利用水平薄膜反應器在模擬廢水中回收酚之研究

Recovery of Phenol from Simulated Waste Water Using Horizontal Membrane Reactor

傅延祥(Yeng-Shing Fu)

指導教授 ： 吳和生

元智大學/工程學院/化學工程與材料科學學系/碩士(2007年)

https://doi.org/10.6838/YZU.2007.00316

摘要

至今有許多研究將陰離子交換觸媒應用在海水淡化、自廢水中回收重金屬離子和電透析相關領域中，其經濟效益不外乎陰離子交換薄膜（四級銨鹽薄膜，Quaternary Ammonium Salt Membrane）不僅可以分隔油相與水相，並在此兩相反應系統中促進反應速率。此研究目的在於製備四級銨鹽陰離子交換薄膜，在一水準薄膜反應器中進行模擬廢水酚丙烯化之反應，利用實驗結果評估自製四級銨鹽陰離子交換薄膜做為相間轉移觸媒的可行性。在此研究中以苯乙烯氯 (vinylbenzylchloride)，二乙烯苯(divinylbenzene）做為聚合之單體，加入SBR橡膠 (styrene-butadiene rubber) 後利用塗佈法（paste method）進行反應合成基膜 (Base Membrane），然後利用不同三級胺溶於甲醇溶液中進行固定化反應，如三甲基胺、三乙基胺…等，將基膜放入溶液後配合不同固定化時間與溫度製成不同種類之四級銨化薄膜觸媒，實驗結果顯示基膜經過固定化反應之後會不規則地膨潤。利用” Volhard method ” 測定薄膜上氯離子的含量，結果顯示隨著四級銨鹽觸媒所架接之碳鏈數目或薄膜交聯度( degree of crosslinkage )的增加，離子交換量（ion-exchange capacity）沒有明顯地改變，但含水率（water content）卻隨之降低。本研究所製備之三甲基銨薄膜 離子交換量最大可達 2.5 mmol/g，利用自製四級銨鹽薄膜與日本旭化成公司所生產之 A172 薄膜，在模擬廢水中酚之丙烯化步驟中扮演觸媒角色，操作條件包括攪拌速率、反應溫度、不同之水平反應器、不同交聯度和油水兩相反應物之莫耳數比，利用回應曲面法 ( respond surface methodology ) 獲得在單位時間內每莫耳觸媒可反應最多反應物週轉數（turn-over number），做為各薄膜間之反應能力比較數值。結果顯示水平反應器所獲得之週轉數為 2.74．10-3 s-1，活化能為 11.69 kcal/mol，在338K溫度下酚初始濃度5000ppm其回收速率為10.98ppm/min；在溫度為328K 時結果為9.37ppm/min.

關鍵字

四級銨化薄膜 ； 酚丙烯化反應 ； 相間轉移觸媒 ； 塗佈法

並列摘要

Many research used anion exchange membrane in seawater desalination, the recovery of metal ions from waste water and electrodialysis experiments up to now. One of commercial benefits was that anion exchange membranes (e.g. quaternary ammonium salt membranes) could not only separate aqueous and organic phase but also increase reactive rate in two phase reaction systems. The purpose of this work was to prepare quaternary membranes and use membranes as catalysts for the allylation of phenol from simulated waste water in a two-phase horizontal membrane reactor. The results are used to estimate the feasibility of using quaternary ammonium membrane as phase transfer catalysts. Firstly, an anion exchange membrane was made of copolymerizing vinylbenzylchloride and divinylbenzene to form a base membrane by using the “Paste Method”. The basic membranes were immobilized with various amines to form various quaternary membranes. The experimental results showed that amines would make a base membrane swell abnormally. The content of chloride ions was titrated by using “Volhard Method”. The results showed that the increment of carbon number of amines or degrees of cross-linkage would male the base membrane decrease the water content. Besides, when a base membrane reacted with 3-dimethylamine, the ion exchange capacity was 2.5 meq/g. In the system, the allylation of phenol in simulated waste water was used tetra-methylamine membrane as a phase-transfer catalyst and operating conditions were agitation rate, reactive temperature, degrees of crosslinkage of membranes and the ratio of concentration of reactants. And used “response surface methodology” to get the turn-over number to decide which membrane was good. Results showed that in reactor, A172 membrane, the initial concentration of phenol is 5000ppm, the turn-over number was 2.74．10-3 s-1, the activation energy was 11.69 kcal/mol and the recovery rate of phenol was 10.98 ppm/min at 338K and 9.37ppm/min at 328K.

並列關鍵字

Quaternary ammonium salt membrane ； allylation of phenol ； phase transfer catalyst ； past method

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