【摘要】：三乙胺是具有較高產(chǎn)品價(jià)值的化工原料,工業(yè)用途十分廣泛。實(shí)際工業(yè)生產(chǎn)過(guò)程中排放的三乙胺廢水,具有毒性大、濃度高、難降解等特點(diǎn),對(duì)生態(tài)環(huán)境和人類(lèi)健康有很大的危害。因此,研究探討經(jīng)濟(jì)、有效的廢水處理方法和回收技術(shù)具有重要的現(xiàn)實(shí)意義。本文對(duì)山東某阻燃劑工廠生產(chǎn)過(guò)程中產(chǎn)生的三乙胺廢水,采用蒸餾回收法,離子交換樹(shù)脂法和Fenton氧化法相結(jié)合進(jìn)行試驗(yàn)研究,以期為處理實(shí)際廢水中的三乙胺提供理論指導(dǎo)。蒸餾法可以將沸點(diǎn)較低的三乙胺分離出并資源化回收,可有效的降低廢水中的COD。采用蒸餾方法處理阻燃劑苯氧基四溴雙酚A碳酸酯齊聚物(RDT-7)車(chē)間產(chǎn)生的,含高濃度三乙胺的合成水洗水和精餾排放水。實(shí)驗(yàn)結(jié)果表明廢水pH的變化對(duì)蒸餾效果有較大的影響,pH值越大COD去除率越高。合成水洗水經(jīng)蒸餾法蒸餾出總水樣的10%后,90%的剩余水樣的COD由原來(lái)的13200mg/L降至170mg/L,COD的去除率達(dá)到98%,釜液中三乙胺由原來(lái)的8432mg/L降至26mg/L。精餾排放水經(jīng)蒸餾法蒸餾出總水樣的10%后,90%的剩余水樣的COD由原來(lái)的9300mg/L降至173mg/L,COD的去除率達(dá)到98%,釜液中三乙胺由原來(lái)的6310mg/L降至15mg/L。由靜態(tài)吸附實(shí)驗(yàn)可知,在室溫,pH為11.5,反應(yīng)時(shí)間為2h的條件下,0.500 g RX01型樹(shù)脂對(duì)初始濃度為1500 mg/L的模擬三乙胺廢水有較強(qiáng)的吸附效果,三乙胺去除率能達(dá)到99%,樹(shù)脂的靜態(tài)飽和吸附量為145 mg/g；靜態(tài)吸附條件下,陽(yáng)離子對(duì)樹(shù)脂吸附三乙胺過(guò)程有較大影響,陽(yáng)離子濃度越高,競(jìng)爭(zhēng)吸附作用力越強(qiáng),樹(shù)脂吸附三乙胺的吸附量越低,相等濃度條件下,陽(yáng)離子影響效果的順序?yàn)镃a2+Mg2+K+Na+。樹(shù)脂吸附熱力學(xué)研究表明：Langmuir吸附模型更能準(zhǔn)確的描述RX01型離子交換樹(shù)脂對(duì)三乙胺的吸附過(guò)程,熱力學(xué)常數(shù)為ΔG°0, ΔH°0, ΔS°0,表明三乙胺在RX01上的吸附過(guò)程是自發(fā)進(jìn)行,且伴隨著熵增加的吸熱過(guò)程。動(dòng)力學(xué)研究結(jié)果表明,準(zhǔn)二級(jí)動(dòng)力學(xué)模型能更好的描述樹(shù)脂吸附交換過(guò)程,計(jì)算測(cè)得的表觀活化能Ea為78.3 KJ/mol,說(shuō)明了樹(shù)脂吸附三乙胺為化學(xué)吸附,顆粒擴(kuò)散為主要控速步驟。由動(dòng)態(tài)吸附實(shí)驗(yàn)可知,當(dāng)廢水pH值為11.5,吸附柱高徑比5.37,吸附流速為60 BV/h的條件下,20 mL(約為20.6 g濕樹(shù)脂)樹(shù)脂處理濃度為1500 mg/L的三乙胺廢水,最終穿透點(diǎn)在70 BV,前70 BV的出水中,三乙胺質(zhì)量濃度非常低,小于3 mg/L,三乙胺去除率可達(dá)99.5%。動(dòng)態(tài)脫附過(guò)程中,以2mol/L的HCl溶液為脫附劑,脫附劑流速為1 BV/h、出水體積為4 BV時(shí),三乙胺的脫附率達(dá)94.8%,濃縮倍數(shù)為17.5；在最優(yōu)動(dòng)態(tài)吸附-脫附條件下重復(fù)進(jìn)行10次實(shí)驗(yàn),樹(shù)脂吸附量沒(méi)有明顯下降,且各項(xiàng)吸附性能穩(wěn)定。采用離子交換樹(shù)脂,對(duì)蒸餾處理后的實(shí)際廢水餾出液進(jìn)行吸附。實(shí)驗(yàn)結(jié)果表明：當(dāng)餾出液中三乙胺初始質(zhì)量濃度為1372mg/L,選擇60 BV/h流量進(jìn)行動(dòng)態(tài)吸附,40BV為穿透體積,此條件下出水三乙胺濃度小于10 mg/L,去除率可達(dá)99.2%以上；動(dòng)態(tài)脫附過(guò)程中,以2 mol/L的HC1溶液為脫附劑,脫附劑流速為1 BV/h、出水體積為4 BV時(shí),三乙胺的脫附率達(dá)92.5%,濃縮倍數(shù)為10；RX01型樹(shù)脂處理實(shí)際廢水餾出液有較好的去除效果。Fenton氧化法對(duì)含有低濃度三乙胺的釜液處理效果較好,在pH值為3.0,H202投加量10mg/L,n(Fe2+):n(H2O2)為1：5,反應(yīng)2h后,廢水在pH為8.0時(shí)反應(yīng)沉淀后,溶液中三乙胺濃度降至2.23 mg/L,去除率90.2%,滿足三乙胺排放標(biāo)準(zhǔn)3 mg/L要求。
[Abstract]:Triethylamine is a kind of chemical raw material with high product value and has a wide range of industrial uses. The wastewater discharged from the actual industrial production process has the characteristics of high toxicity, high concentration and difficult degradation, which is harmful to the ecological environment and human health. Therefore, it is necessary to study the economical and effective wastewater treatment methods and recovery technologies. In this paper, the triethylamine wastewater from a fire retardant factory in Shandong Province was studied by distillation recovery method, ion exchange resin method and Fenton oxidation method in order to provide theoretical guidance for the treatment of triethylamine in actual wastewater. The COD in wastewater can be effectively reduced by recycling. The synthetic washing water and distillation effluent containing high concentration triethylamine produced in the flame retardant phenoxytetrabromobisphenol A carbonate oligomer (RDT-7) workshop are treated by distillation. The experimental results show that the change of wastewater pH has a great influence on the distillation effect, and the higher the pH value, the higher the COD removal rate. After 10% of the total water sample is distilled by distillation, COD of 90% of the remaining water sample is reduced from 13200 mg/L to 170 mg/L, COD removal rate is 98%, triethylamine is reduced from 8432 mg/L to 26mg/L. After 10% of the total water sample is distilled by distillation, COD of 90% of the remaining water sample is reduced from 9300 mg/L. The removal rate of COD reached 98% at 173 mg/L and triethylamine was reduced from 6310 mg/L to 15mg/L. The static adsorption experiment showed that 0.500 g RX01 resin had a strong adsorption effect on the simulated triethylamine wastewater with initial concentration of 1500 mg/L at room temperature, pH 11.5 and reaction time 2 h. The removal rate of triethylamine could reach 99% and the resin had a good adsorption effect. Static saturated adsorption capacity is 145 mg/g; under static adsorption conditions, cations have a greater impact on the resin adsorption process of triethylamine. The higher the cation concentration, the stronger the competitive adsorption force, the lower the resin adsorption capacity of triethylamine. Under the same concentration, the order of cations effect is Ca2+Mg2+K+Na+. Adsorption thermodynamics study of resin The results show that Langmuir adsorption model can describe the adsorption process of triethylamine on RX01 ion exchange resin more accurately. The thermodynamic constants are G 0, H 0 and S 0, indicating that the adsorption process of triethylamine on RX01 is spontaneous and accompanied by the increase of entropy. The adsorption and exchange process of resin was described, and the apparent activation energy Ea was 78.3 KJ/mol. It was shown that the resin adsorption of triethylamine was a chemical adsorption and the particle diffusion was the main speed-controlling step. The resin was used to treat the wastewater containing 1 500 mg/L triethylamine. The final penetration point was 70 BV. The mass concentration of triethylamine in the effluent of the first 70 BV was very low, less than 3 mg/L. The removal rate of triethylamine was 99.5%. In the dynamic desorption process, the flow rate of the desorbent was 1 BV/h, and the volume of the effluent was 4 BV. The removal rate of triethylamine reached 94.5%. The adsorption capacity of the resin was not significantly decreased and the adsorption performance was stable. The ion exchange resin was used to adsorb the distillate of the distillation wastewater. The results showed that the initial concentration of triethylamine in the distillate was 1372 M. G/L, selected 60 BV/h flow rate for dynamic adsorption, 40 BV for the penetration volume, the concentration of effluent triethylamine under this condition is less than 10 mg/L, removal rate can reach 99.2%; in the dynamic desorption process, 2 mol/L HC1 solution as desorbent, desorbent flow rate is 1 BV/h, effluent volume is 4 BV, the desorption rate of triethylamine is 92.5%, concentration times is 10; The Fenton oxidation process has a good effect on treating the distillate of wastewater containing low concentration of triethylamine. The concentration of triethylamine in the solution is reduced to 2.23 mg/L and the removal rate is 90.2% when the pH value is 3.0, the dosage of H202 is 10 mg/L, the dosage of n (Fe2+): n (H2O2) is 1:5 and the reaction time is 2 h. Three ethylamine emission standard 3 mg/L requirements.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：X783

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