacted with porous unburned carbon Combining, and further curing the blank, wherein the inert gas may be one of krypton, neon, argon, krypton, xenon, krypton, nitrogen, or a combination of two or more; and the set heating time is For more than 3 minutes, the heated porous unburned carbon is cooled to room temperature by wind cooling: or low temperature inert gas cooling, or fluid cooling, or natural cooling (cooling in a heating furnace). In considering the price and the convenience of the acquisition, in the preferred embodiment
以體積百分率99%以上的4來隔絕氧的作用，並將加熱爐 中的多孔質未燃碳於9〇η；下加熱3G分鐘，再以自然冷卻 方式將加純的毛歸加錢巾冷卻5至6小時以冷卻至 室溫，而使該毛胚固化。 少驟27疋利用機械加工法加工經該燒結步 驟26的毛胚獲得—石墨材料，其中的機械加卫法可以是切 削加工或研磨加工，於本較佳實施例中，是以研磨加工經 該燒結步驟26的毛胚獲得-具有石墨性能之多孔性材料。 由於’具有石墨性能之多孔性材料的「多孔」特性， 且多孔質未燃碳的平均粒徑以下，所以該較佳實施例 所製成具有石墨性能之多孔性材料比表面積較大，而具有 較好的散熱效果，能廣泛地應用在散熱結構上。 綜上所述，本發明以未燃碳製成具有石墨性能之粉末 =多孔性材料的方法，藉由回收含多孔質未燃碳的含 石反飛灰，以充分利用再生資湃，右 选札 丹生貝/原' 彳政》成少工業廢棄物或污 :物；再經由收集步驟u、純化步驟12、研磨步驟13與石 墨化步驟Μ而獲得可應用在二次㈣池之負極的具有石墨 201114684 陡月b之叙末材料，再者，利用該混合步驟24將黏著劑、添 · 加物與經純化步驟22的多孔質未燃碳相互混合，再經成裂 步驟25成型成該毛胚，然後再利用加熱爐加熱該毛胚使該 毛胚固化成具有石墨性能之多孔性材料，有效應用在高散 熱需求的電子產品上，故確實能達成本發明之目的。 准以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明實施之範圍，即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 修 圖1疋一流程圖，說明本發明以未燃碳製成具有石墨 性能之粉末材料的方法；及 圖2是一流程圖，說明本發明以未燃碳製成具有石墨 性能之多孔性材料的方法。 10 201114684 • 【主要元件符號說明】 11 、 21 •收集步驟 24·· .......混合步驟 12 ' 22· •純化步驟 25 ·· •…·…成型步驟 13 、 23· -研磨步驟 26，· .......燒結步驟 14· ·· 石墨化步驟 27·· .......二次加工步驟 11The effect of oxygen is insulated by a volume percentage of 99% or more, and the porous unburned carbon in the heating furnace is heated at 9 〇η; it is heated for 3 G minutes, and then the pure hair is added to the money towel to cool by natural cooling. The embryo is allowed to solidify by cooling to room temperature for 5 to 6 hours. The graphite material obtained by the blanking process of the sintering step 26 is processed by a machining process, wherein the mechanical reinforcement method may be a cutting process or a grinding process. In the preferred embodiment, the grinding process is performed by the grinding process. The blank of the sintering step 26 obtains a porous material having graphite properties. Due to the "porous" nature of the porous material having graphite properties and the average particle diameter of the porous unburned carbon, the porous material having the graphite property of the preferred embodiment has a larger specific surface area and has a larger specific surface area. Better heat dissipation effect, can be widely applied to the heat dissipation structure. In summary, the present invention uses a non-combustible carbon to produce a powder-porous material having graphite properties by recovering the stone-containing fly ash containing porous unburned carbon to fully utilize the recycled assets. Zadanba / original 'Zhengzheng' into industrial waste or sewage; and through the collection step u, purification step 12, grinding step 13 and graphitization step Μ to obtain a graphite that can be applied to the secondary (four) pool of graphite 201114684 The material of the steep moon b, and further, the mixing step 24 is used to mix the adhesive, the additive and the porous unburned carbon of the purification step 22, and then form the blank by the cracking step 25. Then, the blank is heated by a heating furnace to solidify the blank into a porous material having graphite properties, and is effectively applied to an electronic product having high heat dissipation requirements, so that the object of the present invention can be achieved. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart illustrating a method of producing a powder material having graphite properties from unburned carbon; and FIG. 2 is a flow chart illustrating that the present invention is made of unburned carbon. A method of graphite properties of porous materials. 10 201114684 • [Explanation of main component symbols] 11 , 21 • Collection step 24 · · . . . Mixing step 12 ' 22 · Purification step 25 ·· •...·...Molding step 13 , 23 · - Grinding step 26,· . . . Sintering Step 14 ··· Graphitization Step 27··....Second Processing Step 11