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Student Number 84341001
Author Maw-Suey Kuo(郭茂穗)
Author's Email Address s4341001@cc.ncu.edu.tw
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Department Chemical and Materials Engineering
Year 2002
Semester 2
Degree Ph.D.
Type of Document Doctoral Dissertation
Language zh-TW.Big5 Chinese
Title 以不同方法製備稻殼灰分-氧化鋁擔載鎳觸媒之研究
Date of Defense 2003-06-28
Page Count 332
Keyword
  • methanation
  • nickel catalyst
  • rice husk ash
  • Abstract Rice husk ash (RHA) was impregnated with aluminium nitrate and calcined to form silica alumina oxides (RHA-Al2O3) and used as catalyst support; it is further loaded with nickel by impregnation and deposition-precipitation. Characterization was made with nitrogen adsorption, ICP-AES, SEM, TEM, XRD, XPS, TGA, DSC, H2-TPD, ammonia adsorption, and TPR while the catalytic performance was determined by the hydrogenation of carbon dioxide under normal pressure. Based on the experiment results, model is established to describe the preparation of Ni/RHA-Al2O3 from RHA.
    Silica content is different for RHA of different origin and ranges from 9 to 14wt.% in terms of SiO2. Highly porous RHA with SiO2 content greater than 99.98% can be obtained by hydrolysis following leaching with 3N HCl. Such obtained RHA is of amorphous and mesopore enriched and merits attention of being used as catalyst support.
    For the composite support (RHA-Al2O3), it is found that impregnation of aluminum salt modified the pore size resulting in uniform pores, which is believed in favor of selectivity. In the mean time, the specific surface area of RHA-Al2O3 decreased with increasing Al2O3 content. The acid amount of RHA-Al2O3 is proportional to the surface area。
    In the preparation of I-Ni/RHA-Al2O3 catalysts by incipient wetness impregnation method, three types of nickel oxide can exist, namely, bulk-NiO and two types of NiAl2O4-like, one with Ni-ion deposited on tetrahedral lattice of Al2O3 and the other on octahedral lattice. That on octahedral lattices was reduced easily, that on tetrahedral lattice was much difficult to be reduced. NiAl2O4-like of tetrahedral was observed in lower nickel loading below 10wt.%, when nickel loading went beyond 10wt.% bulk-NiO formed gradually and all three types of nickel oxide were observed. The crystal size of nickel oxide grew with increasing of nickel loading. The dried precursor, complex of nickel aluminum nitrate from incipient wetness impregnation of nickel nitrate, was of net work structure and decomposed at 400ºC and above. From TPR, the solid dissolution was observed; Ni-ions diffused from bulk-NiO to octahedral lattices of Al2O3 then to tetrahedral lattices and became more difficult to be reduced. It is also seen from XRD, the NiO converted to spinel along with the increasing of calcination temperature.
    The specific surface area of I-Ni/RHA-Al2O3 increased with nickel loading during impregnation to the maximum of 200 m2/g at 15wt% nickel loading and then decreased. Though the specific surface area of I-Ni/RHA-Al2O3 is lower than that of commercial I-Ni/SiO2-Al2O3, its pores are larger than that of I-Ni/SiO2-Al2O3 but shallower giving less pore resistance. Results of methanation experiment confirm that I-Ni/RHA-Al2O3 exhibits better activity and selectivity as well than I-Ni/SiO2-Al2O3. The supported nickel catalyst possess good thermal stability, hence the activity of catalysts for the CO2 methanation was not affected by calcination and reduction temperature. However, the catalyst activity increases with reaction temperature until 500 ºC then decreases, therefore, the optimum temperature for CO2 methanation is 500 ºC.
    For the P-Ni/RHA-Al2O3 catalysts prepared by deposition- precipitation, both increasing the Ni-ion concentration and deposition- precipitation time increased the nickel loading. Increasing the deposition- precipitation time also increased the amount of nickel-support interaction. With constant deposition-precipitation time of 24 hours, controlling the nickel loading by adjusting Ni-ion concentration, nickel dispersed very well when nickel loading below 26.4wt.% but gradually formed bulk-NiO when go beyond 26.4wt.%. When keeping the Ni-ion concentration at 0.14M and controlling the nickel loading by deposition-precipitation time, it gave good dispersion when nickel loading was below 12.0wt.%. Therefore, controlling the nickel loading by adjusting Ni-ion concentration gives better dispersion of nickel on catalyst.
    The stability of precipitate from deposition-precipitation is better than Ni-ion, it react only with hydroxides on the support surface and will not diffuse into the support lattice. P-Ni/RHA-Al2O3 from deposition-precipitation method only presented two types of nickel oxides, bulk-NiO and nickel aluminate. With low nickel loading, only nickel aluminate was observed. Both types of nickel oxides were found at higher nickel loading. Similar to the incipient wetness impregnation method, crystal size of nickel oxide increased with nickel loading. But when the deposition-precipitation time extended over 48 hours, the crystal size tended to shrink slightly. The catalyst precursor after drying also presents net work structure and converts to nickel oxide at the calcination temperature of 500 ºC. Calcination of the catalyst precursor gave NiAl2O4 spinel which is very difficult to reduce. From XRD it is found that NiO transformed to spinel gradually along with increasing of calcination temperature but with smaller crystal size than that found in incipient wetness impregnation method. It shows that the X-ray diffraction spectrum of phase change is more obvious with incipient wetness impregnation method than that of deposition-precipitation method.
    The BET specific surface area of P-Ni/RHA-Al2O3 from deposition-precipitation increased with precipitation time ranging from 151 to 176 m2/g, but decreased with increasing of Ni-ions concentration. The surface structure is of mesopore and the pore size can be controlled by Ni-ion concentration. Experimental result shows that the activity of catalyst increases with reaction temperature until 500 ºC and then decreases. Hence the optimum reaction temperature for CO2 methanation is also 500 ºC. Based on the reaction performance on the CO2 methanation, I-Ni/RHA-Al2O3 gives both better activity and selectivity than P-Ni/SiO2-Al2O3 does.
    The RHA-alumina composite oxide prepared in this experiment is a catalyst support with highly promotive. Whether the supported nickel catalyst made from incipient wetness impregnation method or deposition-precipitation, all gives better than 90% yield in the CO2 methanation and is a superior catalyst.
    Table of Content 內容頁數
    中文摘要………………………………………………………………i
    英文摘要……………………………………………………………v
    圖索引………………………………………………………………xii
    表索引………………………………………………………………xxii
    第一章緒論………………………………………………………..1
      1-1研究背景與動機…………………………………………..1
      1-2研究內容與本論文的結構………………………………...8
    第二章文獻回顧………………………………………………….10
      2-1稻殼灰分的性質及製備程序…………………………….10
      2-2擔體的性質………………………………………….…...21
      2-3製備方法對擔體鎳觸媒特性的影響……………….……29
      2-4擔體效應………………………………………….….……37
      2-5二氧化碳氫化生成甲烷反應……………………………40
    第三章理論分析…………………………………………………46
      3-1熱力學的分析………………………………….….………析…………………………………………….46
      3-2動力學的分析……………………………………….…...析…………………………………………….52
      3-3數據的計算………………………………………………54
    第 四章實驗部分………………………………………………….62
      4-1藥品及氣體…………………………………………….…62
      4-2儀器設備…………………………………………………63
      4-3觸媒擔體的製備………………………………….………65
      4-4觸媒的製備……………………………………………….70
      4-5擔體與觸媒的鑑定分析…………………………………..74
      4-6觸媒的活性測試:CO2甲烷化反應………………84
      4-7實驗流程與操作變數……………………………………..87
    第五章含浸法複合擔體鎳觸媒的結果與討論…………………..93
    5-1稻殼灰分的製備…………………………………………..93
    5-2矽鋁氧化物複合擔體的製備……………………………..120
    5-3含浸法I-Ni/RHA-Al2O3觸媒的特性分析………………..145
    5-4I-Ni/RHA-Al2O3觸媒的活性測試………………………...184
    5-5I-Ni/RHA-Al2O3與Ni/SiO2-Al2O3的活性比較…………較…………..193
      5-6I-Ni/RHA-Al2O3觸媒的製備模型………………………..199
    第六章沈澱固著法擔體鎳觸媒的結果與討論…………………..201
    6-1P-Ni/RHA-Al2O3觸媒的特性分析……………………..201
    6-2P-Ni/RHA-Al2O3觸媒的活性測試……………………..257
    6-3P-Ni/RHA-Al2O3與I-Ni/RHA-Al2O3的活性比較…….264
    6-4P-Ni/RHA-Al2O3與P-Ni/SiO2-Al2O3的活性比較……..268
    6-5P-Ni/RHA-Al2O3觸媒的製備模型……………………….273
    第七章結論………………………………………………………..275
    參考文獻……………………………………………………………..279
    附錄實驗數據………………………………………………….294

    圖索引
    Page
    Fig. 2-1Acid amounts for silica-alumina v.s. proportion of silica. ..………………………………………………27
    Fig. 3-1Heats of reaction as functions of temperature……….48
    Fig. 3-2Equilibrium constants as functions of temperature...49
    Fig. 3-3Free energy changes as functions of temperature ....50
    Fig. 4-1Schematic diagram of the apparatus for the acid treatment of rice hsuk………………………………67
    Fig. 4-2Schematic diagram of the apparatus for pyrolysis and calcination of rice husk and catalyst………….……..69
    Fig. 4-3Schematic diagram of H2 temperature-programmed reduction (TPR) /desorption system (TPD) .……….72
    Fig. 4-4Schematic diagram of reaction system for hydrogen- ation of CO2...………………………………………..85
    Fig. 4-5Experimental flow chart on preparation procedure of rice husk ash…………………………………………88
    Fig. 4-6Experimental flow chart on preparation of RHA-Al2O3 supports…………………………………90
    Fig. 4-7Experimental flow chart on preparation of nickel catalysts on RHA-Al2O3 ……….....……….……….92
    Fig. 5-1XRD spectras of rice husk (a) raw rice husk (b) acid-treated (c) raw rice husk pyrolyzed at 700oC (d) acid-treated pryolyzed at 700oC ; pryolyzed and then calcined at (e) 600oC (f) 700oC (g) 800oC(h) 900oC…98
    Fig. 5-2XPS spectra of Si 2p in (a) acid-treated rice husk (b) raw rice husk……………………………………….... 99
    Fig. 5-3XPS spectra of Si 2p in rice husk ash calcined at (a) 600oC (b) 700 oC (c) 900 oC…………………………100
    Fig. 5-4The SEM images of rice husk (a) raw rice husk. (b) rice husk pyrolyzed at 600oC (c) rice husk ash pyrolyzed and then calcined at 600 oC(d) rice husk ash pyrolyzed and then calcined at 700 oC…………101
    Fig. 5-5TGA curve of untreated rice hsuk and acid-treated rice hsuk……………………………………………..106
    Fig. 5-6The DSC curve of rice hsuk ash calcined at 450oC…107
    Fig. 5-7TGA derivative curves of untreated rice hsuk and acid-treated rice hsuk………………………………..108
    Fig. 5-8The SEM images of rice hsuk (a) raw rice husk (b)acid-treated rice husk. (c) rice husk pyrolyzed at 700oC (d) rice husk pyrolyzed and then calcined at 700oC…………………………………………………110
    Fig. 5-9N2 adsorption-desorption isotherm diagram of rice husk ash………………………………………………113
    Fig. 5-10The pore diameter distribution diagram of the raw rice husk ash and acid-treated rice husk ash pyrolyzed and then calcined at different temperature…………………………………………..118
    Fig. 5-11The pore diameter distribution diagram of rice husk ash (a) pyrolyzed at 900oC ; calcined at 7000C (b) pyrolyzed at 500oC ; calcined at 900oC………….….119
    Fig. 5-12TGA curves of the RHA-Al(NO3)3 and Al(NO3) 3 9H2O……………………………………..122
    Fig. 5-13DSC curves of the RHA-Al(NO3)3 andAl(NO3) 39H2O………………………….………….123
    Fig. 5-14XRD spectra of aluminum nitrate calcined at (a)350oC (b)500oC (c)700oC (d)900oC………………125
    Fig. 5-15XRD spectra of aluminum nitrate supported on rice husk ash calcined at (a)350oC (b) 500oC (c)700oC(d)900oC……………………………………126
    Fig. 5-16XPS spectra of Si 2p in RHA-Al2O3 calcined at (a)350oC (b)500oC (c)700oC (d)900oC………………128
    Fig. 5-17XPS spectra of Al 2p in RHA-Al2O3 calcined at (a)350oC (b)500oC (c)700oC (d)900oC……………....129
    Fig. 5-18XPS spectra of O 1s in RHA-Al2O3 calcined at (a)350oC (b)500oC (c)700oC (d)900oC………………130
    Fig. 5-19XPS spectra of O 1s in rice husk ash calcined at (a)500oC (b)700oC (c)900oC…………………………131
    Fig. 5-20N2 adsorption-desorption isotherms diagram of the RHA and RHA-Al2O3 with various alumina content..134
    Fig. 5-21The pore diameter distribution diagram of the (a) RHA (b) RHA-Al2O3………………………………...135
    Fig. 5-22N2 adsorption-desorption isotherms diagram of RHA-Al2O3 calcined at different temperature……….137
    Fig. 5-23The pore diameter distribution diagram of RHA-Al2O3 calcined at 350oC and 500oC…………..138
    Fig. 5-24Effect of alumina loading in RHA-Al2O3 on ammonia adsorbed amount…………………………..142
    Fig. 5-25A model of RHA-Al2O3 supports preparation system………………………………………………..144
    Fig. 5-26TGA curves of nickel nitrate………………………...147
    Fig. 5-27TGA curves of nickel nitrate supported on RHA-Al2O3…………………………………………..148
    Fig. 5-28The DSC curves of (a) nickel nitrate (b) nickel nitrate supported on RHA-Al2O3…………………….150
    Fig. 5-29TPR curves of I-Ni/RHA-Al2O3 catalyst precursors with various nickel loading and unsupported NiO.(a)2.5wt.% (b) 5.0wt.% (c)10.0wt.% (d)15.0wt.% (e) 25.0wt.% (f) unsupported NiO (ramp rate, 10oC/min; calcination temperature, 500oC)…….153
    Fig. 5-30TPR curves of unsupported NiO and 15 wt% I-Ni/RHA-Al2O3 catalyst precursors calcined at .(a)500oC (NiO) (b) 400oC (c) 500oC (d) 700oC (e) 900oC (ramp rate, 10oC/min)………………………...156
    Fig. 5-31XPS spectra of Ni 2p in catalyst precursors calcined at (a)400oC (b)500 oC (c)700 oC(d) 900 oC…………..159
    Fig. 5-32XRD spectras of I-Ni/RHA-Al2O3 catalyst precursors with various nickel loading and unsupported NiO. (a) unsupported NiO (b) 2.5wt.% (c) 5.0wt.% (d)10.0wt.% (e)15.0wt.% (f) 20wt.% (g) 25.0wt.% (ramp rate, 10oC/min; calcination temperature, 500oC)…………………………………………….161
    Fig. 5-33XRD patterns of (a) NiO and 15 wt.% I-Ni/RHA-Al2O3 catalyst precursors calcined at (b) 400oC(c)500oC(d)700oC(e)900oC……………………162
    Fig. 5-34The SEM images of catalyst precursor (a)NiO (b) RHA-Al2O3 (c)15.0wt.%I-Ni/RHA-Al2O3 (d)25.0wt.% I-Ni/RHA-Al2O3………………………167
    Fig. 5-35The SEM images of (a) 15.0wt.% I-Ni/RHA calcined at 500oC (b) 15.0wt.% Ni catalysts prepared by mix up the nickel nitrate with aluminum nitrate and then calcined at 500oC (c) 15.0wt.% I-Ni/RHA-Al2O3 prepared by co-impregnation method (d) 15.0wt.% I-Ni/RHA-Al2O3 calcined at 900oC…………………169
    Fig. 5-36SEM-EDS Si, Al and Ni-mapping of 5% I-Ni/RHA-Al2O3catalyst…………………………….171
    Fig. 5-37The TEM images of supports and I-Ni/RHA-Al2O3 catalyst.(a) RHA-Al2O3 (x 500K) (b) 15wt.% I-Ni/RHA-Al2O3 (x500K) (c) 15wt.% I-Ni/RHA-Al2O3 (x 12600K)(d) 25wt.% I-Ni/RHA-Al2O3(x 12600K)………………………...173
    Fig. 5-38N2 adsorption-desorption isotherms diagram of the catalyst precursors with various nickel loading……..176
    Fig. 5-39The pore diameter distribution diagram of RHA-Al2O3 and I-Ni/RHA-Al2O3 …………….…….178
    Fig. 5-40The pore diameter distribution diagram of 15wt.% I-Ni/RHA-Al2O3 calcined at(a)400oC(b)500 oC (c)700 oC (d)900 oC…………………………………..180
    Fig. 5-41Effect of calcination temperature on hydrogen desorption amount. (a)400oC(b)500 oC (c)700 oC (d)900 o……………………………………………….183
    Fig. 5-42Effect of nickel loading on CO2 conversion and CH4 yield for CO2 hydrogenation over I-Ni/RHA-Al2O3 catalysts ( calcination temperature, 500oC ; reduction temperature, 800oC)………………………………..185
    Fig. 5-43Comparision of CO2 conversion and CH4 yield for CO2 hydrogenation over 15wt% I-Ni/RHA-Al2O3 and 15wt% I-Ni/SiO2-Al2O3 catalysts ( calcination temperature, 500oC ; reduction temperature, 800oC)………………………………………………187
    Fig. 5-44Effect of calcination temperature on CO2 conversion and CH4 yield of CO2 hydrogenation over 15wt% I-Ni/RHA-Al2O3 catalysts.(reaction temperature, 500oC; reduction temperature, 800oC)…………….190
    Fig. 5-45Effect of reduction temperature on CO2 conversion and CH4 yield of CO2 hydrogenation over 15wt% I-Ni/RHA-Al2O3 catalysts. (reaction temperature, 500oC; calcination temperature, 500oC )………….192
    Fig. 5-46Comparision of CH4 selectivity for CO2 hydrogenation over 15wt% I-Ni/RHA-Al2O3 and 15wt% I-Ni/SiO2-Al2O3 catalysts ( calcination temperature, 500oC ; reduction temperature, 800oC) ..194
    Fig. 5-47TPR curves of (a) 15wt% I-Ni/RHA-Al2O3 (b) 15wt% I-Ni/SiO2-Al2O3 catalysts……………………196
    Fig. 5-48The pore diameter distribution diagram of 15wt.% I-Ni/RHA-Al2O3 and I-Ni/SiO2-Al2O3…………….198
    Fig. 5-49A model for the nickel on RHA-Al2O3 system prepared by incipient wetness impregnation………...200
    Fig. 6-1pH curves of thermal hydrolysis for urea and deposition-precipitation of nickel(II) from thermal hydrolysis of urea at 90oC (a) 0.14M nickel (II) with 0.42 M urea on 3.0g support (RHA-Al2O3);(b) 0.42 M urea.203
    Fig. 6-2Nickel loading on P-Ni/RHA-Al2O3 catalyst precursors as a function of solution concentration for 24h deposition-precipitation at 90oC………………...206
    Fig. 6-3Nickel loading on P-Ni/RHA-Al2O3 catalyst precursors as a function of deposition-precipitation time for 0.14 M nickel (II) at 90oC………………….209
    Fig. 6-4TGA curves of precipitate supported on (a)Al2O3 (b) RHA-Al2O3 (c) RHA. 211
    Fig. 6-5TGA derivative curves of precipitate supported on (a)Al2O3 (b) RHA-Al2O3 (c) RHA…………………...212
    Fig. 6-6XRD patterns of precipitate supported on (a)Al2O3 (b) RHA-Al2O3 (c) RHA dried at 110oC…………....215
    Fig. 6-7XRD patterns of RHA and Al2O3 reacted espectively with 0.42M urea at 90oC with various reaction time (a)RHA for 12h (b) RHA for 24h (c) Al2O3 for 1h (d) for 3h (e) Al2O3 for 6h (f) Al2O3 for 12h (g) Al2O3 for 24h (after dried at 110oC)…………………………..217
    Fig. 6-8XRD patterns of P-Ni/RHA-Al2O3 catalyst precursors obtained from 24h deposition-precipitation calcined at 500oC with various nickel (II) concentration. (a) unsupported NiO obtained from 0.14 M (b) 0.035 M (c) 0.07M (d) 0.10M (e) 0.14M (f) 0.28M………….219
    Fig. 6-9XRD patterns of P-Ni/RHA-Al2O3 catalyst precursors obtained from 0.14M nickel (II) solution calcined at 500oC with various deposition-precipitation time (a) unsupported NiO with precipitation time for 24h (b)1h (c)3h (d)6h(e)12h (f) 24h (g)48h………………….……………………………..220
    Fig. 6-10XRD patterns of 14.1 wt.% nickel loading P-Ni/RHA-Al2O3 catalyst precursors calcined at various calcination temperature. (a) unsupported NiO calcined at 500oC (b)400oC (c) 500oC (d)700oC (e)900oC……………………………………………...221
    Fig. 6-11XPS spectra of Ni 2p in 14.1 wt.% nickel loading P-Ni/RHA-Al2O3 catalyst precursors calcined at various temperature (a)400oC (b) 500oC (c)700oC (d)900oC……………………………………………...229
    Fig. 6-12TPR curves of P-Ni/RHA-Al2O3 catalyst precursors obtained from 24h deposition-precipitation with various nickel (II) concentration. (a) 0.035M (b) 0.07M (c) 0.10M (d) 0.14M (e) 0.28M (f) unsupported NiO obtained from 0.14M. (ramp rate, 10oC/min; calcination temperature, 500oC)………….231
    Fig. 6-13TPR curves of P-Ni/RHA-Al2O3 catalyst precursors obtained from 0.14 M nickel (II) concentration with various deposition-precipitation time.(a) 1h (b) 3h (c) 6h (d) 12h (e) 24h (f) 48h (g) unsupported NiO obtained from 24h precipitation. (ramp rate, 10oC/min; calcination temperature, 500oC)………….232
    Fig. 6-14Comparison of TPR behavior of catalyst precursors after calcination at 500oC (a) 12 wt.% nickel loading P-Ni/RHA-Al2O3 obtained from 1h deposition-precipitation for 0.14 M nickel (II) (b) 16.3 wt% nickel loading P- Ni/RHA-Al2O3 obtained from 24h deposition-precipitation for 0.035M nickel (II) (c) 14.1 wt.% nickel loading P-Ni/RHA-Al2O3 obtained from 24h deposition-precipitation for 0.14M nickel with double weight of support………..233
    Fig. 6-15TPR curves of unsupported NiO and P-Ni/RHA-Al2O3 catalyst precursors obtained from 0.14 M Ni (II) with deposition-precipitation time for 24h with various calcination temperature.(a) unsupported NiO (b) 400oC (c) 500oC (d) 700oC (e) 900oC (ramp rate, 10oC/min; calcined for 4h; 14.1 wt.% nickel loading)…………………………………234
    Fig. 6-16Scanning electron micrographs of (a) unsupported NiO (× 50k) (b) P-Ni/RHA catalyst precursors (× 50k) (c) P-Ni/RHA-Al2O3 catalyst precursors (× 50k) (d) P-Ni/Al2O3 catalyst precursors (× 10k)…………240
    Fig. 6-17SEM-EDS, Si, Al and Ni-mapping of 16.3 wt.% P-Ni/RHA-Al2O3 catalyst precursors(× 20k), (obtained from 0.035 M nickel (II) concentration for 24h deposition-precipitation)………………………..242
    Fig. 6-18TEM images of P-Ni/RHA-Al2O3 catalyst precursor (a) 0.14M-1h (× 500K) (b) 0.14M-48h (×500K) (c) 0.035M-24h (×9200K) (d) 0.28M-24h (×9200K)…244
    Fig. 6-19N2 adsorption-desorption isotherms diagram of support and P-Ni/RHA-Al2O3 obtained from 24h deposition-precipitation with various nickel (II) concentration…………………………………………247
    Fig. 6-20The pore diameter distribution diagram of P-Ni/RHA-Al2O3 obtained from 24h deposition-precipitation with various Ni(II) concentration (a)0.035M (b)0.07M (c) 0.1M (d) 0.28M………………………………………………249
    Fig. 6-21The pore diameter distribution diagram of support and P-Ni/RHA-Al2O3 obtained from 0.14M Ni (II) with various deposition-precipitation time (a) 1h (b) 6h (c) 12h (d) 24h (e) 48h (f) RHA-Al2O3………..….251
    Fig. 6-22N2 adsorption-desorption isotherms diagram of P-Ni/RHA-Al2O3 obtained from 0.14M nickel (II) with various deposition-precipitation time.…………253
    Fig. 6-23N2 adsorption-desorption isotherms diagram of P-Ni/RHA-Al2O3 obtained from 0.14M nickel (II) with deposition-precipitation time for 24h calcined at various temperature………….………………………255
    Fig. 6-24The pore diameter distribution diagram of 14.1 wt.% Ni loading P-Ni/RHA-Al2O3 calcined at various temperature.………………………………….256
    Fig. 6-25Effect of nickel loading on CO2 conversion and CH4 yield for CO2 hydrogenation over P-Ni/RHA-Al2O3 catalysts (reaction temperature, 500 oC; reduction temperature, 800 oC)…………………………………258
    Fig. 6-26Comparison of CO2 conversion and CH4 yield for CO2 hydrogenation over 15wt.% I-Ni/RHA-Al2O3 and 16.3wt.% P-Ni/RHA-Al2O3 catalysts. (calcination temperature, 500 oC; reductiontemperature,800 oC)………………………………260
    Fig. 6-27Effect of calcination temperature on CO2 conversion and CH4 yield for CO2 hydrogenation over P-Ni/RHA-Al2O3 catalysts (reaction temperature, 500 oC; reduction temperature, 800 oC)……………..262
    Fig. 6-28Comparison of CH4 selectivity for CO2 hydrogenation over 15wt.% I-Ni/RHA-Al2O3 and 16.3wt.% P-Ni/SiO2-Al2O3 catalysts. (calcination temperature, 500 oC; reduction temperature, 800 oC)………………………………….………………265
    Fig. 6-29Comparison of TPR behavior of catalyst precursors after calcination at 500oC (a) 12 wt% nickel loading P-Ni/RHA-Al2O3 obrtained from 1h deposition- precipitation for 0.14M niekl (II) (b) 16.3 wt.% nickel loading P-Ni/RHA-Al2O3 obtained from 24h deposition-precipitation for 0.035M nickel (II) (c) 15 wt.% nickel loading I-Ni/RHA–Al2O3 obtained fromincipient wetness impregnation tchnique……….….267
    Fig. 6-30Comparison of CO2 conversion and CH4 yield for CO2 hydrogenation over 26.4wt.% P-Ni/RHA-Al2O3 and 26.5wt.% P-Ni/SiO2-Al2O3 catalysts. (calcination temperature, 500 oC; reduction temperature, 800 oC).269
    Fig. 6-31Comparison of CH4 selectivity for CO2 hydrogenation over 26.4wt.% P-Ni/RHA-Al2O3 and 26.5wt.% P-Ni/SiO2-Al2O3 catalysts. (calcination temperature, 500 oC; reduction temperature, 800 oC)270
    Fig. 6-32Comparison of TPR behavior of catalyst precursors obtained from 0.035M-24h deosition-precipitation and calcined at 500oC (a) 26.4wt% nickel loading P-Ni/RHA-Al2O3 (b)26.5 wt.% nickel loading P-Ni/SiO2-Al2O3 (c) unsupported NiO.271
    Fig. 6-33A model for the nickel on RHA-Al2O3 system prepared by precipitation-deposition………………...274

    表索引
    Page
    Table 1-1The utilization of rice husk…………………………6
    Table 2-1Chemical analysis of raw rice husk. ……………...11
    Table 2-2Organic constituent of rice husk……………...……12
    Table 2-3Some physical properties of rice husk……………14
    Table 2-4Amount of metallic ingredients in the rice husk……18
    Table 3-1Thermoldynamic data of methanation……………47
    Table 5-1Ultimate element analysis of rice husk……………..94
    Table 5-2Impurities analysis of rice husk…………………….96
    Table 5-3The ICP-AES analysis of water-rinsed husk and acid-treated husk………………………………….103
    Table 5-4The ICP-AES analysis of rice husk ash acid-treated before and after calcination………………104
    Table 5-5BET of untreated rice husk ash calcined from 25-700oC in air……………………………………..111
    Table 5-6Effect of pyrolysis temperature on the ash residue of acid-treated rice husk………………………………114
    Table 5-7Effect of operation temperature on BET surface area and pore size of acid-treated rice husk ash…………116
    Table 5-8Textural properties of raw material RHA, RHA-Al2O3 and SiO2-Al2O3………………………..133
    Table 5-9Chemisorption of NH3 on supported and unsupported alumina……………………………..140
    Table 5-10Textural properties of unsupported NiO, supports (RHA-Al2O3) and catalysts precursors(I-Ni/RHA-Al2O3)………………………………….163
    Table 5-11Textural properties of catalyst precursors (I-Ni/RHA-Al2O3) with different calcinationstemperature……..…………………………….……165
    Table 5-12Comparison of surface properties of supports (RHA-Al2O3, SiO2-Al2O3) and catalyst precursors (I-Ni/RHA-Al2O3, I-Ni/SiO2-Al2O3)……………….195
    Table 6-1Effect of nickel concentration on the textural properties of catalyst precursors(P-Ni/RHA-Al2O3)………………………..……….207
    Table 6-2Effect of deposition-precipitation time on the textural properties of catalyst precursors(P-Ni/RHA-Al2O3)………………………………….224
    Table 6-3Textural properties of catalyst precursors (Ni/RHA-Al2O3) with different calcinationtemperature………………………………………228
    Table 6-4Comparison of surface properties of catalyst precursors (I-Ni/RHA-Al2O3, P-Ni/RHA-Al2O3)…..266
    Table 6-5Comparison of surface properties of catalyst precursors (P-Ni/RHA-Al2O3, P-Ni/SiO2-Al2O3)272
    Table A-1Effect of nickel loading on CO2 conversion, CH4 yield and CH4 selectivity over I-Ni/RHA-Al2O3 at 500oC.……………………………………………294
    Table A-2Effect of calcination temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation at 500℃over 15 wt.% I-Ni/RHA-Al2O3…………………………………….295
    Table A-3Effect of reduction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 15 wt.% I-Ni/RHA-Al2O3……………………..296
    Table A-4Effect of reaction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 15 wt.% I-Ni/RHA-Al2O3……………………..297
    Table A-5Effect of reaction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 15 wt.% I-Ni/SiO2-Al2O3……………………...298
    Table B-1Effect of nickel loading on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation at 500℃ over P-Ni/RHA-Al2O3 catalysts…………299
    Table B-2Effect of reaction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 16.3wt.% P-Ni/RHA-Al2O3 catalysts………..300
    Table B-3Effect of calcination temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 14.1 wt.%P-NiRHA-Al2O3……301
    Table B-4Effect of reaction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 26.4 wt.% P-Ni/RHA-Al2O3…………………..302
    Table B-5Effect of reaction temperature on CO2 conversion , CH4 yield and CH4 selectivity of CO2 hydrogenation over 26.5 wt.%P-Ni/SiO2-Al2O3…………………………………..303
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    蔡明策,“稻殼灰分和稻殼灰分-氧化鋁擔載鎳觸媒特性與反應性之研究”,國立中央大學博士論文 (2001).
    Advisor
  • F. W. Chang(張奉文)
  • Files
  • 84341001.pdf
  • approve in 1 year
    Date of Submission 2003-07-11

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