Phenol separation from different aqueous and non-aqueous solutions (industrial wastewater and process water) using pervaporation (PV) membranes is of wide interest from environmental and industrial point of view. In the following, applications of these membranes are described. A general review on different membrane processes and membrane reactors in petrochemical industry, such as olefin/paraffin separation processes, light solvent separation, solvent dewaxing, phenol and aromatic recovery, dehydrogenation, oxidative coupling of methane and steam reforming of methane were discussed in detail by Ravanchi et al (2009). Besides, separation using polymer-inorganic nano composite membranes and wastewater treatment using membrane bio-reactors are reported. The available technologies for the abatement of phenol from water and gaseous streams were briefly reviewed, and the recent advancements summarized by Busca et al (2008). In this work separation technologies such as distillation, liquid-liquid extraction with different solvents, adsorption over activated carbons and polymeric and inorganic adsorbents, membrane pervaporation and membrane-solvent extraction, are discussed. Destruction technologies such as non-catalytic, supercritical and catalytic wet air oxidation, ozonation, non-catalytic, catalytic and enzymatic peroxide wet oxidation, electrochemical and photocatalytic oxidation, supercritical wet gasification, destruction with electron discharges as well as biochemical treatments are also considered. In particular, for the abatement of phenol from gases, condensation, absorption in liquids, adsorption on solids, membrane separation, thermal, catalytic, photocatalytic and biological oxidation are also described and the experimental conditions and performances of the different techniques compared. Application of membrane techniques (pervaporation and membrane-based solvent extraction) and adsorption to the removal of phenol from solutions modelling wastewater from phenol production by cumene oxidation process was investigated by Kujawski et al (2004a). The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water-phenol mixtures were determined. It was found that the best removal efficiency of phenol was obtained using the PEBA membrane. MTBE, cumene and the mixture of hydrocarbons were applied in the membrane-based phenol extraction. Extra-Flow contactor with Celgard X-30 polypropylene hollow-fiber porous membranes was used in the experiments. MTBE was found the most efficient extractant. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in the phenol removal from the aqueous solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution. Application of pervaporation and adsorption to the removal of phenol from solutions modeling wastewater from phenol production with cumene oxidation process was investigated by Kujawski et al. (2004b). The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water-acetone, water-phenol and water-phenol-acetone mixtures were determined. It was found that all membranes were selective toward phenol. The PEBA membrane showed the best selectivity. However, this membrane is not actually available on the commercial scale. Thus, in the practical applications PERVAP-1060 and PERVAP-1070 could be used. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in decontamination of aqueous phenol solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution. The separation of a phenol-water mixture using a polyurethane membrane by a pervaporation method was investigated by Hoshi et al (1997). Polyurethane was selected as a membrane material because its affinity for phenol was considered to be high and was prepared by the polyaddition of 1,6-diisocyanatohexane and polytetramethyleneglycol. The polyurethane layer was sandwiched with a porous polypropylene membrane (Celgard(R) 2500). Pervaporation measurements were carried out under vacuum on the permeate side, and the permeate vapor was collected with a liquid nitrogen trap. The phenol concentration in the permeate solution increased from 0 to 65 wt % with increasing feed concentration of phenol from 0 to 7 wt %. The total flux also increased up to 930 g·m-2·h-1 with increasing phenol partial flux. In the sorption measurement at 60°C, the concentration of phenol in the membrane was 68 wt %, which was higher than that of the permeate solution. The effect of the methylene group length in poly(alkylene glycols) on permselectivity and solubility of phenol was studied by Hoshi et al (2000) in dilute aqueous solution through polyurethane membranes by pervaporation. The poly(alkylene glycols) were obtained by polycondensation of 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol with a sulfuric acid catalyst. Polyethyleneglycol and polytetramethyleneglycol were commercially available. Progress of the polymerization in the poly(alkylene glycols) was confirmed by FTIR, 1H-NMR analysis, and size-exclusion chromatography (SEC) measurements. The polyurethanes were obtained by polyaddition reaction of 1,6-hexamethylenediisocyanate and the poly(alkylene glycol), and were confirmed by FTIR analysis and SEC measurements. The phenol concentration in a permeate liquid increased from 25.1 to 36.2 wt %, and the phenol partial flux also increased from 49.3 to 68.9 g·m-2·h-1 with increasing the methylene group length in the poly(alkylene glycols), whereas the water partial flux slightly decreased. As a result of sorption measurements, the change in the degree of swelling was small, and the phenol concentration in the membrane increased from 42.1 to 70.8 wt %. The increase in the methylene group length of the poly(alkylene glycols) should contribute to an increase in the hydrophobicity of the polyurethane so that the solubility of phenol to the membrane should increase. The phenol concentration in the permeate liquid and the phenol partial flux increased with an increase in the methylene group length of the poly(alkylene glycols) due to the increase in the phenol solubility for the polyurethane membranes. References Busca G, Berardinelli S, Resini C, Arrighi L (2008) Technologies for the removal of phenol from fluid streams: A short review of recent developments. Journal of Hazardous Materials 160:265-288 Hoshi M, Kogure M, Saitoh T, Nakagawa T (1997) Separation of aqueous phenol through polyurethane membranes by pervaporation. Journal of Applied Polymer Science 65:469-479 Hoshi M, Ieshige M, Saitoh T, Nakagawa T (2000) Separation of aqueous phenol through polyurethane membranes by pervaporation. III. Effect of the methylene group length in poly(alkylene glycols). Journal of Applied Polymer Science 76:654-664 Kujawski W, Warszawski A, Ratajczak W, Porebski T, Capala W, Ostrowska I (2004a) Removal of phenol from wastewater by different separation techniques. Desalination 163:287-296 Kujawski W, Warszawski A, Ratajczak W, Porebski T, Ostrowska I (2004b) Application of pervaporation and adsorption to the phenol removal from wastewater. Separation and Purification Technology 40:123-132 Ravanchi MT, Kaghazchi T, Tahereh, Kargari A (2009) Application of membrane separation processes in petrochemical industry: a review. Desalination 235:199-244
Phenol separation on PV membrane reactor
MOLINARI, Raffaele
2013-01-01
Abstract
Phenol separation from different aqueous and non-aqueous solutions (industrial wastewater and process water) using pervaporation (PV) membranes is of wide interest from environmental and industrial point of view. In the following, applications of these membranes are described. A general review on different membrane processes and membrane reactors in petrochemical industry, such as olefin/paraffin separation processes, light solvent separation, solvent dewaxing, phenol and aromatic recovery, dehydrogenation, oxidative coupling of methane and steam reforming of methane were discussed in detail by Ravanchi et al (2009). Besides, separation using polymer-inorganic nano composite membranes and wastewater treatment using membrane bio-reactors are reported. The available technologies for the abatement of phenol from water and gaseous streams were briefly reviewed, and the recent advancements summarized by Busca et al (2008). In this work separation technologies such as distillation, liquid-liquid extraction with different solvents, adsorption over activated carbons and polymeric and inorganic adsorbents, membrane pervaporation and membrane-solvent extraction, are discussed. Destruction technologies such as non-catalytic, supercritical and catalytic wet air oxidation, ozonation, non-catalytic, catalytic and enzymatic peroxide wet oxidation, electrochemical and photocatalytic oxidation, supercritical wet gasification, destruction with electron discharges as well as biochemical treatments are also considered. In particular, for the abatement of phenol from gases, condensation, absorption in liquids, adsorption on solids, membrane separation, thermal, catalytic, photocatalytic and biological oxidation are also described and the experimental conditions and performances of the different techniques compared. Application of membrane techniques (pervaporation and membrane-based solvent extraction) and adsorption to the removal of phenol from solutions modelling wastewater from phenol production by cumene oxidation process was investigated by Kujawski et al (2004a). The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water-phenol mixtures were determined. It was found that the best removal efficiency of phenol was obtained using the PEBA membrane. MTBE, cumene and the mixture of hydrocarbons were applied in the membrane-based phenol extraction. Extra-Flow contactor with Celgard X-30 polypropylene hollow-fiber porous membranes was used in the experiments. MTBE was found the most efficient extractant. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in the phenol removal from the aqueous solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution. Application of pervaporation and adsorption to the removal of phenol from solutions modeling wastewater from phenol production with cumene oxidation process was investigated by Kujawski et al. (2004b). The transport and separation properties of composite membranes PEBA, PERVAP 1060 and PERVAP 1070 in pervaporation of water-acetone, water-phenol and water-phenol-acetone mixtures were determined. It was found that all membranes were selective toward phenol. The PEBA membrane showed the best selectivity. However, this membrane is not actually available on the commercial scale. Thus, in the practical applications PERVAP-1060 and PERVAP-1070 could be used. Adsorption of phenol on the different Amberlite resins was also investigated. Among the Amberlite resins of various grades used, the Amberlite XAD-4 had the best properties in decontamination of aqueous phenol solutions. It was shown that regeneration of the adsorbent bed could be effectively performed with sodium hydroxide solution. The separation of a phenol-water mixture using a polyurethane membrane by a pervaporation method was investigated by Hoshi et al (1997). Polyurethane was selected as a membrane material because its affinity for phenol was considered to be high and was prepared by the polyaddition of 1,6-diisocyanatohexane and polytetramethyleneglycol. The polyurethane layer was sandwiched with a porous polypropylene membrane (Celgard(R) 2500). Pervaporation measurements were carried out under vacuum on the permeate side, and the permeate vapor was collected with a liquid nitrogen trap. The phenol concentration in the permeate solution increased from 0 to 65 wt % with increasing feed concentration of phenol from 0 to 7 wt %. The total flux also increased up to 930 g·m-2·h-1 with increasing phenol partial flux. In the sorption measurement at 60°C, the concentration of phenol in the membrane was 68 wt %, which was higher than that of the permeate solution. The effect of the methylene group length in poly(alkylene glycols) on permselectivity and solubility of phenol was studied by Hoshi et al (2000) in dilute aqueous solution through polyurethane membranes by pervaporation. The poly(alkylene glycols) were obtained by polycondensation of 1,6-hexanediol, 1,8-octanediol, and 1,10-decanediol with a sulfuric acid catalyst. Polyethyleneglycol and polytetramethyleneglycol were commercially available. Progress of the polymerization in the poly(alkylene glycols) was confirmed by FTIR, 1H-NMR analysis, and size-exclusion chromatography (SEC) measurements. The polyurethanes were obtained by polyaddition reaction of 1,6-hexamethylenediisocyanate and the poly(alkylene glycol), and were confirmed by FTIR analysis and SEC measurements. The phenol concentration in a permeate liquid increased from 25.1 to 36.2 wt %, and the phenol partial flux also increased from 49.3 to 68.9 g·m-2·h-1 with increasing the methylene group length in the poly(alkylene glycols), whereas the water partial flux slightly decreased. As a result of sorption measurements, the change in the degree of swelling was small, and the phenol concentration in the membrane increased from 42.1 to 70.8 wt %. The increase in the methylene group length of the poly(alkylene glycols) should contribute to an increase in the hydrophobicity of the polyurethane so that the solubility of phenol to the membrane should increase. The phenol concentration in the permeate liquid and the phenol partial flux increased with an increase in the methylene group length of the poly(alkylene glycols) due to the increase in the phenol solubility for the polyurethane membranes. References Busca G, Berardinelli S, Resini C, Arrighi L (2008) Technologies for the removal of phenol from fluid streams: A short review of recent developments. Journal of Hazardous Materials 160:265-288 Hoshi M, Kogure M, Saitoh T, Nakagawa T (1997) Separation of aqueous phenol through polyurethane membranes by pervaporation. Journal of Applied Polymer Science 65:469-479 Hoshi M, Ieshige M, Saitoh T, Nakagawa T (2000) Separation of aqueous phenol through polyurethane membranes by pervaporation. III. Effect of the methylene group length in poly(alkylene glycols). Journal of Applied Polymer Science 76:654-664 Kujawski W, Warszawski A, Ratajczak W, Porebski T, Capala W, Ostrowska I (2004a) Removal of phenol from wastewater by different separation techniques. Desalination 163:287-296 Kujawski W, Warszawski A, Ratajczak W, Porebski T, Ostrowska I (2004b) Application of pervaporation and adsorption to the phenol removal from wastewater. Separation and Purification Technology 40:123-132 Ravanchi MT, Kaghazchi T, Tahereh, Kargari A (2009) Application of membrane separation processes in petrochemical industry: a review. Desalination 235:199-244I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
