PDMS复合膜回收酯化反应废水中的异丁醇

doi:10.11949/0438-1157.20200850

摘要/Abstract

摘要：

乙酸与异丁醇酯化反应生产乙酸异丁酯，产生大量含异丁醇的废水，常规生化处理负荷重，浪费资源。采用PDMS复合膜分离回收酯化废水中的异丁醇，考察了异丁醇浓度对PDMS复合膜溶胀度及分离性能的影响，优化渗透汽化过程操作参数，研究了乙酸异丁酯对PDMS复合膜回收异丁醇效果的影响。结果表明，随着异丁醇浓度从1%增大到3%(质量)，PDMS复合膜溶胀度先增大后趋于平稳，异丁醇的渗透通量呈增大趋势，分离因子保持在15左右；操作温度从30℃升至60℃时，渗透通量增大，异丁醇的分离因子下降，总表观活化能为33.87 kJ/mol；流速增加，Reynolds数增大，异丁醇渗透通量变化不大，但分离因子略有增大；微量乙酸异丁酯的存在可促进渗透汽化膜回收异丁醇。采用PDMS复合膜分离酯化废水中的异丁醇，回收率大于94.0%，渗余液中异丁醇浓度可降至0.1%(质量)左右。研究结果可为PDMS复合膜处理低浓度有机溶剂废水提供依据。

关键词: PDMS复合膜, 酯化废水, 异丁醇, 渗透汽化

Abstract:

The esterification reaction of acetic acid and isobutanol produces isobutyl acetate, which generates a large amount of wastewater containing isobutanol. The conventional biochemical treatment is heavy and wastes resources. The effects of isobutanol concentration on the swelling degree and separation performance of polydimethylsiloxane (PDMS) membrane, the operating parameters of the pervaporation process and the effect of isobutyl acetate on the recovery of isobutanol by PDMS membrane were studied. The results show that with the isobutanol concentration increases from 1%(mass) to 3%(mass), the swelling degree of the PDMS membrane increases first and then stabilizes, the flux of isobutanol increases, and the separation factor is about 15. When the operating temperature increases from 30℃ to 60℃, the flux increases, the separation factor of isobutanol decreases, and the total apparent activation energy is 33.87 kJ/mol. With increase of the flow rate, the isobutanol flux is stability while the separation factor increases slightly. The trace amounts of isobutyl acetate can promote the recovery of isobutanol by the membrane. The recovery rate of isobutanol by PDMS membrane is greater than 94.0%, and the concentration of isobutanol in the retentate can be reduced to 0.1%(mass). The research results can provide a basis for PDMS composite membrane to treat low-concentration organic solvent wastewater.

Key words: PDMS membrane, esterification wastewater, isobutanol, pervaporation

中图分类号:

TQ 028.8

左成业, 涂睿, 丁晓斌, 邢卫红. PDMS复合膜回收酯化反应废水中的异丁醇[J]. 化工学报, 2020, 71(9): 4189-4199.

Chengye ZUO, Rui TU, Xiaobin DING, Weihong XING. Recovery of isobutanol from esterified wastewater by PDMS composite membrane[J]. CIESC Journal, 2020, 71(9): 4189-4199.

图/表 12

表1 异丁醇、乙酸异丁酯和水的物化性质[23-24]

Table 1 Physicochemical properties of isobutanol, isobutyl acetate and water[23-24]

试剂	摩尔质量/(g·mol^-1)	摩尔体积/(cm³·mol^-1)	沸点/℃	蒸气压(20℃)/Pa	溶解度参数/ (cal·cm^-3)^1/2
异丁醇	74.12	91.5	107.9	1170	10.8
乙酸异丁酯	116.16	131.55	116.6	1789	8.3
水	18.02	18.0	100	2340	23.4
PDMS	58000	—	—	—	7.3

图1 PDMS复合膜的扫描电镜图和接触角

Fig.1 SEM and water contact angle of PDMS composite membrane

图2 实验装置流程图

Fig.2 Experimental device diagram

图3 PDMS复合膜的溶胀度随异丁醇浓度(a)和浸泡时间(b)的变化

Fig.3 Effect of isobutanol concentrations(a) and immerse time(b) on swelling degree of PDMS membrane

图4 进料液异丁醇浓度对通量、分离因子(a)和渗透液异丁醇浓度(b)的影响

Fig.4 Effect of isobutanol feed concentration on flux, separation factor(a) and isobutanol concentration(b) in permeate

图5 进料液温度对渗透液、渗余液的异丁醇浓度(a)和通量、分离因子(b)的影响

Fig.5 Effect of feed temperature on isobutanol concentration in permeate and retentate (a), flux and separation factor (b)

图6 Arrhenius关系式拟合温度与对数通量的关系

Fig.6 Fits reciprocal of the temperature and logarithm of the flux by Arrhenius formula

图7 Reynolds数对PDMS复合膜分离性能的影响

Fig.7 Effect of Re on PDMS composite membrane performances

图8 乙酸异丁酯浓度对PDMS复合膜分离性能的影响

Fig.8 Effect of isobutyl acetate concentration on PDMS composite membrane performances

图9 进料液异丁醇浓度对渗余液异丁醇浓度、渗透液异丁醇质量(a)和平均通量、回收率(b)的影响

Fig.9 Effect of isobutanol feed concentrations on isobutanol concentration in retentate and isobutanol quality in permeate (a) and average flux and recovery rate (b)

表2 渗透汽化过程处理含异丁醇的酯化工业废水

Table 2 Treatment of esterified industrial wastewater containing isobutanol by pervaporation

酯化废水批次	异丁醇浓度/ %(质量)	平均总通量/ (g/(m²·h))	异丁醇通量/ (g/(m²·h))	渗余侧浓度/ %(质量)	渗余液质量/kg	渗透液质量/kg	异丁醇回收率/ %
1	7.76	671.3	213.2	0.11	18.958	5.5214	98.9
2	7.27	752.2	199.5	0.12	18.23	5.5986	98.8
3	8.17	751.1	224.9	0.1	18.248	6.3824	99.1
4	7.78	769.7	212.9	0.16	18.072	6.1923	98.5
5	8.33	676.1	229.5	0.09	18.915	6.1297	99.2
6	8.2	801.1	225.9	0.09	17.785	6.1258	99.2

图10 不同批次(a)和不同温度进料液(b)的渗余液中异丁醇浓度随时间变化

Fig.10 Change of isobutanol concentration in the retentate with time different batches (a) and different feed temperatures (b)

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