200823156 九、發明說明： 【發明所屬之技術領域】 本創作屬於環境保護及廢棄物資源再生技術領域。 【先前技術】 國内石材加工業之主要石材種類有花岗岩與大理石兩大類，由於我 國為世界石材產製市場的重要國家之一，因此每年也隨之產生大量之花 岡石與大理石加工污泥，其中大理石加工污泥含有大量碳酸約成分，具 有資源回收價值。目前國内部分大理石加工污泥係送往水泥廠作為水泥 原料，而其他剩餘之大理石加工污泥則是送往掩埋場予以最終處置。 產業所使用之碳酸約粉體傳統上大都係由大理石礦石經一系列破 碎、研磨步驟而產製，此傳統方法會消耗大量之能源，並造成破碎、研 磨之機具耗損。另經查_並無雜針對纽石加工污齡以資源回收 之專利，如中華民國專利編號似观、利用石材污泥再資源化產製水 泥纖維板之方法」，其内容主要係將石材加工污泥、漿紙污泥、紙聚板、 爐石粉及卜特蘭泥等原料，力认少許介面劑，再與水充份混合，並經過 抄造成型、裁切、高壓成型、養生脫膜及高壓養生等餘，產製出具有 防火效能之纖純，該法並無法有效败大理石加#对之有價碳酸 飼之資源。另經查國内有關碳酸賴造之專利，並未發現有利用大理石 加工污泥為原料來製備碳酸敵方法，如中華民國專利編號撕削 「碳酸权製造方法」，其_要是將生石麵行2段献消化，吹 入二氧化韻岭酸化造碳中軌轉利編號撕娜「破 7 200823156200823156 IX. Description of the invention: [Technical field to which the invention belongs] This creation belongs to the field of environmental protection and waste resource recycling technology. [Prior Art] The main stone types in the domestic stone processing industry are granite and marble. Since China is one of the important countries in the world stone production market, a large number of granite and marble processing sludge are also produced each year. Among them, the marble processing sludge contains a large amount of carbonic acid components, which has the value of resource recovery. At present, some domestic marble processing sludge is sent to cement plants as cement raw materials, while other remaining marble processing sludge is sent to the landfill for final disposal. The carbonic acid powders used in the industry have traditionally been produced by a series of crushing and grinding steps of marble ore. This traditional method consumes a large amount of energy and causes the wear and tear of the crushing and grinding machines. In addition, there is no miscellaneous patent for the recycling of resources for the processing of sewage in New Zealand, such as the Republic of China patent number, and the use of stone sludge to re-resource the production of cement fiberboard. Raw materials such as mud, pulp paper sludge, paper polyboard, hearth powder and Butland mud, and a small amount of interface agent, and then mixed with water, and through the shape, cutting, high pressure molding, health release and High-pressure health, etc., to produce a pure fiber with fire-proof performance, this method can not effectively defeat the resources of the valuable plus carbonation of the marble plus #. In addition, the domestic patent on carbonic acid was found. It was not found that the method of using marble processed sludge as raw material to prepare carbonated enemy, such as the Republic of China patent number tearing "carbonation right manufacturing method", if it is to be raw The 2nd section is digested and blown into the oxidized rhythm acidification carbonization middle rail transfer number tearing Na "breaking 7 200823156
酸化且中性化，以獲得懸浮之碳酸辑; 心繁的氣體，而將熟石灰懸浮液碳 ，中華民國專利編號00169321「針 狀文石結晶型碳酸約之製法」，其内容為使文石結晶型碳酸触^(哪 預先混合而製触減狀驗，於錢紐財加人糖闕酸化合物， 並導入⑺2氣體於漿液中，可製得大顆粒的針狀文石結晶型碳酸舞。 綜合上述結果得知，並未發現國内有任何與利用大理石加工污泥 為原料來製備高純度碳酸弼粉體之相關專利與技術。 【發明内容】 碳酸_粉體目前廣泛地運用於各產業，如造紙業、塑/橡膠業、塗/ 顏料業、油墨業及醫療衛生保健等，並隨著科技發達，近幾十年中，發 展出微奈米級碳酸弼粉體，使得碳酸弼不僅可用於填料，更具有特定之 功能性，如補強性，透明性等。根據統計，全球礙酸舞市場在2〇〇1年 時有1481萬噸，其中重質碳酸躬及輕質碳酸妈分別為1〇〇4萬噸及— 萬嘲，每年約以6.27%之成長，預估在2006年會達到2〇15萬领之需求 8 200823156 量。 我國石材工賴始發展至今，已有4G多年敎，目配成為世界 石材加工產品生產的重要國家’其中大理石為相t重要之石材加工材料 之一，應用範圍極廣，包括日常生活中的傢俱、地板、大型的雕刻作品 等’使得姻大理石加X污泥量十分龐大。由敎理石加工污泥係 由天然大理石經切割、研磨與抛光所得之細粉，其中除了含有大量之天 »峡資料’尚含有·鐵砂、卿騎磨_肺，如無法將這 # 些碳酸崎源予以回收再利用，將會造成整體社會資源之浪費，甚為可 惜，另如祕大理石加#辭崎源时，亦可減少該污泥最終處置 之環保壓力。 有鑑於此’本發明乃針對大理石加工污泥中之碳酸約進行資源回收 工作本务明内谷主要是先將大理石加工污泥在室溫下自然陰乾7天 後’將此乾燥污泥予以破碎篩分至通過2Gmesh(讀mm)以下，再使用 G.5 N鹽酸或1 N鑛或1 N醋酸，在固液比為lg/5Gml，溫度為室溫 (27 C) ’攪拌轉速為200φΙη之條件下，將此經破碎筛分之大理石加工 污泥(屬_予赠潰鱗3〇分鐘，以娜麵驗。躲集此含約 溶液以氨水調整其pH值至U，將其巾之雜f细纖，魏過渡後即 可獲得高純度之含雕液。最終將此高純度之麵溶液通入二氧化碳氣 體’使錢巾之输二氧化碳產生碳_麟，麵紐即可獲得高純 度之碳酸鈣粉體。 此高純度碳酸雜體經我國CNS國家標準之「碳酸舞測定方法(總 9 200823156 號1620 ’類!虎K712〇)」予以檢測分析，顯示其碳酸舞含量為娜❶； 另此高純度碳酸辑粉體經元素分析儀分析結果顯示，其「碳」含量佔 m6/。’亚且絲、氫、硫存又此碳簡粉體經能量分散光譜儀(聰) 分析結果顯示，其中只含碳、氧、妈三種元素，其含量分別為碳佔 II.77%、氧佔48.5〇%、約佔39 72%。因此綜合上述之分析結果可以得 知此通入C〇2後所生成之粉體為高純度碳酸與粉體，且無其他雜質。 大理石加#泥經本發明之再生綠處理後，峨得之高純度 ^ 碳酸紐體可供國内外產業界使用，同時亦可解決目前大理石加工污泥 之廢棄處理問題’故本發明可達成大理石加卫污泥魏回收再利用與廢 棄物減量之雙重目的。另大理石加工污泥中所含之碳_為粒徑極細之 粉末，故本發明於製備碳酸_體之過程中不需經過研磨步驟，相較於 傳統由大理石礦石破碎研磨生產碳酸舞粉體之方法，可節省大量之处源 消耗。故本發明應具創新性且可提供國内相關業者作為回收處理大理石 加工污泥與產製碳酸鈣粉體之依據。 【實施方式】 本發明之較佳方法示於第一圖，首先將收集之大理石加工污泥i(其 外觀如第二圖所示），經由乾燥2步驟使樣品去除水分，亦即將其置於 至溫下自然陰乾7天。再將經乾燥2步驟後之污泥予以破碎篩分3，使 其全部通過20 mesh (0.84mm)之篩網。再將此小於2〇 mesh之污泥進行 浸潰溶解4步驟，此浸潰溶解4步驟之操作條件為：固液比， 200823156 溶解溫度=27°C，攪拌轉速=2〇〇_，攪拌時間，分鐘，而浸潰溶解液 則可使周〇·5 N鹽酸或1 N硝酸或！ N醋酸。經浸潰溶解*步驟後，可 將污泥中之继其他金屬雜質溶解於溶液中，其输解回收率為1〇〇 %。再經過濾5步驟予以過濾後，即可獲得含約溶液51，另所收集之殘 渣52，則可直接進行最終處置53。 將所收集之含約洛液51進行調整pH值6步驟，調整pH值6步驟 為使用氨水將含鈣溶液51之pH值調整至12，以使含转溶液51中之金 ^ 屬雜質產生沉澱，而鈣則大部分仍留存於溶液中，待pH調整溶液61 之pH值達到12後，將pH調整溶液61進行過濾7步驟，經過濾7步 驟後，可將金屬雜質形成之沉殿物予以過濾去除，以獲得高純度之含舞 溶液71，另所收集之濾渣72，則可直接進行最終處置73。 接著將經由過濾7步驟後所獲得之高純度含鈣溶液71進行通入 C〇2氣體8步驟，通入C〇2氣體8步驟之目的為使高純度含鈣溶液7ι Φ 中之舞離子與c〇2氣體反應形成碳酸两粉體，高純度含鈣溶液71經通 入C〇2氣體8步驟5分鐘後，原澄清溶液逐漸變成混濁狀，亦即此時正 在進行合成碳酸药粉體9步驟，最終將其混濁溶液91進行過濾1〇步 驟’經過濾10步驟後，即可獲得高純度碳酸約粉體U，其外觀如第 二圖所示，另其掃描式電子顯微鏡(SEM)之照片如第四圖所示，而經過 濾10步驟所留下之濾'液101，則可直接進行最終處置102。 為使本發明更加顯現出其進步性與實用性，茲將本發明之優點列舉 如下： 11 200823156 . 1.本發明可從廢棄大理石加χ污泥巾製備㈣純度魏職體，以供 產業界利用。 2.本發明可達成大理石加工污泥資源再生與減量之雙重目的。 3·本發明可避免大理石加工污泥污染環境。 4·柄明可取代傳統將大理石礦石破碎研磨以生產碳酸妈粉體之方 法’可節省大量之能源消耗與設備損耗。 5·本發明具安全性與進步性。 φ 6·本發明具工商界與產業界之利用價值。 综上所述，本發明誠已符合發明專利之申請要件，並依法提出申 a祈π鈞局審查委貞明鑑，並辭本發明專娜，實感德便。 【圖式簡單說明】 ^ ^ 本lx月；^大理石加工污泥製備尚純度碳酸舞粉體」之實施流 程圖。 ^ 第二圖係本發明所使用之大理石加工污泥外觀照片。 第-圖係本發明所製備出之高純度碳酸約粉體之外觀照片。 * »系本所製備出之高純度碳酸_粉體之掃描式電子顯微鏡照 片。 【主要元件符號說明】 無 12Acidified and neutralized to obtain suspended carbonic acid; heart-combusted gas, and slaked lime suspension carbon, Republic of China Patent No. 00169321 "Acicular aragonite crystal type carbonic acid method", the content of which is aragonite crystal Type of carbonic acid touch ^ (Which pre-mixed to make a touch-reduction test, in the New Zealand to add sugar citrate compound, and introduce (7) 2 gas into the slurry, can produce large particles of acicular aragonite crystal type carbonic acid dance. According to the above results, it has not been found that there are any related patents and technologies in the country for preparing high-purity strontium carbonate powder by using marble processed sludge as raw materials. [Summary of the Invention] Carbonic acid-powder is currently widely used in various industries. Such as paper industry, plastic / rubber industry, coating / pigment industry, ink industry and medical and health care, and with the development of technology, in recent decades, the development of micro-nano-grade barium carbonate powder, so that barium carbonate is not only available In the filler, it has specific functions, such as reinforcement, transparency, etc. According to statistics, the global acid-sucking dance market has 14.81 million tons in 2002, of which heavy barium carbonate and light-carbonated moms are 1〇 40,000 tons and - million ridicule, about 6.27% annual growth, it is estimated that in 2006 will reach 2,150,000 lead demand 8 200823156. China's stone workers began to develop, has been 4G for many years, the match It has become an important country in the production of stone processing products in the world. Among them, marble is one of the most important stone processing materials. It has a wide range of applications, including furniture, flooring and large-scale sculptures in daily life. The amount is very large. The processing sludge from ochre is made from fine marble which is cut, ground and polished by natural marble. In addition to containing a large number of days»xia data' still contains · iron sand, Qing riding grinding _ lung, if not It is a pity that some of the carbonated sources will be recycled and reused, which is a pity. If the secret marble plus #_崎源, it can also reduce the environmental pressure of the final disposal of the sludge. 'The present invention deals with the recycling of carbonic acid in the marble processing sludge. The main task is to dry the marble processing sludge at room temperature for 7 days. The sludge is crushed and sieved to pass 2Gmesh (read mm), and then G.5 N hydrochloric acid or 1 N or 1 N acetic acid is used, the solid-liquid ratio is lg/5Gml, and the temperature is room temperature (27 C). Under the condition of 200φΙη, the crushed and sieved marble processing sludge (genus _ give the crushing scale for 3 〇 minutes, to Na Na test. Hiding this solution containing ammonia to adjust its pH to U, will The towel is made of fine fiber, and after the transition, the high-purity engraving liquid can be obtained. Finally, the high-purity surface solution is introduced into the carbon dioxide gas to make the carbon dioxide of the money towel produce carbon_lin, and the surface can be obtained. High-purity calcium carbonate powder. This high-purity carbonic acid hybrid has been tested and analyzed by the CNS national standard "Carbon Dance Measurement Method (Total 9 200823156 No. 1620 'Class! Tiger K712〇)", which shows that its carbonate dance content is Na ❶; Another high-purity carbonate powder analysis by elemental analyzer showed that its "carbon" content accounted for m6/. 'Affinity, hydrogen, sulfur and carbon thin powder by energy dispersive spectrometer (Cong) analysis results show that it contains only three elements of carbon, oxygen, mother, its content is carbon accounted for II.77%, oxygen accounted for 48.5〇%, accounting for 39 72%. Therefore, based on the above analysis results, it can be known that the powder formed after the introduction of C〇2 is high-purity carbonic acid and powder, and has no other impurities. After the marble and #泥 mud are treated by the regenerating green of the invention, the high purity ^carbonate of Chad can be used by domestic and foreign industrial circles, and can also solve the problem of disposal of the current marble processing sludge, so the invention can achieve marble addition. The dual purpose of sludge recovery and reuse and waste reduction. In addition, the carbon contained in the marble processing sludge is a powder having a very fine particle size. Therefore, the present invention does not need to undergo a grinding step in the process of preparing the carbonic acid body, and the carbonated dance powder is produced by crushing and grinding from marble ore. The method can save a lot of source consumption. Therefore, the present invention should be innovative and provide a basis for domestic related industries to recycle and process marble processed sludge and produce calcium carbonate powder. [Embodiment] The preferred method of the present invention is shown in the first figure. First, the collected marble processed sludge i (the appearance of which is shown in the second figure) is subjected to drying 2 steps to remove moisture from the sample, that is, to be placed It is naturally dry for 7 days until it is warm. The sludge after the drying of 2 steps was crushed and sieved 3, and all passed through a 20 mesh (0.84 mm) sieve. The sludge of less than 2〇mesh is further subjected to four steps of impregnation and dissolution. The operating conditions of the four steps of the impregnation and dissolution are: solid-liquid ratio, 200823156, dissolution temperature=27°C, stirring speed=2〇〇_, stirring time , minutes, and the impregnation solution can be used to make 5 N hydrochloric acid or 1 N nitric acid or! N acetic acid. After the step of impregnation and dissolution*, the other metal impurities in the sludge can be dissolved in the solution, and the recovery rate of the solution is 1%. After filtering by the filtration step 5, the solution containing about 51 and the residue 52 collected can be obtained, and the final treatment 53 can be directly carried out. The collected solution containing the Ilo liquid 51 is adjusted to a pH value of 6 steps, and the pH value is adjusted to 6 to adjust the pH of the calcium-containing solution 51 to 12 by using ammonia water to precipitate the gold-containing impurities in the reaction-containing solution 51. While most of the calcium remains in the solution, after the pH of the pH adjusting solution 61 reaches 12, the pH adjusting solution 61 is filtered for 7 steps, and after the 7 steps of filtration, the metal impurities can be formed into a sink. Filtration and removal to obtain a high-purity containing dance solution 71, and another collected filter residue 72, can be directly subjected to final disposal 73. Then, the high-purity calcium-containing solution 71 obtained after the filtration step 7 is subjected to a step of introducing a C〇2 gas, and the step of introducing the C〇2 gas into the eighth step is to make the dance ions in the high-purity calcium-containing solution 7ι Φ The c〇2 gas reacts to form two carbonic acid powders, and the high-purity calcium-containing solution 71 is passed through the C〇2 gas for 8 minutes, and the original clear solution gradually becomes turbid, that is, the synthetic carbonate powder is being carried out at this time. Step, the turbid solution 91 is finally filtered. 1 〇 Step 10 After filtration, a high-purity carbonic acid powder U can be obtained, the appearance of which is as shown in the second figure, and the scanning electron microscope (SEM) The photo is shown in the fourth figure, and the final treatment 102 can be performed directly by filtering the liquid solution 101 left by the 10 steps. In order to make the present invention more progressive and practical, the advantages of the present invention are enumerated as follows: 11 200823156. 1. The present invention can be prepared from waste marble-added sludge towel (4) purity Wei body for industry use. 2. The invention can achieve the dual purposes of regeneration and reduction of marble processing sludge resources. 3. The invention can avoid the marble processing sludge polluting the environment. 4. The handle can replace the traditional method of crushing and grinding marble ore to produce carbonated mom's powder, which can save a lot of energy consumption and equipment loss. 5. The invention is safe and progressive. φ 6· The invention has the use value of the industrial and commercial circles and the industrial sector. In summary, the invention has met the requirements of the invention patent, and has filed a lawsuit to review the committee, and to resign the invention. [Simple description of the figure] ^ ^ This lx month; ^ Marble processing sludge preparation of the purity of the carbonic acid dance powder" implementation process map. ^ The second figure is a photograph of the appearance of the marble processed sludge used in the present invention. Fig. 1 is a photograph showing the appearance of a high-purity carbonic acid-about powder prepared by the present invention. * » is a scanning electron microscope photograph of high purity carbonic acid powder prepared by our company. [Main component symbol description] None 12