200808676 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種藥劑，其防止生成於石灰燒成裝置內 之被覆，更詳言之，關於一種被覆防止劑及使用它之石灰 燒成裝置的被覆防止方法，該被覆防止劑抑制於石灰燒成 裝置運轉之際，起因於石灰泥中所含之鈉（Na)、鉀（K)、 磷（P)及硫（S)或加熱用燃料之重油內低熔點灰分的石 灰被覆；或是因重油火焰接觸所造成之高溫下被覆；甚至 控制暫時所燒成的氧化鈣（CaO)爲過量之二氧化碳（C02) 環境氣體中，再次變化爲碳酸鈣時被覆等之全面被覆；也 兼具配置於石灰燒成裝置內壁的耐.火磚化學剝落之防止性 能。 【先前技術】 習知窖方式之石灰燒成裝置，尤其，從上方裝入原料（脫 水石灰泥或乾燥石灰微粉），利用重油燃燒器而從下方進 行審內最高1200〜1 45 0°C之高溫加熱，予以乾燥〜燒成（造 粒）之同時，從下方排放製品（燒成石灰）的傾斜型旋轉 式審已被泛用於牛皮紙漿製造工廠等。 通常，於牛皮紙漿製造工廠中，利用鹼性藥品（白液） 與蒸氣以蒸煮木材及軋碎木材之木片，過濾後分離成紙漿 與蒸煮廢液，利用蒸發器以將此蒸煮廢液濃縮至約70%的 固形物，利用所謂鹼性回收鍋爐之燃燒爐（回收鍋爐）以 進行還原燃燒，溶解熔融（熔煉）鹼性（碳酸鈉與硫化鈉 之混合鹽）物（綠液）後送入苛性化裝置，添加生石灰以 作成苛性鈉與硫化鈉之鹼性藥品（白液）後而進行循環。 另外，於苛性化裝置中之反應結果，碳酸鈣成爲沈澱物 (石灰泥）而予以分離，水洗此沈澱物後而使鹼性減低至 200808676 可能之fe圍後’利用如該石灰燒成裝置，作成氧化銘（生 石灰）後再度供應至苛性化裝置。 如此方式，牛皮紙漿製程係根據所有化學品之回收與循 環所構成，若此步驟之一部分不恰當而運轉中止的話，將 對整體製程造成莫大之影響。 尤其，若於高溫下進行粉體燒成之步驟而生成被覆或閉 塞的話，於該紙漿製程等循環型製程中，由於整個製程受 到莫大的影響，習知曾以其安定運轉爲目的而嚐試各種改 善° 具體而言，爲了避免供應石灰泥之水份量、殘留鹼性量 之減低或過熱，傾斜型旋轉式窖之情況，採用定期變更火 焰之長度，或變更審內之溫度而防止局部過熱的方法（例 如，參照專利文獻1 )。 另外，針對牢固且巨大被覆物或閉塞物等，藉由使用鑿 岩機等之機械性去除，也進行於盡可能短時間內去除，現 狀則是藉由交替運用數個石灰燒成裝置相對應。 專利文獻1 :日本專利特開200 1 -25 5072號公報 進一步也曾嚐試將如氧化鎂粉體之高熔點且較難結晶 化的成分混入煤灰中，散布於高溫氣體中之方法。 然而，如此習知的被覆防止方法之中，適合於減低供應 石灰泥水份量的手法，藉由作爲脫水機之連續預被覆的採 用及脫水助劑的添加等改善，脫水性能幾乎達到極限，爲 了減低殘留鹼性量，並不增加水洗次數之外，由於導致廢 水量之增加，也將有其限度。另外，爲了使用從牛皮紙漿 製程回收鍋爐所排放的熔煉溶解液~的綠液或氧化綠液（碳 200808676 酸鈉、硫化鈉混合液），因而添加鹼，基於抑制被覆之觀 點則成爲相反的運用。 另一方面，雖然利用機械式去除方法所進行的剝離作業 有助於時間之縮短，但是由於導致石灰燒成裝置之磚面損 傷而加速其後之被覆。 再者，針對將氧化鎂粉體等混入煤灰中，散布於高溫氣 體中的方法，目標之燒成石灰物（氧化鈣）無法生成，或 進行散布之藥品費用過大，產業、操作上並非有效。 如此方式，由於尙未有人提案實質上能夠基本防止被覆 或閉塞的方法。如此之被覆或閉塞，依然對於整個連續運 轉及循環型製程造成莫大的不良影響。例如，一旦發生被 覆或閉塞時，將導致製造能力之降低及重油基本單價之上 升。 另外，因爲必須要有爲了如該方式交替運用之數個石灰 燒成裝置，也必須要有被覆物或閉塞物之去除作業，既費 事又費時，而且被覆物或閉塞物之去除作業將伴隨危險。 再者，由於大量殘存於燒成裝置內之被覆或閉塞物將使 氧化鈣良率降低，導致石灰泥之過量供應，從石灰泥之熱 分解反應式也能夠容易推測之方式來使地球溫室化氣體之 一的二氧化碳排放量也增加至必要以上。 還有，於日本專利特開2003 -26 1 3 63號公報中，本專利 申請人對於如該被覆或閉塞提出一種石灰燒成裝置之被覆 防止運轉方法，其要點在於使用一種使既定量之球形二氧 .化矽化合物與Na或K安定分散於水中的被覆防止劑，得 知雖然如此方法對於流動層型石灰燒成裝置爲有效的，但 200808676 是對於所泛用之傾斜型旋轉式石灰燒成審則未必有效。 【發明內容】 發明所欲解決之技術問題 本發明係有鑑於具有如此習用技術之課題所完成的，其 目的在於提供一種簡易、有效且低成本可防止被覆之石灰 燒成裝置的被覆防止劑，及使用它之石灰燒成裝置的被覆 防止方法。 解決問題之技術手段 本發明人等爲了達成該目的，重複鑽硏的結果，發現藉 由使用既定粒徑之鎂化合物等，能達成該目的，於是完成 了本發明。 亦即，本發明石灰燒成裝置之被覆防止劑，其特徵爲含 有粒徑0.1〜3 0 μπι之鎂化合物。 另外，本發明石灰燒成裝置之被覆防止劑的合適形態， 該鎂化合物係由氫氧化鎂、碳酸鎂與氧化鎂所組成之群組 中所選出之至少一種化合物。 其他的合適形態更含有水與/或油，該鎂化合物係以水性 組成物、0/W型乳膠、W/0型乳膠或油性組成物之形式所 含有。 再者，本發明石灰燒成裝置之被覆防止劑的另外其他合 適形態，其係利用MgO換算量，以20〜60%之比例含有 該鎂化合物。 另一方面，本發明石灰燒成裝置之被覆防止方法，其係 如上所述，將被覆防止劑間歇投入燒成爐中的同時，進行 石灰燒成裝置之運轉。 200808676 本發明石灰燒成裝置之被覆防止方法的合適形態，其係 利用燒成用石灰原料之每It絕對乾燥處理量的MgO換算 量，將0·1〜10kg之該被覆防止劑，於10〜60分鐘/曰之 範圍對該燒成爐進行均勻投入。 【實施方式】 以下，針對本發明之被覆防止劑及被覆防止方法，進行 詳加說明。還有，於本專利說明書中，針對塡充量、摻合 量及濃度等之「％」，只要無特別說明，均表示質量百分 >♦4 〇 首先，本發明之前提係針對石灰燒成裝置中的石灰之燒 成或被覆之發生加以說明。 如上所述，石灰燒成裝置代表例之審方式的燒成裝置也 適用於脫水石灰泥、乾燥石灰微粉中任一種。基本上，爲 一種有效率地使碳酸鈣（CaC〇3 )予以熱分解，製造粒狀 (1〜1 0mm )〜塊狀（10〜1 〇〇mm)氧化鈣（CaO )的裝置， 此時之燒成反應係以下式（1 )表示：200808676 IX. The invention relates to a chemical agent for preventing a coating formed in a lime burning device, and more particularly to a coating preventing agent and a lime burning device using the same In the coating prevention method, the coating inhibitor is inhibited from the operation of the lime burning device, and is caused by sodium (Na), potassium (K), phosphorus (P), sulfur (S) or heating fuel contained in the lime mud. Lime coating of low melting point ash in heavy oil; or coating at high temperature caused by heavy oil flame contact; even controlling temporarily calcined calcium oxide (CaO) as excess carbon dioxide (C02) in the ambient gas, again changing to carbonic acid It is fully covered with calcium and the like, and it also has the resistance to chemical peeling of the fire brick disposed on the inner wall of the lime burning device. [Prior Art] A lime burning device of a conventional method, in particular, a raw material (dehydrated lime mud or dry lime fine powder) is loaded from above, and a heavy oil burner is used to perform a maximum of 1200 to 1 45 0 ° C from below. The high-temperature heating, drying, and sintering (granulation), while tilting the rotary type of the product (burning lime) from below, has been widely used in kraft pulp production plants. Usually, in a kraft pulp production factory, an alkaline medicine (white liquor) and steam are used to cook wood chips and wood chips, which are separated into pulp and cooking waste liquid by filtration, and the cooking waste liquid is concentrated by an evaporator to About 70% of the solids are used in a so-called alkaline recovery boiler (recycling boiler) for reduction combustion, dissolved (melted) alkaline (mixed salt of sodium carbonate and sodium sulfide) (green liquid) and then fed The causticizing device is circulated by adding quicklime to form an alkaline drug (white liquor) of caustic soda and sodium sulfide. In addition, as a result of the reaction in the causticizing device, the calcium carbonate becomes a precipitate (lime mud) and is separated, and after washing the precipitate, the alkalinity is reduced to 200,808,676, and after the use of the lime burning device, After being made into oxidized (lime), it is re-supplied to the causticizing device. In this way, the kraft pulp process is based on the recycling and recycling of all chemicals. If one of the steps is not properly performed and the operation is stopped, it will have a great impact on the overall process. In particular, if the coating is performed at a high temperature to form a coating or a clogging, in the circulation process such as the pulping process, since the entire process is greatly affected, it has been conventionally tried to stabilize the operation. Improvement ° Specifically, in order to avoid the supply of lime mud, the reduction of residual alkali amount or overheating, in the case of a tilt type rotary type, the length of the flame is periodically changed, or the temperature in the trial is changed to prevent local overheating. Method (for example, refer to Patent Document 1). Further, the solid and large coverings, occlusions, and the like are removed in the shortest possible time by mechanical removal using a rock drill or the like, and the present state is correspondingly employed by alternately using a plurality of lime burning devices. Further, a method of mixing a component having a high melting point and a hard crystallizing property of a magnesium oxide powder into a coal ash and dispersing it in a high-temperature gas has been attempted. However, among such conventional coating prevention methods, a method suitable for reducing the amount of water supplied to the lime mud is improved by the use of continuous pre-coating as a dewatering machine and the addition of a dewatering aid, and the dewatering performance is almost reached, in order to reduce The amount of residual alkali does not increase the number of washings, and there is a limit due to an increase in the amount of wastewater. In addition, in order to use the green liquid or the oxidized green liquid (carbon 200808676 sodium or sodium sulfide mixed liquid) which is discharged from the kraft pulp process to recover the molten solution discharged from the boiler, the addition of the alkali is the opposite of the viewpoint of suppressing the coating. . On the other hand, although the peeling operation by the mechanical removal method contributes to the shortening of the time, the subsequent coating is accelerated due to the damage of the brick surface of the lime burning device. In addition, in the method of mixing magnesium oxide powder or the like into coal ash and dispersing it in a high-temperature gas, the target calcined lime material (calcium oxide) cannot be produced, or the cost of spreading the drug is too large, and the industrial and operation are not effective. . In this way, since no one has proposed a method that can substantially prevent the covering or occlusion substantially. Such a cover or occlusion still has a great adverse effect on the entire continuous operation and cycle type process. For example, once a cover or occlusion occurs, it will result in a decrease in manufacturing capacity and a rise in the basic unit price of heavy oil. In addition, since it is necessary to have a plurality of lime burning devices alternately used in this manner, it is necessary to remove the covering or the occlusion, which is both time consuming and time consuming, and the removal of the covering or the occlusion is accompanied. Danger. In addition, since a large amount of coating or occlusion material remaining in the firing device lowers the calcium oxide yield and causes excessive supply of lime mud, the thermal decomposition reaction formula of the lime mud can be easily estimated. The carbon dioxide emissions of one of the gases have also increased to more than necessary. Further, in Japanese Laid-Open Patent Publication No. 2003-26-13336, the applicant of the present application proposes a coating prevention operation method for a lime burning device as described in the coating or occlusion, and the point is to use a spherical shape The oxidizing compound of dioxin and arsenic compound and Na or K are stably dispersed in water, and it is known that the method is effective for the fluidized layer type lime burning apparatus, but the 200808676 is for the inclined inclined type rotary lime burning. The trial is not necessarily effective. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a coating agent which can prevent the coating of a lime burning device from being easily and efficiently. And a coating prevention method of the lime burning device using the same. MEANS FOR SOLVING THE PROBLEMS In order to achieve the object, the present inventors have succeeded in achieving the object by repeating the results of the drill collar, and have found that the present invention has been accomplished by using a magnesium compound having a predetermined particle diameter or the like. That is, the coating preventing agent of the lime burning apparatus of the present invention is characterized by containing a magnesium compound having a particle diameter of 0.1 to 30 μm. Further, in a suitable form of the coating preventing agent for the lime burning apparatus of the present invention, the magnesium compound is at least one selected from the group consisting of magnesium hydroxide, magnesium carbonate and magnesium oxide. Other suitable forms further contain water and/or oil, and the magnesium compound is contained in the form of an aqueous composition, a 0/W type latex, a W/0 type latex or an oily composition. In addition, in another suitable form of the coating agent for preventing the lime burning apparatus of the present invention, the magnesium compound is contained in an amount of 20 to 60% by the amount of MgO. On the other hand, in the method for preventing coating of the lime burning apparatus of the present invention, as described above, the coating preventing agent is intermittently introduced into the baking furnace, and the operation of the lime burning apparatus is performed. 200808676 A suitable form of the method for preventing the coating of the lime burning apparatus of the present invention is to use the coating inhibitor of 0·1 to 10 kg per 10% of the amount of MgO per absolute dry processing amount of the lime raw material for firing. The firing furnace was uniformly charged in a range of 60 minutes/曰. [Embodiment] Hereinafter, the coating prevention agent and the coating prevention method of the present invention will be described in detail. In addition, in the present specification, the "%" of the charge amount, the blending amount, the concentration, and the like, unless otherwise specified, indicates the mass percentage > ♦ 4 〇 First, the present invention is directed to lime burning. The occurrence of the burning or coating of the lime in the apparatus will be described. As described above, the calcining apparatus of the lime burning apparatus representative embodiment is also applicable to any of dehydrated lime mud and dry lime fine powder. Basically, a device for efficiently dissolving calcium carbonate (CaC〇3) to produce granular (1 to 10 mm) to massive (10 to 1 〇〇mm) calcium oxide (CaO). The firing reaction is represented by the following formula (1):
CaC〇3(固體）—CaO (固體）+ C〇2(氣體）…（1) 其中，純粹CaC03之熱分解（燒成）溫度爲898°C (解 離壓爲0.1 MPa)，實際上，由於含有各種不純物，於稍微 較8 98 °C爲低之溫度下熱分解。含有CaC03之實際石灰泥 的分解溫度爲82〇°C附近。 一般而言，用於如此燒成裝置加熱的燃料爲重油，於火 焰附近之溫度到達1 200〜1 45 0 °C。燒成物之CaO的熔點極 高而到達2570°C，因熔點之關係，其本身將黏著（黏性化）， 不會生成硬化物，亦即被覆物。 200808676 但是，相當於燒成爐之審長度超過最大的1 00m，此情形 下，離火焰最遠之審入口溫度約爲室溫。 習知被覆之原因係石灰泥中所含微量之Na、K及P等低 熔點成分或因硫成分所造成之硬化；及過量之C02(二氧 化碳）氣體環境中，於8 00 °C以下引起的CaO再碳酸化現 象所造成之硬化，被覆係歸因於下式（2)所示之反應而發 現：CaC〇3 (solid)—CaO (solid)+ C〇2 (gas) (1) where the thermal decomposition (baking) temperature of pure CaC03 is 898 ° C (dissociation pressure is 0.1 MPa), in fact, due to Contains various impurities and is thermally decomposed at a slightly lower temperature than 8 98 °C. The decomposition temperature of the actual lime mud containing CaC03 is around 82 °C. In general, the fuel used for heating by such a firing device is heavy oil, and the temperature near the flame reaches 1 200 to 1 450 °C. The CaO of the fired product has a very high melting point and reaches 2570 ° C. Due to the melting point, it adheres itself (viscous) and does not form a cured product, that is, a coated object. 200808676 However, the length of the trial furnace is more than the maximum of 100 m. In this case, the temperature of the entrance farthest from the flame is about room temperature. The reason for the conventional coating is the low-melting component such as Na, K and P contained in the lime mud or the hardening caused by the sulfur component; and the excessive CO 2 (carbon dioxide) gas environment, which is caused by the temperature below 800 ° C. The hardening caused by the phenomenon of CaO recarbonation, the coating system is found due to the reaction shown by the following formula (2):
CaO (固體）+ C02(氣體）->CaC03(固體）…（2) _ 通常，如此被覆物係在從窖中央部至火焰前爲止之間的 區域，生成於因再碳酸化之附著溫度區域。於第1圖顯示 因再碳酸化所造成之碳酸鈣被覆膜的附著槪念。 還有，雖然於石灰泥中含有Mg，由於在燒成過程成爲 錯鹽形式，並未發現防止CaO之再碳酸化的機能。 接著，將實際所操作之審型石灰燒成裝置配設於如牛皮 法紙漿製造線上之任意位置，連同關聯設備一起顯示於第 2圖。 於同一圖之關聯設備中，一般而言，於利用苛性化裝置 進行木片蒸煮藥品（氫氧化鈉與硫化鈉之混合液，習慣上 稱爲白液）之製造時，所供應之氧化鈣係形成碳酸鈣後而 被沈澱分離，於洗淨脫水後，以濕餅（CaC03 )之方式供 應至石灰燒成裝置。 此濕餅係於調整旋轉蜜6中燒成時之濕餅（石灰泥）的 黏性之目的下所用之乾燥石灰1中，一面利用槳式混合器 12進行添加，並一面進行混合，藉由從旋轉窖6發生的燃 燒廢氣（約50〜3 00 °C )，利用速乾機2予以半乾燥而送 -10- 200808676 入送料儲槽1 3。 還有，此時所發生之微粉飛散的粉塵係被旋風集塵器3 所捕捉而送回槳式混合器12。 利用送料儲槽1 3所調整的半乾燥石灰泥將被螺旋送料 機1 4所輸送而供應至旋轉審6。 設置於旋轉審6出口側之加熱燃燒器7附近的氣體溫度 保持於12Q0〜145〇°C，——面將所供應的半乾燥石灰泥造粒 成球形，並一面進行燒成。 旋轉窖6係使加熱燃燒器7側成爲低位置而傾斜數度， ^ 燒成物將因本身重量而從旋轉窖6之出口（加熱燃燒器7 側）落下，利用石灰冷卻器8予以冷卻，成爲製品（石灰 九粒）後而貯藏於石灰儲槽9中。未完全被石灰儲槽9完 全捕捉的石灰粉將被袋濾器1 0所捕捉。最後燃燒廢氣經洗 滌器4等所處理，再經排氣冷卻裝置5予以冷卻後而排放 至大氣中。 爲了使如此審型石灰燒成裝置的問題點予以明確化，將 被覆現象（發生場所）與問題點及關聯事項顯示於第3圖。 • 還有，被覆之實際發生場所係顯示於第2圖之符號1 1 (旋 轉蜜6內）。 本發明係爲了防止如該說明的被覆，尤其爲了防止窖型 石灰燒成裝置中的被覆，如上所述，要點在於藉由使用既 定粒徑之鎂化合物，根據石灰泥中之微量鹼金屬與二氧化 碳氣體而使具有黏著性的鈣化合物以不具黏著性的氧化鈣 之形式存在。 若以代表性鎂化合物之氫氧化鎂爲例詳加說明時，於富 中進行石灰泥（濾泥）之燒成而作成燒成石灰（氧化鈣） -11- 200808676 造粒物，一旦加熱燃燒器之不安定燃燒發生時，根據燒成 帶之溫度變得較石灰之燒成溫度爲低，從燃燒氣體或石灰 泥（濾泥）所發生的二氧化碳氣體，在因燒成所生成的氧 化鈣造粒物表面上，再碳酸化將發生而生成碳酸鈣（參照 第1圖）。 另外此時，若使用於加熱用燃燒器之燃料中大量含硫分 之C重油等的話，根據因燃燒所產生的硫氧化物，燒成物 之硫酸化將發生，硫酸鈣將在氧化鈣造粒物表面上生成， ^ 或是該硫氧化物與石灰泥中所含之鹼性成分（Na、K )相 鍵結，低熔點之硫酸鈉等將生成。 然後，因燃燒器之不安定燃燒，部分之燒成石灰將被過 度加熱，氧化鈣之燒結將發生。 於此等現象中，若石灰泥中之鹼性成分，尤其因鈉之碳 酸化物、硫酸化物，燒成物之熔點將降低（820°C附近）時， 表面已再碳酸化之燒成石灰造粒物形成具有高度黏著性的 碳酸鈣，生成物附著於審磚壁，在窖內溫度約800°C附近 形成所謂堰環（dam ring )之附著帶而引起窖之閉塞。另外， ^ 因附著物之離析而導致窖之偏重，或是損壞窖內壁殼而使 審之旋轉不安定，使得連續操作成爲困難。 針對於此，本發明人等發現：於石灰泥或高溫氣體中所 暫時添加的氫氧化鎂，於較碳酸鈣本身之分解溫度爲低的 溫度區域（700〜7 8 0°C )，分解再碳酸化所生成的碳酸鈣 層後而形成氧化鈣，利用高熔點之氧化鎂以進行此氧化鈣 表面之表面被覆而防止再碳酸化。 如此方式，藉由利用高熔點物之氧化鎂以進行氧化鈣造 -12- 200808676 粒物表面之表面被覆，實現極爲良好之被覆防止。 還有，如後所述，若於既定時間內集中既定量間歇添加 本發明之被覆防止劑的話，由於降低鎂化合物之添加總量 爲可能的，也具有不使用以製造之氧化鈣比例降低的優點。 但是，習知即使於水泥富也將發生被覆。然而，水泥蜜 之被覆與石灰蜜之被覆在技術上不相關聯係同業者之常 識。此係歸因於兩窖化學上或溫度上顯著不同。 接著，針對本發明之被覆防止劑詳加說明。 如上所述，本發明之被覆防止劑含有粒徑0.1〜30 μιη之 鎂化合物。還有，此粒徑意指在電子顯微鏡視野之一次粒 於此，鎂化合物只要能表現有效成分之MgO ·χΗ20，並 未予以特別限定，可列舉：氫氧化鎂、碳酸鎂、氧化鎂或 此等鎂化合物之任意混合物，尤以氫氧化鎂特別理想。 另外，如此鎂化合物之粒徑爲0.1〜30μπι，較宜爲〇·5 〜1 0 μιη 〇 若粒徑（一次粒徑）超過30μπι的話，無法得到充分之 被覆防止效果。 本發明之被覆防止劑最好含有該鎂化合物，也可以僅由 該鎂化合物所構成，與其他材料之組合也爲可能的，典型 例係藉由添加約3〜1 2 %之界面活性劑而能夠作成分散、 懸浮或溶解於水及油之至少一種的被覆防止劑組成物。 如此被覆防止劑組成物，具體而言，可例舉：使該鎂化 合物分散或溶解於水中之水性組成物、分散或溶解於油中 之油性組成物、分散或懸浮於水與油中之水中油滴型（〇/w -13- 200808676 型）乳膠組成物及油中水滴型（w/ο型）乳膠組成物。 於本發明中，可以採用任一種組成物形式，能夠使分散 安定性或濕潤性等性能得以提高，再者，應注意粉體形狀 情形之粉麈對策將變得不需要。 能夠用於該被覆防止劑組成物之界面活性劑，具體而 言，可列舉：烷芳磺酸鹽、烷硫酸酯鹽、聚氧乙烯烷醚醋 酸鹽、二烷磺琥珀酸鹽、聚氧乙烯烷硫酸酯鹽、聚氧乙烯 烷磷酸酯鹽及聚羧酸鹽等陰離子界面活性劑；或聚氧乙烯 Φ 烷酚醚、聚氧乙烯脂肪酸酯、聚氧乙烯醇醚、聚氧乙烯去 水山梨醇脂肪酸酯、聚氧乙烯山梨醇脂肪酸酯、高級脂肪 酸甘油酯、聚氧乙烯烷胺及烷醇醯胺等非離子界面活性劑。 另外，雖然本發明被覆防止劑之該鎂化合物濃度能夠因 應於使用狀況而進行適度變更，對象設備係以乾燥及燒成 爲目的，根據使用上之添加設備容量，較宜爲高濃度，以 MgO換算量較宜含有20〜60%。 若濃度超過60%時，可能使有效成分之MgO ·χΗ20粒 φ 子彼此間相接觸而凝聚，形成肥大粒子而降低被覆防止效 率。另一方面，濃度低於20 %之彳青況，帶有水份或油份將 變多，有效成分變得過少而無法得到所期望之效果。 接著，採用使氫氧化鎂安定分散於水或油中的組成物爲 例，說明本發明之被覆防止劑作用。 藉由使氫氧化鎂安定分散於水或油之中，變得容易確保 有效表現被覆防止機能之一次粒徑0.1〜30μπι。若將如此 一次粒徑0.1〜30μιη之氫氧化鎂安定分散於水或油中的組 成物集中添加於害內時，伴隨水份之蒸發或油份之燃燒， -14- 200808676 此等之一部分將附著於窖的爐壁而形成具有高熔點平滑性 與脫模性之被覆防止效率佳的薄被覆膜。與此同時，其他 一部分附著於石灰表面，由於一次粒徑爲0.1〜30 μπι，能 夠再度使再碳酸化之石灰表面恢復成石灰而直接附著於表 面，防止再度再碳酸化而使固結性降低成爲可能。 另外，如此被覆防止劑組成物之情況，由鎂化合物之一 次粒徑爲0.1〜3〇μπι，於短時間內容易大量添加與投入於 *內，容易形成氧化鎂被覆層，能夠抑制氧化鈣造粒物以 0 燒成物之方式附著於審內壁。 本發明係根據該此等作用之單獨或所複合的效果而有 效防止石灰之被覆。 還有，如上所述，該鎂化合物粒子之一次粒徑係0.1〜 3 0 μπι，粒徑較其上限爲大的話，雖然說明無法得到充分之 被覆防止效果，粒徑大至例如數百μπι之鎂化合物之情況， 由於相對於燒成的氧化鈣造粒物之粒徑過大，被覆其表面 幾乎爲不可能，使再碳酸化之鈣成爲氧化鈣，防止再碳酸 _ 化將變得不可能。另外，粒徑小於〇 . 1 μιη之情形，粒子之 凝聚性極高，難以作爲高濃度之被覆防止劑而進行製造或 保存，產業與費用並不平衡。 接著，針對本發明之被覆防止方法加以說明。 如上所述，本發明之被覆防止方法係將該本發明之被覆 防止劑間歇投入燒成爐（窖）的同時，進行石灰燒成裝置 之運轉。 於此，針對投入之方法並未予以特別限定，推薦直接將 此被覆防止劑均勻混入石灰燒成爐內之石灰泥中，或是欲 -15- 200808676 進一步均勻混合之情形，利用水或油等進行適當稀釋的同 時，於石灰燒成爐內之高溫氣體中進行噴霧的方法。 還有，於本發明中，若使該被覆防止劑與石灰泥相接觸 的話，因爲能夠防止被覆之生成，例如，也可以將該被覆 防止劑預先散布於投入燒成爐前之石灰泥中，再者，於燒 成爐內被覆生成之前，將被覆防止劑投入燒成爐內，藉此， 抑制被覆之生成也爲可能的。 另外，於本發明中，藉由設計該被覆防止劑之添加與投 Φ 入方法，能夠利用更少的用量而使更大的效果得以發揮。 具體而言，較宜利用燒成用石灰原料之每It絕對乾燥處 理量的MgO換算量，將0.1〜10kg之該被覆防止劑，於10 〜60分鐘/日之短時間內，對該燒成爐進行均勻間歇之大量 添加，藉由此添加方法，能夠使被覆之防止效果得以大幅 度提昇。 若MgO換算量低於0.1kg的話，將無法確保附著於石灰 表面而避免再碳酸化的量，若超過l〇kg的話，則有可能將 ^ 投入實質上無助於被覆防止之過剩的鎂化合物，成本上不 佳。 另外，若投入時間少於1 〇分鐘的話，有可能將投入實 質上無助於被覆防止之過剩的鎂化合物。另外，由於短時 間內添加大量之被覆防止劑，有助於使.燒成物中之石灰濃 度降低。另一方面，若超過60分鐘的話，有可能無法確保 附著於石灰表面而避免再碳酸化的量。 即使連續添加本發明之被覆防止劑，藉由該作用也能夠 使燒成石灰予以多孔質化（不予以熔融）而使其強度降低， -16- 200808676 此情形下，不得不添加大量之被覆防止劑，不預估約盡可 能防止被覆之強度降低，其用量將變多。 針對於此，若如上所述間歇大量添加的話，於添加該被 . 覆防止劑的期間，強度夠低的燒成石灰將附著成層狀，於 未添加被覆防止劑的期間，強度高的燒成石灰將附著於其 上。因而，假設即使某種程度厚的燒成石灰予以形成的話， 也會根據燒成石灰本身之重量或撞擊等而從強度低的層部 分剝離，與此同時，能夠與其上之強度高的層部分一起脫 ⑩ 落。 利用此投入方法的話，因爲短時間內集中添加大量之被 覆防止劑，合計用量變得較連續添加之情形爲少。因而， 若根據此投入方法的話，能夠利用更少之用量而發揮更大 的效果。 再者，若5〜1 0日期間實行該投入方法的話，於構成燒 成爐內壁之耐火磚表面形成保護層，防止因鹼等所造成之 化學剝落也爲可能的。 0 實施例 以下，根據實施例及比較例進一步詳細說明本發明’但 是本發明並不受此等實施例所限定。 (實施例1〜9、比較例1〜3 ) 採用顯示於下表1之摻合配方而作成各例之被覆防止 劑。亦即，針對水性組成物系之被覆防止劑，一面於容器 中稱取既定量之水與界面活性劑，利用均質機攪拌’並一 面添加既定量之氫氧化鎂，形成幾近均勻的糊漿。其次’ 將一般作爲減黏劑所用之聚磷酸鹽加入此糊漿後而進行攪 -17- 200808676 拌混合，得到均勻糊漿之實施例1〜3與比較例1〜3的被 覆防止劑。 另外，針對ο/w型乳膠系被覆防止劑，稱取既定量之水 與界面活性劑，一面利用均質攪拌機攪拌，並一面添加既 定量之氫氧化鎂，形成幾近均勻的糊漿。接著，將油加入 此糊漿後而進行攪拌混合，得到均勻水中油滴型乳膠之實 施例4及5的被覆防止劑。 另一方面，針對W/0型乳膠系被覆防止劑，稱取既定量 0 之油與界面活性劑，一面利用均質攪拌機攪拌，並一面添 加既定量之氫氧化鎂，形成幾近均勻的糊漿。接著，將水 加入此糊漿後而進行攪拌混合，得到均勻油中水滴型乳膠 之實施例6及7的被覆防止劑。 再者，針對油性組成物系之被覆防止劑，藉由稱取既定 量之油與界面活性劑，一面利用均質攪拌機攪拌，並一面 添加既定量之氫氧化鎂，形成幾近均勻的糊漿，得到實施 例8及9的被覆防止劑。 0 『模型試驗』 將所得的各例之被覆防止劑供應至下列之性能評估試 〔被覆物之強度降低試驗（壓碎強度之測定）〕 甲）採取蜜中產生的被覆物，切斷成1 00x5 0x5 0mm後而作 成市試驗片。 乙）將各例之被覆防止劑，於既定溫度之電爐中，以N2 氣體作爲噴射劑而進行噴霧。 丙）被覆防止劑之噴霧係設爲每日一次進行MgO換算1.5g -18- 200808676 之30分鐘噴霧。 丁）試驗時間設爲10日。 戊）將試驗裝置之槪要顯示於第4圖。 己）試驗結果係將各6次試驗之平均値顯示於表1。 〔’表 1〕CaO (solid) + C02 (gas) - > CaC03 (solid) (2) _ Generally, such a coating is formed in a region from the center of the crucible to the front of the flame, and is formed at the attachment temperature due to recarbonation. region. Fig. 1 shows the adhesion of the calcium carbonate coating film due to recarbonation. Further, although Mg is contained in the lime mud, since it is in the form of a wrong salt in the firing process, the function of preventing recarbonation of CaO is not found. Next, the actually operated calcined lime burning apparatus is disposed at any position, such as a kraft pulp production line, and is shown in Fig. 2 together with associated equipment. In the related equipment of the same figure, in general, in the manufacture of wood chip cooking drugs (a mixture of sodium hydroxide and sodium sulfide, which is customarily called white liquor), the calcium oxide system is supplied during the manufacture of the causticizing device. After the calcium carbonate is separated by precipitation, it is supplied to the lime burning apparatus as a wet cake (CaC03) after washing and dehydration. This wet cake is added to the dry lime 1 used for the purpose of adjusting the viscosity of the wet cake (lime mud) when the roast honey 6 is fired, and is mixed by the paddle mixer 12 while being mixed. The combustion exhaust gas (about 50 to 300 ° C) generated from the rotary crucible 6 is semi-dried by the quick-drying machine 2 to be sent to the 10-200808676 feed storage tank 13 . Further, the dust scattered by the fine powder generated at this time is captured by the cyclone 3 and sent back to the paddle mixer 12. The semi-dry lime mud adjusted by the feed reservoir 13 will be conveyed by the screw feeder 14 and supplied to the spin test 6. The temperature of the gas in the vicinity of the heating burner 7 disposed on the exit side of the rotary audit 6 was maintained at 12Q0 to 145 °C, and the supplied semi-dry lime mud was granulated into a spherical shape and fired. The rotary crucible 6 is such that the heating burner 7 side is lowered to a low position and tilted by a few degrees. ^ The burned material is dropped from the outlet of the rotary crucible 6 (on the side of the heating burner 7) by its own weight, and is cooled by the lime cooler 8. After being a product (nine pieces of lime), it is stored in the lime storage tank 9. The lime powder that is not completely captured by the lime storage tank 9 will be captured by the bag filter 10. Finally, the combustion exhaust gas is treated by the scrubber 4 or the like, and then cooled by the exhaust gas cooling device 5 to be discharged to the atmosphere. In order to clarify the problem of the lime burning apparatus thus described, the phenomenon of covering (the place of occurrence), the problem point, and related matters are shown in Fig. 3. • Also, the actual occurrence of the overlay is shown in symbol 1 1 of Figure 2 (within the rotating honey 6). The present invention is for preventing the coating as described, and particularly for preventing the coating in the lime-type lime burning device. As described above, the main point is to use a trace amount of alkali metal and carbon dioxide in the lime mud by using a magnesium compound having a predetermined particle diameter. The gas causes the adhesive calcium compound to exist in the form of non-adhesive calcium oxide. If the magnesium hydroxide of the representative magnesium compound is used as an example, the lime mud (filter sludge) is fired in Yufu to form calcined lime (calcium oxide) -11- 200808676 granules, once heated and burned When the unstable combustion occurs, the temperature of the firing zone becomes lower than the calcination temperature of the lime, and the carbon dioxide gas generated from the combustion gas or the lime mud (filter sludge) is generated by the calcination. On the surface of the granulated material, recarbonation will occur to form calcium carbonate (see Fig. 1). In addition, at this time, if a large amount of sulfur-containing C heavy oil or the like is used in the fuel for the burner for heating, the sulfurization of the fired product will occur depending on the sulfur oxides generated by the combustion, and the calcium sulfate will be made in the calcium oxide. It is formed on the surface of the grain, ^ or the sulfur oxide is bonded to the alkaline component (Na, K) contained in the lime mud, and a low-melting sodium sulfate or the like is formed. Then, due to the unstable combustion of the burner, part of the calcined lime will be excessively heated, and sintering of calcium oxide will occur. Among these phenomena, if the alkaline component in the lime mud, especially the sodium carbonate or sulfate, the melting point of the fired product is lowered (near 820 ° C), the surface is recarbonated and calcined. The particles form calcium carbonate having high adhesion, and the product adheres to the brick wall, and a so-called dam ring attachment band is formed in the vicinity of the crucible temperature of about 800 ° C to cause clogging of the crucible. In addition, the continuous operation becomes difficult because the segregation of the attachment causes the weight of the crucible or damages the inner wall of the crucible to make the rotation unstable. In view of the above, the present inventors have found that magnesium hydroxide temporarily added to lime mud or high-temperature gas is decomposed in a temperature region (700 to 780 ° C) which is lower than the decomposition temperature of calcium carbonate itself. After the calcium carbonate layer formed by carbonization, calcium oxide is formed, and high-melting magnesium oxide is used to cover the surface of the calcium oxide surface to prevent recarbonation. In this manner, extremely high coating prevention is achieved by utilizing the magnesium oxide of the high melting point material to carry out the surface coating of the surface of the calcium oxide -12-200808676. Further, as will be described later, if the coating inhibitor of the present invention is added in a predetermined amount within a predetermined period of time, it is possible to reduce the total amount of the addition of the magnesium compound, and also to reduce the proportion of the calcium oxide to be produced. advantage. However, it is known that even if cement is rich, it will be covered. However, the coverage of cement honey and the coating of lime honey are technically unrelated to the common sense of the industry. This is due to the fact that the two oximes are chemically or temperature significantly different. Next, the coating preventing agent of the present invention will be described in detail. As described above, the coating preventing agent of the present invention contains a magnesium compound having a particle diameter of 0.1 to 30 μm. In addition, the particle diameter means that the magnesium compound is a primary particle in the field of view of the electron microscope, and the magnesium compound is not particularly limited as long as it exhibits an effective component of MgO·χΗ20, and examples thereof include magnesium hydroxide, magnesium carbonate, magnesium oxide or the like. Any mixture of magnesium compounds, especially magnesium hydroxide, is particularly preferred. Further, the particle size of the magnesium compound is preferably from 0.1 to 30 μm, more preferably from 5% to 10 μm. If the particle diameter (primary particle diameter) exceeds 30 μm, a sufficient coating prevention effect cannot be obtained. The coating preventing agent of the present invention preferably contains the magnesium compound, or may be composed only of the magnesium compound, and a combination with other materials is also possible, and a typical example is by adding about 3 to 12% of a surfactant. It is possible to form a coating agent composition which is dispersed, suspended or dissolved in at least one of water and oil. Specifically, the coating agent composition may be an aqueous composition in which the magnesium compound is dispersed or dissolved in water, an oily composition dispersed or dissolved in oil, or dispersed or suspended in water and oil. Oil droplet type (〇/w -13- 200808676 type) latex composition and oil droplet type (w/o type) latex composition. In the present invention, any of the composition forms can be used, and the properties such as dispersion stability and wettability can be improved. Further, it should be noted that the powdery measures in the case of the powder shape are not required. Specific examples of the surfactant which can be used for the coating agent composition include an alkane sulfonate, an alkane sulfate, a polyoxyethylene alkyl ether acetate, a dialkyl sulfosuccinate, and a polyoxyethylene. Anionic surfactants such as alkane sulfates, polyoxyethylene alkane phosphates and polycarboxylates; or polyoxyethylene Φ alkanophene ethers, polyoxyethylene fatty acid esters, polyoxyethylene ethers, polyoxyethylene deionized water Nonionic surfactants such as sorbitol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, higher fatty acid glycerides, polyoxyethylene alkylamines, and alkanolamines. In addition, the concentration of the magnesium compound of the coating agent of the present invention can be appropriately changed depending on the state of use, and the target equipment is intended to be dried and burned, and it is preferably a high concentration depending on the capacity of the added equipment used, and is converted into MgO. The amount is preferably 20 to 60%. When the concentration exceeds 60%, MgO·χΗ20 particles of the active ingredient may be brought into contact with each other to form agglomerated particles, thereby reducing the coating prevention efficiency. On the other hand, if the concentration is less than 20%, the water content or the oil content will increase, and the active ingredient will become too small to obtain the desired effect. Next, the action of the coating preventing agent of the present invention will be described by taking, as an example, a composition in which magnesium hydroxide is stably dispersed in water or oil. By dispersing the magnesium hydroxide in water or oil, it is easy to ensure an effective primary particle diameter of 0.1 to 30 μm. If the composition in which the magnesium hydroxide having a particle diameter of 0.1 to 30 μm is dispersed in water or oil is added to the inside in a concentrated manner, the evaporation of water or the burning of the oil is accompanied by -14-200808676. The film is adhered to the furnace wall to form a thin coating film having high melting point smoothness and mold release property and excellent coating prevention efficiency. At the same time, the other part adheres to the surface of the lime. Since the primary particle size is 0.1 to 30 μm, the surface of the recarbonated lime can be restored to lime and directly adhered to the surface, preventing re-carbonation and reducing the consolidation. become possible. Further, in the case where the agent composition is coated as described above, the primary particle diameter of the magnesium compound is 0.1 to 3 μm μm, and it is easy to add and put in a large amount in a short period of time, and it is easy to form a magnesium oxide coating layer, thereby suppressing the formation of calcium oxide. The granules are attached to the inner wall of the trial in the form of a burnt of zero. The present invention effectively prevents the coating of lime in accordance with the effects of the effects alone or in combination. In addition, as described above, when the primary particle diameter of the magnesium compound particles is 0.1 to 30 μm, and the particle diameter is larger than the upper limit, it is described that a sufficient coating prevention effect cannot be obtained, and the particle diameter is as large as, for example, several hundred μm. In the case of the magnesium compound, since the particle size of the calcined calcium oxide granule is too large, it is almost impossible to coat the surface, and the calcium which is recarbonated becomes calcium oxide, and it is impossible to prevent recarbonation. Further, when the particle diameter is less than 〇 1 μm, the particle is highly cohesive, and it is difficult to manufacture or store it as a high-concentration coating preventing agent, and the industry and the cost are not balanced. Next, the coating prevention method of the present invention will be described. As described above, in the coating prevention method of the present invention, the coating preventing agent of the present invention is intermittently introduced into a baking furnace, and the operation of the lime burning apparatus is performed. Here, the method of inputting is not particularly limited, and it is recommended to directly mix the coating preventing agent into the lime mud in the lime burning furnace, or to further uniformly mix the -15-200808676, using water or oil, etc. A method of spraying in a high-temperature gas in a lime burning furnace while appropriately diluting. Further, in the present invention, when the coating preventing agent is brought into contact with the lime mud, since the formation of the coating can be prevented, for example, the coating preventing agent may be previously dispersed in the lime mud before being placed in the baking furnace. In addition, it is also possible to suppress the formation of the coating by putting the coating preventing agent into the firing furnace before the coating is formed in the firing furnace. Further, in the present invention, by designing the addition of the coating preventing agent and the method of casting, it is possible to exert a larger effect with a smaller amount. Specifically, it is preferable to use 0.1 to 10 kg of the coating inhibitor in a short period of time of 10 to 60 minutes/day by using the amount of MgO per an absolute dry processing amount of the lime raw material for firing. The furnace is uniformly added in a large amount of intermittently, and by this addition method, the effect of preventing the coating can be greatly improved. When the amount of MgO is less than 0.1 kg, the amount of adhesion to the surface of the lime to avoid recarbonation cannot be ensured. If it exceeds 1 〇kg, it is possible to put in excess of the magnesium compound which is substantially unhelpful for coating prevention. The cost is not good. In addition, if the investment time is less than 1 minute, there is a possibility that the magnesium compound which is practically unhelpful to be prevented from being covered may be invested. Further, since a large amount of the coating preventing agent is added in a short period of time, it contributes to lowering the lime concentration in the fired product. On the other hand, if it exceeds 60 minutes, there is a possibility that the amount of adhesion to the lime surface cannot be ensured to avoid recarbonation. Even if the coating agent of the present invention is continuously added, the calcined lime can be made porous (not melted) by the action, and the strength is lowered. -16-200808676 In this case, a large amount of coating must be added to prevent it. It is not expected to reduce the strength of the coating as much as possible, and the amount thereof will increase. On the other hand, when the amount of the coating agent is added as described above, the calcined lime having a sufficiently low strength is adhered to a layered state, and the high-strength burning is performed while the coating agent is not added. Lime will adhere to it. Therefore, even if a certain amount of calcined lime is formed, it is peeled off from the layer of the low-strength layer depending on the weight or impact of the calcined lime itself, and at the same time, the layer portion having a higher strength can be formed thereon. Take off 10 together. When this input method is used, since a large amount of the coating inhibitor is added in a short time, the total amount is less than that of continuous addition. Therefore, according to this input method, it is possible to exert a larger effect with a smaller amount. Further, when the input method is carried out during the period of 5 to 10 days, it is also possible to form a protective layer on the surface of the refractory brick constituting the inner wall of the firing furnace to prevent chemical peeling due to alkali or the like. EXAMPLES Hereinafter, the present invention will be described in further detail based on examples and comparative examples, but the present invention is not limited by the examples. (Examples 1 to 9 and Comparative Examples 1 to 3) The coating formulations shown in the following Table 1 were used to prepare coating inhibitors of the respective examples. That is, in the case of the coating agent for the aqueous composition, a predetermined amount of water and a surfactant are weighed in a container, and a predetermined amount of magnesium hydroxide is added by a homogenizer to form a nearly uniform syrup. . Next, the polyphosphates generally used as the viscosity reducing agent were added to the paste, and then stirred and mixed to obtain a coating agent of Examples 1 to 3 and Comparative Examples 1 to 3 of the uniform paste. Further, for the ο/w type latex-based coating preventing agent, a predetermined amount of water and a surfactant are weighed, and while stirring with a homomixer, a predetermined amount of magnesium hydroxide is added to form a nearly uniform syrup. Then, the oil was added to the syrup, and the mixture was stirred and mixed to obtain a coating inhibitor of Examples 4 and 5 of the oil-drop type latex in a uniform water. On the other hand, for the W/0 type latex-based coating preventive agent, a predetermined amount of oil and a surfactant are weighed, and while stirring with a homomixer, a predetermined amount of magnesium hydroxide is added to form a nearly uniform syrup. . Next, water was added to the syrup, and the mixture was stirred and mixed to obtain coating inhibitors of Examples 6 and 7 of the water-repellent type latex in the uniform oil. Further, the coating agent for the oil-based composition is stirred by a homomixer while weighing a predetermined amount of the oil and the surfactant, and a predetermined amount of magnesium hydroxide is added to form a nearly uniform syrup. The coating preventing agents of Examples 8 and 9 were obtained. 0 "Model test" The obtained coating inhibitors of each case are supplied to the following performance evaluation test [strength reduction test of the covering (measurement of crushing strength)] A) The coated material produced by the honey is taken and cut into 1 00x5 0x5 0mm and then made a city test piece. B) The coating inhibitor of each example is sprayed with an N 2 gas as a propellant in an electric furnace of a predetermined temperature. C) The spray of the coating preventive agent is set to be sprayed once a day for a 30 minute period of MgO conversion of 1.5 g -18 to 200808676. D) The test time is set to 10 days.戊) A summary of the test apparatus is shown in Fig. 4. The test results are shown in Table 1 for the average enthalpy of each of the six tests. 〔'Table 1〕
鎂化合物 粒徑 分散系中之 MgO換算濃度 分散系 其他成分 壓碎強度 剝離強度 μπι % kg kg 實施例1 0·1 〜20 40 水 水、界面活性劑 11.5 3.0 實施例2 20 〜30 60 水 水、界面活性劑 15.8 6.1 實施例3 1〜10 40 水 水、界面活性劑 9.7 2.0 實施例4 1〜10 40 水中油滴 水、油、界面活性劑 10.9 2.5 實施例5 10 〜30 50 水中油滴 水、油、界面活性劑 13.4 4.1 實施例6 0.1 〜10 30 油中水滴 油、水、界面活性劑 11.9 3.2 實施例7 10 〜30 50 油中水滴 油、水、界面活性劑 14.9 6.2 實施例8 1〜10 20 油 油、界面活性劑 12.2 3.5 實施例9 10 〜30 55 油 油、界面活性劑 15.3 7.8 比較例1 小於0.1 20 水 水、界面活性劑 60.8 13.5 比較例2 50 〜100 50 水 水、界面活性劑 62.1 15.1 比較例3 50 〜80 50 水中油滴 水、油、界面活性劑 63.5 14.8 比較例4 — — 水 水、界面活性劑 70.1 14.4 由表1可明確得知，摻合比較例1之小於φ 0.1 μπι鎂粒 子的被覆防止劑之情況，試驗後之壓碎強度與比較例4(無 添加）之壓碎強度的差爲小的，分析被覆物剖面之後，得 知由於因鎂粒子所形成的保護被覆之膜厚過薄而無法防止 -19- ‘200808676 再碳酸化。 ' 同樣地，摻合比較例2及3之φ 50 μιη以上鎂粒子的被 覆防止劑之情況，存在粒徑過大而未形成膜之部分，無法 抑制再碳酸化物。 由以上之結果，推測由於鎂粒子過大，於被覆物外表面 上之附著力爲弱的，於氣體流速大的真實爐中，無論如何 也無法有效實現被覆膜形成及被覆膜維持。 針對於此，摻合實施例1〜9之φ 〇 . 1〜30，111範圍鎂粒 子的被覆防止劑之情況，確認充分壓碎強度之降低效果， 得知尤其使用Φ 0.1〜10 μπι範圍鎂粒子的實施例1、3、4、 6及8之被覆防止劑顯示更進一步優異的效果。 〔被覆成長抑制試驗（剝離強度之測定）〕 甲）於9 0 0 °C電爐中，將實施例1〜9、比較例1〜3之被覆 防止劑，以MgO換算0.5kg/m2之噴霧量，30分鐘噴霧於 燒磨土磚表面。維持1小時後，施加50kg/cm2之載重，將 熔點9 6 5 °C之被覆物予以10小時、900°(：壓黏。 乙）冷卻後，求得磚與被覆物之剝離強度。 丙）將試驗裝置之槪要顯不於第5圖。 丁）試驗結果係將各5次試驗之平均値顯示於表1。 由表1可明確得知，摻合比較例1之小於φ 〇. 1 μπι鎂粒 子的被覆防止劑之情況，於磚上無法形成被覆膜，相反的， 摻合比較例2及3之φ 50μιη以上鎂粒子的被覆防止劑之 情況，歸因於成爲砂狀，進行流動飛散而無法發揮所要求 之效果。 針kf於此’㉟合實施例1〜9之φ 〇. 1〜3 0 μ m範圍錢粒 -20 - 200808676 子的被覆防止劑之情況，確認顯著之剝離強度降低效果。 『真實機試驗』 使用顯示於表1之實施例3及6與比較例2之被覆防止 劑，供應至作爲真實機之2系列窖的通常2個月運轉。 被覆防止劑係利用顯示於第6圖之高濃度/短時間注入 方法以進行投入與添加。 ~ 於第6圖，被覆防止劑貯槽2 1後而使用容量11之化學 容器，而此貯槽21具備排氣管22、停止閥23、液面計24。 φ 雖然被覆防止劑係一種氫氧化鎂分散液，但是考量粉塵 等之混入，設置公稱直徑25 Ax40篩孔之粗濾器25，利用 定量泵26進行既定量之添加。注入時間之管理係藉由利用 組裝於控制盤2 8內之計時器以使定量泵馬達27起動及停 止。還有，符號29係壓力指示計、30係槳式混合器（既 設）。利用槳式混合器3 0均勻混合石灰餅、乾燥煤泥、被 覆防止劑，必要時也混合實施例3之水、實施例6之油而 送至螺旋送料機1 4。將所得的結果顯示於表2。MgO conversion concentration in magnesium particle size dispersion system, other components, crushing strength, peeling strength, μπι % kg kg, Example 1 0·1 to 20 40 water, surfactant 1,1.5 3.0 Example 2 20 to 30 60 water Surfactant 15.8 6.1 Example 3 1~10 40 Water, surfactant 9.7 2.0 Example 4 1~10 40 Oil dripping in water, oil, surfactant 10.9 2.5 Example 5 10 ~ 30 50 Oil dripping in water, Oil, surfactant 13.4 4.1 Example 6 0.1 ~ 10 30 oil droplets in oil, water, surfactant 11.9 3.2 Example 7 10 ~ 30 50 oil droplets in oil, water, surfactant 14.9 6.2 Example 8 1~ 10 20 Oil, surfactant 12.2 3.5 Example 9 10 ~ 30 55 Oil, surfactant 15.3 7.8 Comparative Example 1 Less than 0.1 20 Water, surfactant 60.8 13.5 Comparative Example 2 50 ~ 100 50 Water, interface Active agent 62.1 15.1 Comparative Example 3 50 ~ 80 50 Oil in water, oil, surfactant, surfactant 63.5 14.8 Comparative Example 4 — Water, surfactant 70.1 14.4 It can be clearly seen from Table 1, blending comparative example When the coating agent of 1 is less than φ 0.1 μπι magnesium particles, the difference between the crush strength after the test and the crush strength of Comparative Example 4 (without addition) is small, and after analyzing the profile of the coating, it is known that The film thickness of the protective coating formed by the particles is too thin to prevent the re-carbonation of -19- '200808676. In the same manner, in the case where the coating agent for the magnesium particles of φ 50 μm or more of Comparative Examples 2 and 3 was blended, the film having a large particle diameter and not forming a film was formed, and the recarbonate could not be suppressed. From the above results, it is presumed that since the magnesium particles are too large, the adhesion to the outer surface of the coated object is weak, and in the actual furnace having a large gas flow rate, the formation of the coating film and the maintenance of the coating film cannot be effectively achieved. On the other hand, in the case of the coating inhibitor of the magnesium particles in the range of φ 〇. 1 to 30, 111 of Examples 1 to 9, the effect of reducing the crushing strength was confirmed, and it was found that magnesium in the range of Φ 0.1 to 10 μm was particularly used. The coating preventing agents of Examples 1, 3, 4, 6 and 8 of the particles showed further excellent effects. [Covering growth inhibition test (measurement of peel strength)] A) The coating agent of Examples 1 to 9 and Comparative Examples 1 to 3 was sprayed in an amount of 0.5 kg/m 2 in terms of MgO in an electric furnace at 900 ° C. Spray on the surface of the burnt bricks for 30 minutes. After maintaining for 1 hour, a load of 50 kg/cm 2 was applied, and the coating material having a melting point of 965 ° C was cooled for 10 hours and 900 ° (pressure bonding. B), and the peel strength of the brick and the coating was determined. C) The outline of the test device is not shown in Figure 5. D) The test results are shown in Table 1 for the average enthalpy of each of the five tests. As is clear from Table 1, in the case where the coating preventing agent of Comparative Example 1 was less than φ 〇. 1 μπι magnesium particles, the coating film could not be formed on the brick, and conversely, the φ of Comparative Examples 2 and 3 was blended. In the case where the coating agent for the magnesium particles of 50 μm or more is formed into a sand shape, the flow is scattered and the desired effect cannot be exhibited. The needle kf was used in the case of the φ 〇. 1 to 3 0 μ m range of the granules -20 - 200808676, and the significant peel strength reduction effect was confirmed. "Real Machine Test" Using the coating inhibitors of Examples 3 and 6 and Comparative Example 2 shown in Table 1, the two-month operation was carried out to the two series of 作为 as a real machine. The coating preventing agent was subjected to the high concentration/short time injection method shown in Fig. 6 for input and addition. In Fig. 6, after the agent tank 21 is covered, a chemical container having a capacity of 11 is used, and the tank 21 is provided with an exhaust pipe 22, a stop valve 23, and a level gauge 24. φ Although the coating preventing agent is a magnesium hydroxide dispersion, a coarse filter 25 having a nominal diameter of 25 Ax40 mesh is provided in consideration of the mixing of dust or the like, and the quantitative pump 26 is used for the quantitative addition. The administration of the injection time is to start and stop the metering pump motor 27 by using a timer assembled in the control panel 28. Further, reference numeral 29 is a pressure indicator meter and a 30-series paddle mixer (supplied). The lime cake, the dried coal slurry, and the coating preventive agent were uniformly mixed by the paddle mixer 30, and if necessary, the water of Example 3 and the oil of Example 6 were mixed and sent to the screw feeder 14. The results obtained are shown in Table 2.
-21- 200808676 〔表2〕 被覆 乾燥石灰泥量 添加量 九粒粒 九粒排放管清掃 被覆量 防止劑 (t/hr) 比率 時間(分鐘） 度特性 手動作業次數(次） (0 割古 未使用時 8 1/100 60 不均与 15 32.0 一 實施例3 8 1/100 30 常態分布 1 6.4 〇 8 1/100 60 常態分布 0 3.2 ◎ 實施例6 8 1/100 30 常態分布 2 9.6 〇 8 1/100 60 常態分布 1 5.4 〇 比較例2 8 1/100 60 不均勻 13 23.1 χ〜Δ 註1真實爐運轉時間進行60日。 註2石灰泥量爲8.0±0.4t之範圍。 註3 1/1 00、60分鐘添加係相當於每it乾燥石灰泥、4kg/ 小時之MgO純物質。1/100、30分鐘添加係同樣相當於 2kg/小時° 註4粒度特性之「不均勻」係指二個波峰分布。 由表2可明確得知，以1/100之添加比率，進行30分鐘 及60分鐘（任一種均爲1次/日之添加頻率）之添加實施 例3及6的被覆防止劑之結果，可以得到極大的改善效果。 還有，此添加量係相當於每11乾燥石灰泥、MgO純物質 2kg/30分鐘及4kg/60分鐘。另外，此4kg/60分鐘係以 1/2400之添加比率進行連續添加之情形與1日之合計添加 量爲等量的，如此方式，短時間內集中式進行大量間歇添 加，與被覆防止劑之摻合成分同樣重要。 另外，於比較例2中，利用相同於實施例3及6之條件 (1/10 0、60分鐘）來嚐試添加，得知與未使用時幾乎不變， -22- 200808676 鎂化合物於高溫下成爲氧化鎂時點的MgO粒 之要因。 亦即，進行如石灰泥之原本高熔點成分燒成 被覆防止中，爲了使粒徑0.1〜3 0 μ m、最好爲 MgO與高溫下之MgO本身得以均勻散布，使鎂 安定分散於水或油中之組成物爲有效的。 另外，此真實機試驗係以添加比率1/100，^ 及60分鐘之二等級添加實施例3及6的被覆Κ 結果，推測添加比率及添加時間之增減將對被 將造成影響。 而且，於此實施例3及6中，雖然可以得 1/100、60分鐘添加者爲較佳之結果，由於燒成 條件、尤其供應至裝置之石灰泥中的不純物濃 之燃燒溫度等係依各裝置而有所不同，認爲除 置之被覆相關聯的事項之外，最好決定適當之 加時間。 另外，由表2可明確得知，針對於試驗期間 期間，以MgO換算量12.0kg、60分鐘/1日之 每11絕對乾燥處理量之實施例3的被覆防止齊 容易推測於磚表面形成保護層的結果。 以上，雖然根據一些實施例更詳細說明了本 本發明並不受此等實施例所限定，於本發明 內，各種變形爲可能的。 例如，實施例1等之被覆防止劑的調製方法 製順序所限定。 爲極重要 的設備內之 1〜1 0 μπι之 化合物得以 I行30分鐘 「止劑，由此 覆防止效果 到添加比率 裝置之使用 度、燒成爐 了掌握各裝 添加量與添 之最初7日 範圍來添加 !，可以得到 :發明，但是 要旨之範圍 :並不受該調 -23- 200808676 [產業上利用之可能性] 若根據本發明，由於作成使用既定粒徑之鎂化合物等， 能夠提供一種簡易、有效且低成本可防止被覆之石灰燒成 裝置的被覆防止劑、及使用它之石灰燒成裝置的被覆防止 方法。 亦即，若根據本發明石灰燒成裝置之被覆防止方法，由 於防止牢固且巨大被覆物之發生，也改善因脫落被覆物所 造成之閉塞，能夠達成包含省能量、環境對策、安全作業 之長期安定運用。 【圖式簡單說明】 第1圖係顯示因再碳酸化所造成之碳酸鈣被覆膜之附著 槪念的槪念圖。 第2圖係顯示牛皮法紙漿製程中之蜜型石灰燒成裝置之 配設位置的配置圖。 第3圖係顯示被覆現象（發生場所）與問題點及關聯事 項的說明圖。 第4圖係用於被覆物強度降低試驗之試驗裝置的槪念 第5圖係用於被覆物成長抑制試驗之試驗裝置的槪念 圖。 、第6圖係顯示被覆防止劑之注入方法的說明圖。 【主要元件符號說明】 1 乾燥石灰 2 速乾機 3 旋風集麈器 4 洗滌器 -24- 200808676 5 排氣冷卻裝置 6 旋轉塞 7 加熱燃燒器 8 石灰冷卻器 9 石灰儲槽 10 袋濾器 11 被覆之實際發生場所 12 槳式混合器 13 送料儲槽-21- 200808676 [Table 2] Coated dry lime mud amount added amount Nine grain nine-pipe discharge pipe cleaning amount inhibitor (t/hr) Ratio time (minutes) Degree characteristic manual operation times (times) (0 Chougu When used 8 1/100 60 uneven and 15 32.0 an embodiment 3 8 1/100 30 normal distribution 1 6.4 〇 8 1/100 60 normal distribution 0 3.2 ◎ Example 6 8 1/100 30 Normal distribution 2 9.6 〇8 1/100 60 Normal distribution 1 5.4 〇Comparative example 2 8 1/100 60 Uneven 13 23.1 χ~Δ Note 1 The actual furnace operation time is 60 days. Note 2 The amount of lime mud is 8.0±0.4t. Note 3 1 /1 00, 60 minutes addition is equivalent to 4kg / hour of MgO pure material per dry lime mud. 1 / 100, 30 minutes addition is also equivalent to 2kg / hour ° Note 4 "granularity characteristics" of the "uneven" Two peak distributions As can be clearly seen from Table 2, the coating prevention of the addition examples 3 and 6 was carried out at intervals of 1/100 for 30 minutes and 60 minutes (any one was added once/day). As a result of the agent, a great improvement effect can be obtained. Also, this addition amount is equivalent to every 11 dry Stucco, MgO pure material 2kg/30min and 4kg/60min. In addition, this 4kg/60min is added continuously at a ratio of 1/2400, and the total amount added on the 1st is equal. It is also important to carry out a large amount of intermittent addition in a concentrated manner in a short period of time, and it is also important as a blending component of the coating preventing agent. Further, in Comparative Example 2, the conditions (1/10 0, 60 minutes) which are the same as those of Examples 3 and 6 are used. Try to add, and know that it is almost unchanged when it is not used. -22- 200808676 Magnesium compound is the cause of MgO particles when it is magnesia at high temperature. That is, the original high-melting-point component of the lime mud is prevented from being baked and coated. In order to make the particle size of 0.1 to 30 μm, preferably MgO, and the MgO itself at a high temperature are uniformly dispersed, it is effective to disperse the composition of magnesium in water or oil. In addition, this real machine test is added. The ratios of 1/100, ^ and 60 minutes were added to the coatings of Examples 3 and 6. As a result, it is presumed that the increase and decrease of the addition ratio and the addition time will affect the influence. Moreover, in Examples 3 and 6, Although you can get 1/100, 60 minutes As a result of the addition, since the firing conditions, in particular, the combustion temperature of the impurities in the lime mud supplied to the apparatus, are different depending on the respective devices, it is considered that the most relevant matters other than the covering is the most In addition, as shown in Table 2, it is clear from the table 2 that the coating of Example 3 is prevented by the amount of MgO in the period of the test period of 12.0 kg and 60 minutes per day. It is easy to speculate on the result of forming a protective layer on the surface of the brick. In the above, although the present invention is not limited by the embodiments in detail, it is possible that various modifications are possible within the present invention. For example, the preparation method of the coating preventing agent of Example 1 or the like is defined. For the extremely important equipment, the compound of 1~1 0 μπι can be used for one minute for 30 minutes. This prevents the effect from being added to the ratio of the device, and the firing furnace controls the amount of each additive and adds the first 7 In addition, it is possible to obtain the invention, but the scope of the gist is not to be adjusted. -23-200808676 [Possibility of industrial use] According to the present invention, it is possible to use a magnesium compound having a predetermined particle diameter or the like. Provided is a simple, effective, and low-cost coating preventing agent for preventing a coated lime burning device, and a coating preventing method for a lime burning device using the same, that is, a coating preventing method for a lime burning device according to the present invention, By preventing the occurrence of strong and large coverings and improving the occlusion caused by falling off the covering, it is possible to achieve long-term stability and use including energy saving, environmental measures, and safe operation. [Simplified illustration] Figure 1 shows the reason A view of the attachment of the calcium carbonate coating caused by carbonation. Fig. 2 shows the honey-type lime burning in the kraft pulp process. Fig. 3 is a diagram showing the phenomenon of the covering phenomenon (place of occurrence), the problem point, and the related items. Fig. 4 is a view of the test device for the strength reduction test of the covering. Fig. 6 is an explanatory view showing a method of injecting a coating preventing agent. [Explanation of main component symbols] 1 Dry lime 2 Quick-drying machine 3 Cyclone collector 4 Scrubber-24- 200808676 5 Exhaust cooling device 6 Rotary plug 7 Heating burner 8 Lime cooler 9 Lime storage tank 10 Bag filter 11 Actual place where the coating is covered 12 Paddle mixer 13 Feeding tank
1 4 螺旋送料機 21 貯槽 22 排氣管 23 停止閥 24 液面計 25 粗濾器 2 6 定量栗 27 定量泵馬達 28 控制盤 29 壓力指示計 30 槳式混合器 -251 4 Screw feeder 21 Storage tank 22 Exhaust pipe 23 Stop valve 24 Level gauge 25 Strainer 2 6 Quantitative pump 27 Quantitative pump motor 28 Control panel 29 Pressure gauge 30 Paddle mixer -25