TWI715300B

TWI715300B - Refractory sintered body

Info

Publication number: TWI715300B
Application number: TW108142265A
Authority: TW
Inventors: 崔大倫; 邱浩然
Original assignee: 林園先進材料科技股份有限公司
Priority date: 2019-11-21
Filing date: 2019-11-21
Publication date: 2021-01-01
Also published as: TW202120457A

Abstract

The present invention provides a refractory sintered body comprising a refractory substrate, and a plurality of inorganic fibers embedded in the refractory substrate. Accordingly, the refractory sintered body is able to withstand high temperature and high flow rate flue gas.

Description

Refractory sintered body

本發明係關於一種燒結體，特別係關於一種可耐受高溫及高流速煙氣之耐火燒結體。The present invention relates to a sintered body, in particular to a refractory sintered body that can withstand high temperature and high flow rate flue gas.

耐火材廣泛使用於化學工業之反應器中，一般而言，耐火材主要為金屬氧化物之燒結體，並依據其實際應用，而須承受數百至數千攝氏度(℃)之高溫。以碳黑生產為例，由於須於1900℃以上之高溫環境中反應，且須使用200 m/s以上流速之煙氣，故其反應器內部之耐火材必須承受高溫及高煙氣流速之環境。此外，當生產品級轉換或產線異常停止時，反應器內的溫度會劇烈變化，因而衍生熱震(thermal shock)現象。上述高溫、高煙氣流速及熱震現象，易使耐火材產生裂縫與剝離之情形，而若此剝離的耐火材混入碳黑成品中，將導致雜質(grit)升高，影響碳黑成品之品質，同時，若耐火材因產生裂縫與剝離而損壞時，則須停止產線更換反應器，更造成產能損失。 Refractories are widely used in reactors in the chemical industry. Generally speaking, refractories are mainly sintered bodies of metal oxides. Depending on their actual application, they must withstand high temperatures of hundreds to thousands of degrees Celsius (°C). Take the production of carbon black as an example. Since the reaction must be performed in a high temperature environment above 1900℃ and the flue gas with a flow rate of 200 m/s or above must be used, the refractory inside the reactor must withstand the environment of high temperature and high flue gas flow rate. . In addition, when the production-level conversion or the production line stops abnormally, the temperature in the reactor will change drastically, resulting in a thermal shock phenomenon. The above-mentioned high temperature, high flue gas velocity and thermal shock can easily cause cracks and peeling of the refractory. If the peeled refractory is mixed into the carbon black product, it will cause the increase of impurities (grit) and affect the quality of the carbon black product. At the same time, if the refractory material is damaged due to cracks and peeling, the production line must be stopped to replace the reactor, which will cause a loss of production capacity.

本發明藉由提供包含無機纖維之耐火燒結體，而使該耐火燒結體可耐受高溫及高流速煙氣。因此，本發明提供一種耐火燒結體，包含：一耐火基材；及複數條無機纖維，嵌入該耐火基材中。本發明亦提供一種碳黑反應器，其包含前述之耐火燒結體。 The present invention provides a refractory sintered body containing inorganic fibers, so that the refractory sintered body can withstand high temperature and high flow rate of flue gas. Therefore, the present invention provides a refractory sintered body comprising: A refractory substrate; and A plurality of inorganic fibers are embedded in the refractory base material. The present invention also provides a carbon black reactor, which contains the aforementioned refractory sintered body.

本發明提供一種耐火燒結體，包含：一耐火基材；及複數條無機纖維，嵌入該耐火基材中。如圖1所示，於一比較例中，耐火燒結體1’僅由一耐火基材2組成，而未包含無機纖維。其中，部分耐火基材2於燒結後團聚形成顆粒狀之晶體21，其餘部分為較為鬆散之非晶體22。當遭受高溫、高流速煙氣時，容易於非晶體22處產生裂縫10，且裂縫10將沿晶體21之邊緣延伸，貫穿該耐火燒結體1’，而導致該耐火燒結體1’剝離。然而，參照圖2所示，本發明之耐火燒結體1則包含一耐火基材2及複數條無機纖維3，該無機纖維3嵌入該耐火基材2中。類似地，部分耐火基材2於燒結後團聚形成顆粒狀之晶體21，其餘部分為較為鬆散之非晶體22。雖不願為理論所限制，惟咸信該無機纖維3可提供錨定(bolting)之效果，亦即可連結於晶體21及非晶體22之間，以提升該耐火燒結體1之強度。當遭受高溫、高流速煙氣時，縱使於非晶體22處產生裂縫，裂縫沿晶體21之邊緣延伸時即會被該無機纖維3所阻斷，故不會貫穿該耐火燒結體1。因此，可避免該耐火燒結體1於遭受高溫、高流速煙氣時，因沖蝕所產生的接觸面裂縫生成及剝離，而使該耐火燒結體1具有良好的抗沖蝕性及耐熱性。參照圖3及圖4，其分別顯示本發明耐火燒結體之斷裂面的光學放大鏡及電子顯微鏡照片，圖中圓圈處可見該無機纖維之斷面，且該無機纖維及耐火基材緊密結合。由圖3及圖4可知，在該耐火燒結體遭受外力導致斷裂時，該無機纖維仍然存在於斷裂面中，亦即該無機纖維於受力過程中可承受應力，並能有效發揮錨定的效果，以補強該耐火燒結體，並延緩其裂縫生成及剝離之速率。於本發明一較佳實施例中，該耐火基材可為氧化物陶瓷材料，例如氧化鋁(Al ₂O ₃)、氧化矽(SiO ₂)、氧化鉻(Cr ₂O ₃)、氧化鋯(ZrO ₂)、氧化鈦(IV)(TiO ₂)、氧化鎂(MgO)、氧化鈣(CaO)、氧化錫(SnO)、氧化鉿(HfO ₂)或氮化矽(Si ₃N ₄)等。於本發明之一更佳實施例中，該耐火基材係以氧化鋁(Al ₂O ₃)及氧化鉻(Cr ₂O ₃)為主要成分，並可選擇添加氧化鋯(ZrO ₂)等。於該耐火燒結體中，該耐火基材可團聚形成晶體，或呈現非晶體之形態。舉例而言，該耐火基材可包含約50wt%至約90%wt之氧化鋁、約0wt%至約40wt%之氧化鉻、總計約0wt%至約10wt%之氧化鈣及氧化矽、及約0wt%至約10wt%之氧化鋯。較佳的比例為約67wt%至約90%wt之氧化鋁、約7wt%至約30wt%之氧化鉻，以及總計約3wt%至約10wt%之氧化鈣及氧化矽。為達到提升性能等目的，例如，為了提升耐火材的抗熱震性，可加入氧化鋯進行改質。較佳地，該耐火基材可包含約1wt%至約10wt%之氧化鋯。氧化鋁、氧化鉻及氧化鋯之性質及功能說明如下表1所示。表1：氧化鋯。氧化鋁、氧化鉻及氧化鋯之性質及功能說明材料 Al ₂O ₃氧化鋁 Cr ₂O ₃氧化鉻 ZrO ₂氧化鋯熔點 (℃) 2,054 2,435 2,715 莫氏硬度 9 8.0~8.5 8.0~8.5 抗熱震性好好優組成比例 (%) 50-90 5-40 0-10 功能說明耐火材料基本原料提昇耐火材料工作溫度、抗沖蝕性提昇抗熱震性、耐火材料工作溫度於本發明一較佳實施例中，所述無機纖維可為氧化鋁－二氧化矽纖維(Al ₂O ₃-SiO ₂)、玻璃纖維(SiO ₂)、連續玻璃纖維(SiO ₂-Al ₂O ₃-B ₂O ₃-CaO)、玻璃絨(SiO ₂-Al2O ₃-CaO-Na ₂O)、耐鹼玻璃纖維(SiO ₂-ZrO ₂-CaO-Na ₂O)、岩絨(SiO ₂-Al2O ₃-Fe2O ₃-MgO-CaO)、渣絨(SiO ₂-Al ₂O ₃-MgO-CaO)、鈦酸鉀纖維、氧化鋁晶鬚、碳化矽晶鬚、氮化矽晶鬚、碳酸鈣晶鬚、鹼式硫酸鎂晶鬚、硫酸鈣晶鬚(石膏纖維)、氧化鋅晶鬚、氧化鋯纖維、磷酸酯鹽纖維、鹼土金屬矽酸鹽纖維(SiO ₂-CaO-MgO)、硼纖維、石墨纖維或金屬纖維（可為單一金屬或金屬合金製成）等。須特別注意的是，本發明所述無機纖維係排除有機纖維。由於有機纖維的熔點、熱裂解溫度低，當該耐火燒結體遭受高溫、高流速煙氣時，有機纖維將裂解並於該耐火燒結體之內部或表面形成孔洞，此類孔洞將形成連續裂縫，而使該耐火燒結體剝離。於本發明一較佳實施例中，該無機纖維之直徑可為約3 μm至約15 μm，例如可為約3 μm至約5 μm、約5 μm至約10 μm或約10 μm至約15μm，較佳為約6 μm至約8 μm，更佳為約7 μm。藉由選擇適當之直徑，可使該無機纖維具有較佳之強度及彈性，以提升該耐火基材之抗沖蝕性及耐熱性。較佳地，該無機纖維可為氧化鋁－二氧化矽纖維，其係由氧化鋁與二氧化矽共熔物所製作，例如可為Nitivy Co. Ltd., Japan所製造之R-3840A，其材料性質如下表2所示。表2：氧化鋁－二氧化矽纖維R-3840A之材料性質材料性質 Al ₂O ₃-SiO ₂ 數據 R-3840A 化學分析 (%) Al ₂O ₃ 72±2 72 SiO ₂ 28±2 28 纖維直徑 micron 7.0±1.0 7.5 密度 g/cm ³ 2.9±0.2 3.0 該無機纖維也可使用碳化矽所製作，例如可為Haydale Technologies Inc. 所製造之SF-1，其材料性質如下表3所示。表3：碳化矽纖維SF-1之材料性質材料性質 SiC SF-1 纖維直徑 micron 11.0±1.0 密度 g/cm ³ 3.21 於本發明一較佳實施例中，該無機纖維之長度係為該耐火燒結體之厚度的約0.8倍以下，較佳為約0.6倍以下、約0.4倍以下或約0.25倍以下，但較佳不低於約0.05倍及／或不低於約1公分。此處所述之「厚度」係指該耐火燒結體之最小邊長尺寸。舉例而言，若該無機纖維之長度大於該耐火燒結體之厚度的0.8倍，則該無機纖維易大幅度突出於該耐火燒結體之表面，而使該耐火燒結體容易因高溫、高流速煙氣而損壞；另一方面，若該無機纖維之長度小於該耐火燒結體之厚度的0.05倍或小於1公分，則無法達成錨定效果，故難以提升該耐火燒結體之強度。根據本發明之耐火基材的製備，係可將該耐火基材與該無機纖維混合，而後共同燒結形成。較佳地，若該耐火基材包含多種成分（例如包含氧化鋁、氧化鉻、氧化鈣、氧化矽及氧化鋯），則先將多種成分分別秤重後進行拌合，而後，將該無機纖維加入該耐火基材中，進行攪拌並確認該無機纖維無團聚之現象，續加入適量溶劑（例如水）以進行濕拌合。於此過程中，視情況可加入黏合劑等。舉例而言，可將約0.1重量份至約9重量份之無機纖維加入約100重量份之耐火基材中，於攪拌後再加入約7至14重量份之水進行拌合。亦即，於燒結去除水分後，該耐火燒結體中該耐火基材及該無機纖維之重量比可為約1000：1至約100：9。待該耐火基材與該無機纖維混合均勻後，將其共同形成之摻配物倒入模具中，續進行養生、乾燥與燒結。舉例而言，可於室溫下靜置約12至36小時後，移入110℃之烘箱中乾燥12至36小時，續放入高溫爐中以約1300℃至約1800℃之溫度燒結2至5小時，以完成該耐火燒結體。依據應用之需求，該耐火燒結體可做為耐火澆注層或耐火磚等形式提供，故其形狀可為板狀、塊狀或任意形狀等，本發明不加以限制。於本發明一較佳實施例中，該耐火燒結體係用於碳黑反應器之反應段的耐火材料。碳黑反應器之反應段為碳黑生產過程中的重要設備，用於碳黑生產之原料油於此處注入，並與來自前端的高溫氣流混合，以使原料油於高溫下發生熱分解(thermal decomposition)，而產出氣體與碳黑晶核。同時，混合後的煙氣以1900℃以上的高溫及200 m/s以上的速率通過此喉口段，此高溫、高流速煙氣易對反應段內的耐火材料產生沖蝕，並導致耐火材料被破壞而剝離。剝離的耐火材料混合於碳黑中，導致所產出的碳黑中雜質含量上升。因此，為使該耐火燒結體可耐受高溫、高流速煙氣，故於拌合及後續燒結過程中，應盡可能使該耐火基材及該無機纖維緊密結合，避免其中產生氣泡或縫隙等，以避免該耐火燒結體崩裂。舉例而言，該耐火燒結體之孔隙度較佳為約30%以下，例如可為約25%以下，或為約20%至約25%。此外，該耐火燒結體之鬆密度(bulk density)可為約1.6 g/cm ³以上，例如可為約2 g/cm ³以上、約2.5 g/cm ³以上或約3 g/cm ³以上。視所選擇之耐火基材及無機纖維之材質而定，該耐火燒結體之鬆密度可為約3 g/cm ³至約4 g/cm ³。本發明亦提供一種碳黑反應器，其包含前述之耐火燒結體。茲以下列實施例詳細說明本發明之耐火基材，唯並不意謂本發明僅侷限於此等實例所揭示之內容。 耐火燒結體的製備以下表4至8之比例，分別準備實施例E1至E18及比較例C1所需量之無機纖維、耐火基材及水，並以前述之方法拌合形成摻配物，倒入模具並進行養生、乾燥與燒結等步驟。其中，所使用之無機纖維係為前述氧化鋁－二氧化矽纖維R-3840A，所使用之耐火基材則包含78wt%之氧化鋁、14wt%之氧化鉻、6wt%之氧化鈣及2wt%之氧化矽，且燒結溫度為1500℃。實施例E1至E18及比較例C1皆分別製備二份耐火燒結體樣品，以確認其再現性。表4：實施例E1至E4之組成比例 E1 E2 E3 E4 無機纖維（重量份） 0.5 1.0 1.5 2.0 耐火基材（重量份） 100 100 100 100 拌合水量（重量份） 7.5 8 8 8 表5：實施例E5至E8之組成比例 E5 E6 E7 E8 無機纖維（重量份） 2.5 3.0 3.5 4.0 耐火基材（重量份） 100 100 100 100 拌合水量（重量份） 9 9 8 9 表6：實施例E9至E12之組成比例 E9 E10 E11 E12 無機纖維（重量份） 4.5 5.0 5.5 6.0 耐火基材（重量份） 100 100 100 100 拌合水量（重量份） 9 10 10 11 表7：實施例E13至E16及比較例C1之組成比例 E13 E14 E15 E16 無機纖維（重量份） 6.5 7.0 7.5 8.0 耐火基材（重量份） 100 100 100 100 拌合水量（重量份） 12 13 13 13 表8：實施例E17至E18及比較例C1之組成比例 E17 E18 C1 無機纖維（重量份） 8.5 9.0 0 耐火基材（重量份） 100 100 100 拌合水量（重量份） 14 14 7 耐火燒結體的鬆密度及孔隙度測定分別測定實施例E1至E3及比較例C1的耐火燒結體樣品的鬆密度及孔隙度，並紀錄如下表9所示。其中，實施例E1至E3及比較例C1的耐火燒結體樣品的鬆密度約為3 g/cm ³左右，而孔隙度約為23%至約25%之間，且實施例E1至E3及比較例C1之鬆密度及孔隙度皆大致相近。表9：實施例E1至E3及比較例C1之鬆密度及孔隙度 E1 E2 E3 C1 無機纖維（重量份） 0.5 1.0 1.5 0 鬆密度 (g/cm ³) 3.02 3.02 3.02 3.05 孔隙度 (%) 23.86 23.97 24.15 23.52 耐火燒結體的抗熱震測試結果將前述製備之實施例E1至E3及比較例C1的耐火燒結體樣品，分別置於1200℃下20分鐘，而進行氣冷10分鐘，於五個循環後觀察其表面裂縫狀況，重複二次試驗，並紀錄如下表10所示。其中，實施例E1至E3包含無機纖維之耐火燒結體皆可抗熱震，而無裂縫產生；反之，比較例C1之耐火燒結體則有明顯裂縫產生，顯示其抗熱震性質較差。表10：實施例E1至E3及比較例C1之抗熱震測試結果 E1 E2 E3 C1 無機纖維（重量份） 0.5 1.0 1.5 0 試驗I ＞5次＞5次＞5次裂縫產生試驗II ＞5次＞5次＞5次裂縫產生針對實施例E4至E10之抗熱震測試結果與上表類似，且針對實施例E11至E18之抗熱震測試結果亦顯示其具有抗熱震之效果。 耐火燒結體用於碳黑反應器的測試結果分別將前述實施例E1及比較例C1的耐火燒結體用於碳黑反應器之反應段，在相同的碳黑生產參數下進行生產，並於碳黑反應器出口處取樣分析產出碳黑產品的雜質，以及以原子吸收光譜(atomic absorption spectroscopy, AA)量測灰份中鋁及鉻離子的含量，以比對實施例E1及比較例C1的耐火燒結體的抗沖蝕性及對碳黑品質的影響。測試生產之碳黑品級為N234以及N339，爐溫為1982℃，於燃燒空氣流量為9000 Nm ³/h的高溫、高流速條件（煙氣流速大於500 m/s）下進行碳黑生產，並取樣比較產品中的雜質含量。雜質分析時因篩網的尺寸不同，可分為35 mesh、100 mesh以及325 mesh。針對實施例E1及比較例C1的分析結果如圖5（N234）及圖6所示（N339）。其中，圖5及圖6中縱軸為不同篩網分析時的測得的碳黑雜質含量，單位為PPM；橫軸為碳黑的生產日期。參照圖5及圖6所示，使用實施例之耐火燒結體所產出碳黑中的雜質成份明顯下降，相較於使用比較例C1之耐火燒結體平均可降低約20%（針對N234，35 mesh平均降低約22%，100 mesh平均降低約16%，325 mesh平均降低約18%；針對N339，35 mesh平均降低約26%，100 mesh平均降低約25%，325 mesh平均降低約20%）。此外，分別針對實施例E1及比較例C1所產出之碳黑，每週在相同生產及取樣條件下於碳黑反應器出口處取樣A至F（其中A為第一週，B為第二週，以此類推），分析其灰份含量以及其中的金屬離子含量。灰份測試係將碳黑在550±25℃的高溫爐中加熱16小時，使碳黑受熱揮發，僅灰份（主要為金屬氧化物）殘存，秤重其殘餘物並紀錄如下表11至13所示。接著於灰份中加入鹽酸，加熱後，再以原子吸收光譜分析其中的鋁、鉻金屬離子的含量如下表11至13所示。因碳黑中並無鋁、鉻金屬存在，故原子吸收光譜分析結果也可作為耐火材穩定性的指標之一。由下表11至13可知，使用實施例E1之耐火燒結體所產出之碳黑的灰份較少，且其中鋁、鉻金屬離子的含量亦相較於比較例C1大幅下降，顯示實施例E1之耐火燒結體之剝落顯著降低。表11：實施例E1及比較例C1之灰份分析結果(1) 樣品編號 A B 耐火燒結體 E1 C1 E1 C1 成品灰份含量 (%) 0.82 2.33 1.10 3.54 灰份AA分析結果鋁離子 (PPM) ＜0.1 21.1 1.1 42.3 鉻離子 (PPM) ＜0.1 50.8 1.8 96.2 表12：實施例E1及比較例C1之灰份分析結果(2) 樣品編號 C D 耐火燒結體 E1 C1 E1 C1 成品灰份含量 (%) 1.24% 3.94% 0.83% 2.46% 灰份AA分析結果鋁離子 (PPM) 50.1 255.5 64.9 169.8 鉻離子 (PPM) ＜0.1 63.1 0.2 17.8 表13：實施例E1及比較例C1之灰份分析結果(3) 樣品編號 E F 耐火燒結體 E1 C1 E1 C1 成品灰份含量(%) 0.38% 0.60% 1.77% 5.31% 灰份AA分析結果鋁離子 (PPM) 12.7 40.7 11.7 157.7 鉻離子 (PPM) ＜0.1 5.9 5.7 82.3 由上述試驗結果顯示，本發明之耐火燒結體，藉由包含無機纖維，而可達成優異的高溫與抗熱震性質。該耐火燒結體運用於碳黑生產之反應器時，可產出具有較低雜質的碳黑，有利於碳黑品質的提昇。同時，由於該耐火燒結體不易產生裂縫及剝離，而有助於反應器壽命的延長，降低設備的支出及更換時間成本等。上述實施例僅為說明本發明之原理及其功效，而非限制本發明。本發明所屬技術領域中具通常知識者對上述實施例所做之修改及變化仍不違背本發明之精神。本發明之權利範圍應如後述之申請專利範圍所列。 The present invention provides a refractory sintered body, comprising: a refractory substrate; and a plurality of inorganic fibers embedded in the refractory substrate. As shown in FIG. 1, in a comparative example, the refractory sintered body 1 ′ consists only of a refractory substrate 2 and does not contain inorganic fibers. Among them, part of the refractory base material 2 is agglomerated to form granular crystals 21 after sintering, and the remaining part is relatively loose amorphous 22. When subjected to high-temperature and high-velocity flue gas, cracks 10 are likely to occur at the amorphous 22, and the cracks 10 will extend along the edge of the crystal 21 and penetrate the refractory sintered body 1', causing the refractory sintered body 1'to peel off. However, referring to FIG. 2, the refractory sintered body 1 of the present invention includes a refractory substrate 2 and a plurality of inorganic fibers 3, and the inorganic fibers 3 are embedded in the refractory substrate 2. Similarly, part of the refractory base material 2 is agglomerated to form granular crystals 21 after sintering, and the remaining part is relatively loose amorphous 22. Although not wishing to be limited by theory, it is believed that the inorganic fiber 3 can provide a bolting effect, that is, it can be connected between the crystal 21 and the amorphous 22 to enhance the strength of the refractory sintered body 1. When subjected to high-temperature and high-velocity flue gas, even if cracks are generated at the amorphous 22, the cracks will be blocked by the inorganic fibers 3 when they extend along the edge of the crystal 21, and therefore will not penetrate the refractory sintered body 1. Therefore, when the refractory sintered body 1 is exposed to high-temperature and high-velocity flue gas, the formation and peeling of contact surface cracks due to erosion can be avoided, so that the refractory sintered body 1 has good erosion resistance and heat resistance. 3 and 4, which respectively show the optical magnifying glass and the electron micrograph of the fracture surface of the refractory sintered body of the present invention. The cross section of the inorganic fiber can be seen at the circle in the figure, and the inorganic fiber and the refractory substrate are tightly combined. It can be seen from Figures 3 and 4 that when the refractory sintered body is broken by external force, the inorganic fiber still exists in the fracture surface, that is, the inorganic fiber can withstand stress during the stress process and can effectively exert the anchoring The effect is to reinforce the refractory sintered body and delay the rate of crack formation and peeling. In a preferred embodiment of the present invention, the refractory substrate may be an oxide ceramic material, such as alumina (Al ₂ O ₃ ), silicon oxide (SiO ₂ ), chromium oxide (Cr ₂ O ₃ ), zirconia ( ZrO ₂ ), titanium (IV) oxide (TiO ₂ ), magnesium oxide (MgO), calcium oxide (CaO), tin oxide (SnO), hafnium oxide (HfO ₂ ), or silicon nitride (Si ₃ N ₄ ). In a more preferred embodiment of the present invention, the refractory substrate is made of alumina (Al ₂ O ₃ ) and chromium oxide (Cr ₂ O ₃ ) as main components, and can optionally add zirconium oxide (ZrO ₂ ). In the refractory sintered body, the refractory base material may agglomerate to form crystals, or present an amorphous form. For example, the refractory substrate may include about 50wt% to about 90%wt of alumina, about 0wt% to about 40wt% of chromium oxide, a total of about 0wt% to about 10wt% of calcium oxide and silicon oxide, and about 0wt% to about 10wt% zirconia. The preferred ratio is about 67wt% to about 90%wt of alumina, about 7wt% to about 30wt% of chromium oxide, and a total of about 3wt% to about 10wt% of calcium oxide and silicon oxide. In order to achieve the purpose of improving performance, for example, to improve the thermal shock resistance of refractories, zirconia can be added for modification. Preferably, the refractory substrate may contain about 1 wt% to about 10 wt% of zirconia. The properties and functions of alumina, chromium oxide and zirconia are shown in Table 1 below. Table 1: Zirconia. Description of the properties and functions of alumina, chromium oxide and zirconia material Al ₂ O ₃ alumina Cr ₂ O ₃ chromium oxide ZrO ₂ Zirconia Melting point (℃) 2,054 2,435 2,715 Moh's hardness 9 8.0~8.5 8.0~8.5 Thermal shock resistance it is good it is good excellent Composition ratio (%) 50-90 5-40 0-10 Function Description Basic refractory materials Improve the working temperature and erosion resistance of refractory materials Improve thermal shock resistance and refractory working temperature In a preferred embodiment of the present invention, the inorganic fiber can be alumina-silica fiber (Al ₂ O ₃ -SiO ₂ ), glass fiber (SiO ₂ ), continuous glass fiber (SiO ₂ -Al ₂ O ₃ -B ₂ O ₃ -CaO), glass wool (SiO ₂ -Al2O ₃ -CaO-Na ₂ O), alkali-resistant glass fiber (SiO ₂ -ZrO ₂ -CaO-Na ₂ O), stone wool (SiO _2- Al2O ₃ -Fe2O ₃ -MgO-CaO), slag (SiO ₂ -Al ₂ O ₃ -MgO-CaO), potassium titanate fiber, alumina whisker, silicon carbide whisker, silicon nitride whisker, calcium carbonate Whiskers, basic magnesium sulfate whiskers, calcium sulfate whiskers (gypsum fiber), zinc oxide whiskers, zirconia fiber, phosphate ester fiber, alkaline earth metal silicate fiber (SiO ₂ -CaO-MgO), boron fiber , Graphite fiber or metal fiber (may be made of single metal or metal alloy), etc. It is important to note that the inorganic fibers described in the present invention exclude organic fibers. Due to the low melting point and thermal cracking temperature of organic fibers, when the refractory sintered body is exposed to high temperature and high flow rate of flue gas, the organic fibers will crack and form holes inside or on the surface of the refractory sintered body. Such holes will form continuous cracks. The refractory sintered body is peeled off. In a preferred embodiment of the present invention, the diameter of the inorganic fiber may be about 3 μm to about 15 μm, for example, about 3 μm to about 5 μm, about 5 μm to about 10 μm, or about 10 μm to about 15 μm. , Preferably about 6 μm to about 8 μm, more preferably about 7 μm. By choosing an appropriate diameter, the inorganic fiber can have better strength and elasticity, so as to improve the erosion resistance and heat resistance of the refractory substrate. Preferably, the inorganic fiber can be alumina-silica fiber, which is made of a eutectic of alumina and silica, for example, it can be R-3840A manufactured by Nitivy Co. Ltd., Japan. The material properties are shown in Table 2 below. Table 2: Material properties of alumina-silica fiber R-3840A Material properties Al ₂ O ₃ -SiO ₂ data R-3840A Chemical analysis(%) Al ₂ O ₃ 72±2 72 SiO ₂ 28±2 28 Fiber diameter micron 7.0±1.0 7.5 density g/cm ³ 2.9±0.2 3.0 The inorganic fiber can also be made of silicon carbide, for example, SF-1 manufactured by Haydale Technologies Inc. The material properties are shown in Table 3 below. Table 3: Material properties of silicon carbide fiber SF-1 Material properties SiC SF-1 Fiber diameter micron 11.0±1.0 density g/cm ³ 3.21 In a preferred embodiment of the present invention, the length of the inorganic fiber is about 0.8 times or less of the thickness of the refractory sintered body, preferably about 0.6 times or less, about 0.4 times or less, or about 0.25 times or less, but preferably Not less than about 0.05 times and/or not less than about 1 cm. The "thickness" mentioned here refers to the minimum side length dimension of the refractory sintered body. For example, if the length of the inorganic fiber is greater than 0.8 times the thickness of the refractory sintered body, the inorganic fiber is likely to protrude largely on the surface of the refractory sintered body, and the refractory sintered body is prone to smoke due to high temperature and high flow rate. On the other hand, if the length of the inorganic fiber is less than 0.05 times the thickness of the refractory sintered body or less than 1 cm, the anchoring effect cannot be achieved, so it is difficult to increase the strength of the refractory sintered body. According to the preparation of the refractory substrate of the present invention, the refractory substrate can be mixed with the inorganic fiber, and then co-sintered to form. Preferably, if the refractory base material contains multiple components (such as aluminum oxide, chromium oxide, calcium oxide, silicon oxide, and zirconium oxide), the multiple components are weighed separately and then mixed, and then the inorganic fiber Add to the refractory base material, stir and confirm that the inorganic fibers have no agglomeration, and then add an appropriate amount of solvent (such as water) for wet mixing. During this process, adhesives can be added as appropriate. For example, about 0.1 parts by weight to about 9 parts by weight of inorganic fibers can be added to about 100 parts by weight of the refractory substrate, and after stirring, about 7 to 14 parts by weight of water are added for mixing. That is, after sintering to remove moisture, the weight ratio of the refractory base material and the inorganic fiber in the refractory sintered body may be about 1000:1 to about 100:9. After the refractory base material and the inorganic fiber are uniformly mixed, the blend formed by them is poured into the mold, and the curing, drying and sintering are continued. For example, it can be left at room temperature for about 12 to 36 hours, then transferred to an oven at 110°C to dry for 12 to 36 hours, and then placed in a high temperature furnace for sintering at a temperature of about 1300°C to about 1800°C for 2 to 5 Hours to complete the refractory sintered body. According to application requirements, the refractory sintered body can be provided in the form of refractory cast layer or refractory brick, so its shape can be plate, block or any shape, etc., and the present invention is not limited. In a preferred embodiment of the present invention, the refractory sintering system is used as a refractory material in the reaction section of a carbon black reactor. The reaction section of the carbon black reactor is an important equipment in the carbon black production process. The raw oil used for carbon black production is injected here and mixed with the high-temperature air flow from the front end to cause the raw oil to thermally decompose at high temperature ( thermal decomposition), and produce gas and carbon black nuclei. At the same time, the mixed flue gas passes through this throat section at a high temperature above 1900℃ and a velocity above 200 m/s. This high temperature and high velocity flue gas is likely to cause erosion of the refractory materials in the reaction section and cause refractory materials. Destroyed and stripped. The peeled refractory material is mixed in the carbon black, resulting in an increase in the impurity content of the produced carbon black. Therefore, in order to make the refractory sintered body can withstand high temperature and high flow rate of flue gas, during the mixing and subsequent sintering process, the refractory base material and the inorganic fiber should be closely combined as much as possible to avoid bubbles or gaps. To avoid the refractory sintered body from cracking. For example, the porosity of the refractory sintered body is preferably about 30% or less, for example, it may be about 25% or less, or about 20% to about 25%. In addition, the bulk density of the refractory sintered body can be about 1.6 g/cm ³ or more, for example, it can be about 2 g/cm ³ or more, about 2.5 g/cm ³ or more, or about 3 g/cm ³ or more. Depending on the selected refractory base material and inorganic fiber materials, the bulk density of the refractory sintered body can be about 3 g/cm ³ to about 4 g/cm ³ . The present invention also provides a carbon black reactor, which contains the aforementioned refractory sintered body. The following examples are used to illustrate the refractory substrate of the present invention in detail, but it does not mean that the present invention is limited to the content disclosed in these examples. Preparation of refractory sintered body in the following proportions in Tables 4 to 8, prepare the inorganic fibers, refractory base material and water required in Examples E1 to E18 and Comparative Example C1, respectively, and mix them to form a blend by the aforementioned method. Put it into the mold and perform the steps of curing, drying and sintering. Among them, the inorganic fiber used is the aforementioned alumina-silica fiber R-3840A, and the refractory substrate used contains 78wt% alumina, 14wt% chromium oxide, 6wt% calcium oxide and 2wt% Silicon oxide, and the sintering temperature is 1500°C. In Examples E1 to E18 and Comparative Example C1, two refractory sintered body samples were prepared to confirm their reproducibility. Table 4: Composition ratio of Examples E1 to E4 E1 E2 E3 E4 Inorganic fiber (parts by weight) 0.5 1.0 1.5 2.0 Refractory base material (parts by weight) 100 100 100 100 Mixing water amount (parts by weight) 7.5 8 8 8 Table 5: Composition ratio of Examples E5 to E8 E5 E6 E7 E8 Inorganic fiber (parts by weight) 2.5 3.0 3.5 4.0 Refractory base material (parts by weight) 100 100 100 100 Mixing water amount (parts by weight) 9 9 8 9 Table 6: Composition ratio of Examples E9 to E12 E9 E10 E11 E12 Inorganic fiber (parts by weight) 4.5 5.0 5.5 6.0 Refractory base material (parts by weight) 100 100 100 100 Mixing water amount (parts by weight) 9 10 10 11 Table 7: Composition ratio of Examples E13 to E16 and Comparative Example C1 E13 E14 E15 E16 Inorganic fiber (parts by weight) 6.5 7.0 7.5 8.0 Refractory base material (parts by weight) 100 100 100 100 Mixing water amount (parts by weight) 12 13 13 13 Table 8: Composition ratio of Examples E17 to E18 and Comparative Example C1 E17 E18 C1 Inorganic fiber (parts by weight) 8.5 9.0 0 Refractory base material (parts by weight) 100 100 100 Mixing water amount (parts by weight) 14 14 7 Measurement of bulk density and porosity of refractory sintered body The bulk density and porosity of the refractory sintered body samples of Examples E1 to E3 and Comparative Example C1 were measured, and recorded as shown in Table 9 below. Among them, the bulk density of the refractory sintered body samples of Examples E1 to E3 and Comparative Example C1 is about 3 g/cm ³ , and the porosity is between about 23% to about 25%, and Examples E1 to E3 and comparison The bulk density and porosity of Example C1 are roughly similar. Table 9: Bulk density and porosity of Examples E1 to E3 and Comparative Example C1 E1 E2 E3 C1 Inorganic fiber (parts by weight) 0.5 1.0 1.5 0 Bulk density (g/cm ³ ) 3.02 3.02 3.02 3.05 Porosity(%) 23.86 23.97 24.15 23.52 Thermal shock resistance test results of the refractory sintered body. The refractory sintered body samples prepared in Examples E1 to E3 and Comparative Example C1 were placed at 1200°C for 20 minutes, and air-cooled for 10 minutes, and observed after five cycles Repeat the second test for the surface crack status and record it as shown in Table 10. Among them, the refractory sintered bodies of Examples E1 to E3 containing inorganic fibers can resist thermal shock without cracks; on the contrary, the refractory sintered body of Comparative Example C1 has obvious cracks, indicating that its thermal shock resistance is poor. Table 10: Thermal shock resistance test results of Examples E1 to E3 and Comparative Example C1 E1 E2 E3 C1 Inorganic fiber (parts by weight) 0.5 1.0 1.5 0 Test I ＞5 times ＞5 times ＞5 times Cracks Test II ＞5 times ＞5 times ＞5 times Cracks The thermal shock resistance test results for Examples E4 to E10 are similar to the above table, and the thermal shock resistance test results for Examples E11 to E18 also show that it has a thermal shock resistance effect. Test results of the use of refractory sintered bodies in carbon black reactors. The refractory sintered bodies of the foregoing Example E1 and Comparative Example C1 were used in the reaction section of the carbon black reactor, and were produced under the same carbon black production parameters. Sampling at the outlet of the black reactor to analyze the impurities in the carbon black product, and measuring the content of aluminum and chromium ions in the ash by atomic absorption spectroscopy (AA) to compare the results of Example E1 and Comparative Example C1 The erosion resistance of refractory sintered body and its influence on the quality of carbon black. The carbon black grades tested and produced are N234 and N339, the furnace temperature is 1982℃, and the combustion air flow rate is 9000 Nm ³ /h at high temperature and high flow rate (flue gas flow rate greater than 500 m/s). And take a sample to compare the impurity content in the product. In the analysis of impurities, due to the size of the screen, it can be divided into 35 mesh, 100 mesh and 325 mesh. The analysis results of Example E1 and Comparative Example C1 are shown in Figure 5 (N234) and Figure 6 (N339). Among them, the vertical axis in Figures 5 and 6 is the measured carbon black impurity content during the analysis of different screens, in PPM; the horizontal axis is the production date of the carbon black. Referring to Figures 5 and 6, the impurity content in the carbon black produced by the refractory sintered body of the example is significantly reduced, which can be reduced by about 20% on average compared to the refractory sintered body of the comparative example C1 (for N234, 35 The average reduction of mesh is about 22%, the average reduction of 100 mesh is about 16%, the average reduction of 325 mesh is about 18%; for N339, the average reduction of 35 mesh is about 26%, the average reduction of 100 mesh is about 25%, and the average reduction of 325 mesh is about 20%) . In addition, for the carbon black produced in Example E1 and Comparative Example C1, samples A to F are sampled at the outlet of the carbon black reactor under the same production and sampling conditions each week (where A is the first week and B is the second Zhou, and so on), analyze its ash content and metal ion content. The ash test is to heat the carbon black in a high-temperature furnace at 550±25℃ for 16 hours to volatilize the carbon black. Only the ash (mainly metal oxide) remains. Weigh the residue and record the following table 11 to 13 Shown. Then, hydrochloric acid was added to the ash, and after heating, the content of aluminum and chromium metal ions was analyzed by atomic absorption spectroscopy, as shown in Tables 11 to 13. Because there is no aluminum and chromium in carbon black, the results of atomic absorption spectroscopy can also be used as one of the indicators of refractory stability. From Tables 11 to 13 below, it can be seen that the ash content of the carbon black produced by using the refractory sintered body of Example E1 is less, and the content of aluminum and chromium metal ions are also significantly lower than that of Comparative Example C1. The peeling of the refractory sintered body of E1 is significantly reduced. Table 11: Ash analysis results of Example E1 and Comparative Example C1 (1) Sample serial number A B Refractory sintered body E1 C1 E1 C1 Ash content of finished product (%) 0.82 2.33 1.10 3.54 Ash AA analysis result Aluminum ion (PPM) ＜0.1 21.1 1.1 42.3 Chromium ion (PPM) ＜0.1 50.8 1.8 96.2 Table 12: Ash analysis results of Example E1 and Comparative Example C1 (2) Sample serial number C D Refractory sintered body E1 C1 E1 C1 Ash content of finished product (%) 1.24% 3.94% 0.83% 2.46% Ash AA analysis result Aluminum ion (PPM) 50.1 255.5 64.9 169.8 Chromium ion (PPM) ＜0.1 63.1 0.2 17.8 Table 13: Ash analysis results of Example E1 and Comparative Example C1 (3) Sample serial number E F Refractory sintered body E1 C1 E1 C1 Ash content of finished product (%) 0.38% 0.60% 1.77% 5.31% Ash AA analysis result Aluminum ion (PPM) 12.7 40.7 11.7 157.7 Chromium ion (PPM) ＜0.1 5.9 5.7 82.3 The above test results show that the refractory sintered body of the present invention can achieve excellent high temperature and thermal shock resistance by containing inorganic fibers. When the refractory sintered body is used in a reactor for carbon black production, carbon black with lower impurities can be produced, which is beneficial to the improvement of carbon black quality. At the same time, since the refractory sintered body is not prone to cracks and peeling, it helps to extend the life of the reactor, reduce equipment expenditures and replacement time costs. The above-mentioned embodiments only illustrate the principles and effects of the present invention, but do not limit the present invention. Modifications and changes made to the above embodiments by those with ordinary knowledge in the technical field of the present invention do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.

1’:比較例之耐火燒結體 1:本發明之耐火燒結體 2:耐火基材 3:無機纖維 10:裂縫 21:晶體 22:非晶體 1’: Refractory sintered body of comparative example 1: The refractory sintered body of the present invention 2: Refractory substrate 3: Inorganic fiber 10: Crack 21: Crystal 22: Amorphous

圖1顯示習知之耐火燒結體的剖視示意圖；圖2顯示本發明之耐火燒結體的剖視示意圖；圖3顯示本發明之耐火燒結體之斷裂面的光學放大鏡照片；圖4顯示本發明之耐火燒結體之斷裂面的電子顯微鏡照片；圖5顯示使用實施例E1及比較例C1之耐火燒結體所產出之N234碳黑的雜質分析結果；及圖6顯示使用實施例E1及比較例C1之耐火燒結體所產出之N339碳黑的雜質分析結果。 Figure 1 shows a schematic cross-sectional view of a conventional refractory sintered body; Figure 2 shows a schematic cross-sectional view of the refractory sintered body of the present invention; Figure 3 shows an optical magnifying glass photo of the fracture surface of the refractory sintered body of the present invention; Figure 4 shows an electron micrograph of the fracture surface of the refractory sintered body of the present invention; Figure 5 shows the results of impurity analysis of N234 carbon black produced by using the refractory sintered bodies of Example E1 and Comparative Example C1; and Figure 6 shows the results of impurity analysis of N339 carbon black produced by using the refractory sintered bodies of Example E1 and Comparative Example C1.

1:本發明之耐火燒結體 1: The refractory sintered body of the present invention

2:耐火基材 2: Refractory substrate

3:無機纖維 3: Inorganic fiber

21:晶體 21: Crystal

22:非晶體 22: Amorphous

Claims

A refractory sintered body includes a sintered refractory substrate and a plurality of inorganic fibers, wherein the plurality of inorganic fibers are embedded in the refractory substrate.

The refractory sintered body of claim 1, wherein the refractory base material comprises a refractory ceramic material selected from the group consisting of aluminum oxide, chromium oxide, zirconium oxide, silicon oxide, titanium oxide, magnesium oxide, calcium oxide, tin oxide, and hafnium oxide And silicon nitride or other metal oxides.

The refractory sintered body of claim 2, wherein the refractory substrate comprises about 50wt% to about 90wt% alumina, about 0wt% to about 40wt% chromium oxide, a total of about 0wt% to about 10wt% calcium oxide and oxide Silicon, and about 0wt% to about 10wt% zirconia.

Such as the refractory sintered body of claim 1, wherein the inorganic fiber is alumina-silica fiber, glass fiber, boron fiber, graphite fiber, metal fiber, continuous glass fiber, glass wool, alkali-resistant glass fiber, rock wool, Slag wool, potassium titanate fiber, alumina whisker, silicon carbide whisker, silicon nitride whisker, calcium carbonate whisker, basic magnesium sulfate whisker, calcium sulfate whisker, zinc oxide whisker, zirconia fiber, Phosphate fiber or alkaline earth metal silicate fiber.

The refractory sintered body of claim 1, wherein the diameter of the inorganic fiber is about 3 μm to about 15 μm.

The refractory sintered body of claim 1, wherein the length of the inorganic fiber is the refractory sintered body The thickness is about 0.8 times or less.

The refractory sintered body of claim 1, wherein the weight ratio of the refractory base material and the inorganic fiber is about 1000:1 to about 100:9.

Such as the refractory sintered body of claim 1, which is sintered at a temperature of about 1300°C to about 1800°C.

For example, the refractory sintered body of claim 1 has a porosity of about 30% or less.

For example, the refractory sintered body of claim 1 has a bulk density of about 1.6 g/cm ³ or more.

A carbon black reactor comprising the refractory sintered body according to any one of claims 1 to 10.