石油工業廢觸媒作為波索蘭材料之可行性研究

曾鋆生

指導教授 ： 許貫中

國立臺灣師範大學/理學院/化學系/碩士(2001年)

摘要

隨著經濟和科技的持續發展，愈來愈多的工業廢棄物伴隨而生，台灣地區每年約產生3000噸廢觸媒，為了避免環境遭受廢棄物污染，本研究著重於廢觸媒的再生利用，評估廢觸媒作為混凝土中礦物摻料的可行性。實驗所採用的廢棄物來自於石油裂解廠的廢觸媒(EPcat、Ecat)，主要由Al2O3及SiO2所組成且具有部份非結晶相和波索蘭材料之特性，EPcat 的平均粒徑為1.7μｍ、比表面積為47 m2/g，而Ecat的平均粒徑為69.8μｍ、比表面積為114 m2/g。研究的方法主要分為二部份，第一部份以波索蘭活性試驗（PAI）及藉由DSC測量CH消耗量來評估廢觸媒的波索蘭活性，探討廢觸媒對水泥漿或砂漿的抗壓強度與凝結時間的影響，並利用XRD、DSC、SEM等儀器來分析廢觸媒對波索蘭反應的影響；第二部份針對Ecat進行熱處理，在不同燒結溫度、時間下找出較佳操作條件來提昇其波索蘭活性。實驗結果顯示EPcat、矽灰比高嶺土、Ecat具有較高的波索蘭活性指數，且其砂漿的抗壓強度均較高；由XRD和DSC圖譜中可明顯看出 EPcat會消耗CH進行波索蘭反應；在SEM照片中可觀察到不同水化產物，如C-S-H膠體、鈣釩石、單硫鋁酸鈣等；水泥漿的凝結時間會因添加EPcat 加速水泥的水化反應而縮短；Ecat在600∼800℃溫燒結1小時並加以研磨後，可顯著增加波索蘭活性，因此廢觸媒應可作為混凝土中的礦物摻料。 As the economy and technology continue to grow, more and more industrial wastes will be generated. In Taiwan, over 3,000 tons of spent FCC (fluidized catalytic cracking) catalysts were produced from petroleum refining companies every year. In order to protect our environment from been polluted by these wastes, this study focuses on the reuse of spent FCC catalysts (EPcat, Ecat). Namely, these catalysts were evaluated as mineral admixtures of concrete. Both catalysts consist mainly of aluminum oxide and silicon oxide, and show some amorphous nature and pozzolanic properties. EPcat has an average particle size of 1.7μｍ and a specific surface area of 47m2/g. Ecat has an average particle size of 69.8μｍ and a specific surface area of 114 m2/g. Experimentally, the pozzolanic activity of these catalysts was examined by the pozzolanic activity index (PAI) test and the consumption of CH determined by DSC measurements. The effects of catalysts on the compressive strength of mortars and setting time of cement pastes were examined. The pozzolanic activity of these materials was also analyzed by XRD, DSC and SEM. Besides, Ecat was calcined at different temperatures and time so that its pozzolanic activity could be improved. Test results indicate that EPcat, like silica fume, shows higher pozzolanic activity than metakaolin and Ecat. It can increase the compressive strength of the resulting mortars. From the analysis of XRD and DSC, we have found that EPcat can undergo the pozzolanic reaction by consuming CH. We also have observed various hydrated products such as C-S-H, ettringite and monosulfoaluminate in the EPcat pastes from SEM micrographs. The pastes incorporated with EPcat exhibit shorter setting time because the catalyst can accelerate the cement hydration by undergoing the pozzolanic reaction. The pozzolanic activity of Ecat could be enhanced significantly when this catalyst was heat treated at 600∼800℃ for 1 hr and then ball-milled. Therefore, spent FCC could be potentially used as mineral admixtures of concrete.

關鍵字

廢觸媒 ； 波索蘭

並列摘要

As the economy and technology continue to grow, more and more industrial
wastes will be generated. In Taiwan, over 3,000 tons of spent FCC (fluidized
catalytic cracking) catalysts were produced from petroleum refining companies
every year. In order to protect our environment from been polluted by these
wastes, this study focuses on the reuse of spent FCC catalysts (EPcat, Ecat).
Namely, these catalysts were evaluated as mineral admixtures of concrete.
Both catalysts consist mainly of aluminum oxide and silicon oxide, and show
some amorphous nature and pozzolanic properties. EPcat has an average particle
size of 1.7μｍ and a specific surface area of 47m2/g. Ecat has an average
particle size of 69.8μｍ and a specific surface area of 114 m2/g.
Experimentally, the pozzolanic activity of these catalysts was examined by the
pozzolanic activity index (PAI) test and the consumption of CH determined by
DSC measurements. The effects of catalysts on the compressive strength of
mortars and setting time of cement pastes were examined. The pozzolanic
activity of these materials was also analyzed by XRD, DSC and SEM.　Besides,
Ecat was calcined at different temperatures and time so that its pozzolanic
activity could be improved.
Test results indicate that EPcat, like silica fume, shows higher pozzolanic
activity than metakaolin and Ecat. It can increase the compressive strength of
the resulting mortars. From the analysis of XRD and DSC, we have found that
EPcat can undergo the pozzolanic reaction by consuming CH. We also　have
observed various hydrated products such as C-S-H, ettringite and
monosulfoaluminate in the EPcat pastes from SEM micrographs. The pastes
incorporated with EPcat exhibit shorter setting time because the catalyst can
accelerate the cement hydration by undergoing the pozzolanic reaction. The
pozzolanic activity of Ecat could be enhanced significantly when this catalyst
was heat treated at 600∼800℃ for 1 hr and then ball-milled. Therefore, spent
FCC could be potentially used as mineral admixtures of concrete.