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研究生： 盧釩達
Lumbantoruan, Franky Juanda
論文名稱： 煉焦爐燃燒合成熱間修補材料之開發
Development of Hot Repairing Material for Coke Oven based on Combustion Synthesis
指導教授： 鍾賢龍
Chung, Shyan-Lung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2011
畢業學年度： 99
語文別： 英文
論文頁數： 135
外文關鍵詞： hot repairing material, combustion synthesis, penetration and corrosion, pouring and spraying, coke oven
相關次數： 點閱：76  下載：1 
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    • 煉焦爐為將煤煉製成焦炭之反應爐體。其通常使用在高溫下有高強度的防火矽磚當防火內襯，但因矽磚接觸冷空氣並易受煤炭腐蝕，故造成矽磚的損耗和剝落。近年發展出將熱間修補材料搭配噴補技術以達延長煉焦爐之年限。本論文旨在使用自我蔓延高溫合成技術(SHS)開發熱間修補材料。熱間修補材料藉由滲透與腐蝕矽磚表面來達到修補材料與矽磚之間有好的鍵結與穩定性。為評估不同熱間修補材料之機械性能，故使用數種不同系統。本論文之熱間修補材料主要有四種組成:燃料(矽、鋁、鎂)、氧化劑(氧化鐵(三價)與錳(四價))、惰性物質(如二氧化矽)及添加劑。當矽含量為27.97 wt%、鎂為2.25 wt%、鋁為1.13 wt%、41.64 wt%三氧化二鐵、13.5 wt%二氧化錳、4.5 wt%三氧化二鉻與9 wt%二氧化矽之比例時，可得到高方石英相，且其修補損失為21.28%，孔隙度為7.58%、鍵結強度0.6 MPa、耐熱衝擊為九個循環。

    A coke oven is a device used to produce coke by heating under controlled atmosphere from coal. Coke ovens are normally constructed with refractory silica brick which has a high mechanical strength at high temperatures. The coke oven suffers from wear and spalling because of variation of temperature during operation and the charged coal. Repairing technology and repairing materials are required when wearing, cracks or other damages occurs with the coke oven. Hot repairing material with gunning technique was developed in recent years to overcome this situation. This experiment is aimed at developing hot repairing materials based on combustion synthesis for coke oven refractory. The repairing was based on penetration and corrosion of hot repairing material to the silica brick, which promotes a good formation of bonding at the interface. Hot repairing materials were formulated to be composed of four major constituents: silicon, aluminum and magnesium as fuels, iron(III) oxide and manganese(IV) oxide as oxidizer, SiO2 (original lining refractory) as framework and additives. To evaluate the mechanical properties and the performance, various repairing material systems have been developed and tested. The composition for the best performance is 27.97 wt% of Si, 2.25 wt% of Mg, 1.13 wt% of Al, 41.64 wt% of Fe2O3, 13.5 wt% of MnO2, 4.5 wt% of Cr2O3, 9 wt% of SiO2. With this composition, the rebound loss is 21.28%, apparent porosity is 7.58%, refractoriness test 1450 0C, bonding strength is 0.6 Mpa, thermal shock is 9 cycle and high intensity of cristobalite phase after coal and tar attack test.

    摘要 II ABSTRACT III ACKNOWLEDGEMENTS IV TABLE OF CONTENTS V LIST OF TABLES X LIST OF FIGURES XIII CHAPTER I INTRODUCTION 1 CHAPTER II LITERATURE REVIEW 3 II.1 Coke oven refractory 3 II.1.1 Coke Oven 3 II.1.2 Damage to Coke Oven 5 II.2 Spraying/Gunning as Repairing Technique 6 II.3 The Solid State and Thermite Reaction 8 II.3.1 The Solid State 8 II.3.2 Thermite reactions 10 II.4 Reaction Propagation Mechanism 11 II.5 Equivalence Ratio 16 II.6 Combustion Wave Stability 16 II.7 Carbon Deposit. 17 II.7.1 Influence of temperature of fine particles on carbon deposition rate 17 II.7.2 Influence of the concentration of fines on the carbon deposition rate 18 II.7.3 Adhesion mechanism of carbon fine particle 19 II.8 Wear Mechanism of Monolithic Refractories 19 II.8.1 Abrasion 19 II.8.2 Spalling 20 II.9 Penetration 22 II.10 Amount of water in gunning installation. 25 CHAPTER III EXPERIMENTAL SECTION 26 III.1 Properties and Characteristic of reactant 26 III.2 Experimental Procedure 27 III.2.1 Surface treatment 27 III.2.2 Preliminary Ignition and combustion temperature measurement 28 III.2.3 Combustion reaction synthesis 30 III.2.3 Rebound loss 32 III.2.4 Apparent porosity, water absorption and density measurement 33 III.2.5 Modulus of rupture (bonding strength) 34 III.2.6 Abrasion test resistance 35 III.2.7 Thermal shock test resistance 36 III.2.8 Carbon/tar attack resistance 38 III.2.9 Spraying hot repairing material to the silica brick 38 III.3 Element and Compound Identification 39 III.4 Microstructure 39 CHAPTER IV RESEARCH POLICY, METHODS AND STEPS 41 IV.1 Basic information 41 IV.2 Requirement to the SHS hot repairing material 41 IV.2.1 General requirement 41 IV.2.2 Specific requirement 42 CHAPTER V RESULTS AND DISCUSSION 43 V.1 Temperature profile during repairing 43 V.2 The properties of old silica brick 44 V.3 Preliminary study of reactant 47 V.3.1 Effect of Mg addition to temperature profile 48 V.3.2 Effect of KNO3 content to temperature profile 48 V.3.3 Effect of oxidizer to temperature profile 49 V.3.4 Effect of framework content 51 V.4 Study of the hot repairing material for coke oven 52 V.4.1 Iron (III) oxide system 52 V.4.2 Iron (II,III) oxide system 55 V.4.3 Manganese (IV) oxide system 58 V.4.4 Iron(III) oxidizer - manganese(IV) oxidizer system 59 V.4.5 Iron (II) oxide – titanium (IV) oxide system 61 V.5 Frame work particle size and content investigation 65 V.6 Reduce the fayalite (2FeO.SiO2) content on the burned specimen 67 V.6.1 Manganese(IV) as oxidizer 68 V.6.2 Addition aluminum to the hot repairing material 69 V.6.3 Aluminum as substitute to silicon as fuel 70 V.7 Effect of temperature in the surface of silica brick 72 V.8 Sodium silicate as binder to the hot repairing material 73 V.9 Effect of additive with different composition 75 V.9.1 Addition of magnesium to the reagent 75 V.9.2 Addition of yttrium(III) oxide to the reagent 77 V.9.3 Addition of zirconium(IV) oxide to the reagent 81 V.9.4 Addition of titanium(IV) oxide to the reagent 84 V.9.5 Addition of chromium(III) oxide to the reagent 87 V.10.1 Effect of Mechanical activation 90 V.10.1 Silicon-Iron(III) oxide system 90 V.10.2 Silicon-Manganese(IV) oxide system 94 V.11 Rebound loss measurement 97 V.12 Microstructure observation and interface 98 V.12.1 F92 system – pouring method 98 V.12.2 Ma 60 system – pouring method 105 V.12.3 Ma 60 system – spraying method 107 V.12.4 Surface of hot repairing material 112 V.13 Bonding strength of hot repairing material to the silica brick 113 V.13.1 Bonding strength conducted by pouring method 113 V.13.2 Bonding strength conducted by spraying method 115 V.14 Abrasion resistance test at room temperature 116 V. 15 Thermal shock resistance test 117 V.15.1 The behavior of hot repairing material conducted by pouring method subjected to the thermal shock 118 V.15.2 The behavior of hot repairing material conducted by spraying subjected to the thermal shock 119 V.16 Carbon attack test 122 V.17 Proposed reaction of repairing material for coke oven by combustion synthesis 127 CHAPTER VI CONCLUSION 131 REFERENCES 133

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