Formation and transformation of schwertmannite in the classic Fenton process
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摘要
The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention.Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study,SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity,elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO_4~(2-) in the solution decreased by8.7%–26.0% at different molar ratios of Fe(II) to H_2 O_2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate(Fe-SO_4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH > 3.70. Goethite was found to form when the final p H was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron(hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.
The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention.Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study,SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity,elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO_4~(2-) in the solution decreased by8.7%–26.0% at different molar ratios of Fe(II) to H_2 O_2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate(Fe-SO_4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH > 3.70. Goethite was found to form when the final p H was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron(hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.
The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention.Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study,SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity,elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO_4~(2-) in the solution decreased by8.7%–26.0% at different molar ratios of Fe(II) to H_2 O_2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate(Fe-SO_4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH > 3.70. Goethite was found to form when the final p H was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron(hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.
引文
Abid,S.R.,Nahhab,A.H.,Al-aayedi,H.K.H.,Nuhair,A.M.,2018.Expansion and strength properties of concrete containing contaminated recycled concrete aggregate.Case Stud.Constr.Mater.9,e00201.
Amin,S.K.,Abdel Hamid,E.M.,El-Sherbiny,S.A.,Sibak,H.A.,Abadir,M.F.,2018.The use of sewage sludge in the production of ceramic floor tiles.HBRC J.14,309-315.
Babuponnusami,A.,Muthukumar,K.,2014.A review on Fenton and improvements to the Fenton process for wastewater treatment.J.Environ.Chem.Eng.2,557-572.
Banerjee,K.,Amy,G.L.,Prevost,M.,Nour,S.,Jekel,M.,Gallagher,P.M.,et al.,2008.Kinetic and thermodynamic aspects of adsorption of arsenic onto granular ferric hydroxide(GFH).Water Res.42,3371-3378.
Bautista,P.,Mohedano,A.F.,Casas,J.A.,Zazo,J.A.,Rodriguez,J.J.,2008.An overview of the application of Fenton oxidation to industrial wastewaters treatment.J.Chem.Tech.&Biotechnol.83,1323-1338.
Bigham,J.M.,Schwertmann,U.,Carlson,L.,Murad,E.,1990.Apoorly crystallized oxyhydroxysulfate of iron formed by bacterial oxidation of Fe(II)in acid mine waters.Geochim.Cosmochim.Acta 54,2743-2758.
Bigham,J.M.,Schwertmann,U.,Traina,S.,Winland,R.L.,Wolf,M.,1996.Schwertmannite and chemical modeling of iron in acid sulfate waters.Geochim.Cosmochim.Acta 60,2111-2121.
Burton,E.D.,Bush,R.T.,Sullivan,L.A.,2006.Sedimentary iron geochemistry in acidic waterways associated with coastal lowland acid sulfate soils.Geochim.Cosmochim.Acta 70,5455-5468.
Campos,A.,López,C.M.,Blanco,A.,Aguado,A.,2018.Effects of an internal sulfate attack and an alkali-aggregate reaction in a concrete dam.Constr.Build.Mater.166,668-683.
Cao,G.M.,Sheng,M.,Niu,W.F.,Fei,Y.L.,Li,D.,2009.Regeneration and reuse of iron catalyst for Fenton-like reactions.J.Hazard.Mater.172,1446-1449.
Caraballo,M.A.,Rimstidt,J.D.,Macías,F.,Nieto,J.M.,Hochella,M.F.,2013.Metastability,nanocrystallinity and pseudo-solid solution effects on the understanding of schwertmannite solubility.Chem.Geol.360-361,22-31.
Collins,R.N.,Jones,A.M.,Waite,T.D.,2010.Schwertmannite stability in acidified coastal environments.Geochim.Cosmochim.Acta 74,482-496.
Debieb,F.,Courard,L.,Kenai,S.,Degeimbre,R.,2010.Mechanical and durability properties of concrete using contaminated recycled aggregates.Cem.Concr.Compos.32,421-426.
Dold,B.,2003.Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by differential X-ray diffraction(DXRD).Appl.Geochem.18,1531-1540.
Elmoaty,A.E.M.A.,2018.Four-years carbonation and chloride induced steel corrosion of sulfate-contaminated aggregates concrete.Constr.Build.Mater.163,539-556.
Fitzpatrick,R.W.,Mosley,L.M.,Raven,M.D.,Shand,P.,2017.Schwertmannite formation and properties in acidic drain environments following exposure and oxidation of acid sulfate soils in irrigation areas during extreme drought.Geoderma308,235-251.
Gamaralalage,D.,Sawai,O.,Nunoura,T.,2018.Reusing the generated sludge as Fe source in Fenton process for treating crepe rubber wastewater.J.Mater.Cycl.Waste Manag.https://doi.org/10.1007/s10163-018-0784-8.
Gypser,S.,Hirsch,F.,Schleicher,A.M.,Freese,D.,2018.Impact of crystalline and amorphous iron-and aluminum hydroxides on mechanisms of phosphate adsorption and desorption.J.Environ.Sci.70,175-189.
Kartashevsky,M.,Semiat,R.,Dosoretz,C.G.,2015.Phosphate adsorption on granular ferric hydroxide to increase product water recovery in reverse osmosis-desalination of secondary effluents.Desalination 364,53-61.
Kattel,E.,Trapido,M.,Dulova,N.,2016.Treatment of landfill leachate by continuously reused ferric oxyhydroxide sludgeactivated hydrogen peroxide.Chem.Eng.J.304,646-654.
Li,X.,Zhang,Y.,Xie,Y.,Zeng,Y.,Li,P.,Xie,T.,et al.,2018.Ultrasonic-enhancedFenton-like degradation of bisphenol Ausing a bio-synthesized schwertmannite catalyst.J.Hazard.Mater.344,689-697.
Liao,Y.,Zhou,L.,Bai,S.,Liang,J.,Wang,S.,2009.Occurrence of biogenic schwertmannite in sludge bioleaching environments and its adverse effect on solubilization of sludge-borne metals.Appl.Geochem.24,1739-1746.
Liao,Y.,Liang,J.,Zhou,L.,2011.Adsorptive removal of As(III)by biogenic schwertmannite from simulated As-contaminated groundwater.Chemosphere 83,295-301.
Liu,H.,Li,P.,Zhu,M.,Wei,Y.,Sun,Y.,2007.Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite.J.Solid State Chem.180,2121-2128.
Magnone,E.,Kim,S.D.,Park,J.H.,2018.A systematic study of the iron hydroxide-based adsorbent for removal of hydrogen sulphide from biogas.Microporous Mesoporous Mater.270,155-160.
Mahmood,T.,Din,S.U.,Naeem,A.,Tasleem,S.,Alum,A.,Mustafa,S.,2014.Kinetics,equilibrium and thermodynamics studies of arsenate adsorption from aqueous solutions onto iron hydroxide.J.Ind.Eng.Chem.20,3234-3242.
Mezenner,N.Y.,Bensmaili,A.,2009.Kinetics and thermodynamic study of phosphate adsorption on iron hydroxide-eggshell waste.Chem.Eng.J.147,87-96.
Neyens,E.,Baeyens,J.,2003.A review of classic Fenton's peroxidation as an advanced oxidation technique.J.Hazard.Mater.98,33-50.
Paikaray,S.,Schr?der,C.,Peiffer,S.,2017.Schwertmannite stability in anoxic Fe(II)-rich aqueous solution.Geochim.Cosmochim.Acta 217,292-305.
Ponomar,V.P.,2018.Thermomagnetic properties of the goethite transformation during high-temperature treatment.Miner.Eng.127,143-152.
Regenspurg,S.,Brand,A.,Peiffer,S.,2004.Formation and stability of schwertmannite in acidic mining lakes 1 1 Associate editor:C.M.Eggleston.Geochim.Cosmochim.Acta 68,1185-1197.
Rezaee,F.,Danesh,S.,Tavakkolizadeh,M.,Mohammadi-Khatami,M.,2019.Investigating chemical,physical and mechanical properties of eco-cement produced using dry sewage sludge and traditional raw materials.J.Clean.Prod.214,749-757.
Sánchez Espa?a,J.,López Pamo,E.,Santofimia Pastor,E.,2007.The oxidation of ferrous iron in acidic mine effluents from the Iberian Pyrite Belt(Odiel Basin,Huelva,Spain):field and laboratory rates.J.Geochem.Explor.92,120-132.
?wierczek,L.,Cie?lik,B.M.,Konieczka,P.,2018.The potential of raw sewage sludge in construction industry-a review.J.Clean.Prod.200,342-356.
Xie,Y.,Lu,G.,Ye,H.,Yang,C.,Xia,D.,Yi,X.,et al.,2017.Fulvic acid induced the liberation of chromium from CrO42--substituted schwertmannite.Chem.Geol.475,52-61.
Xiong,Y.,Tong,Q.,Shan,W.,Xing,Z.,Wang,Y.,Wen,S.,et al.,2017.Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon.Appl.Surf.Sci.416,618-627.
Yu,J.-Y.,Park,M.,Kim,J.,2002.Solubilities of synthetic schwertmannite and ferrihydrite.Geochem.J.36,119-132.
Zhang,K.,Dwivedi,V.,Chi,C.,Wu,J.,2010.Graphene oxide/ferric hydroxide composites for efficient arsenate removal from drinking water.J.Hazard.Mater.182,162-168.
Zhao,X.,Su,Y.,Li,S.,Bi,Y.,Han,X.,2018.A green method to synthesize flowerlike Fe(OH)3 microspheres for enhanced adsorption performance toward organic and heavy metal pollutants.J.Environ.Sci.73,47-57.
Zhu,Y.,Zhu,R.,Yan,L.,Fu,H.,Xi,Y.,Zhou,H.,et al.,2018.Visiblelight Ag/AgBr/ferrihydrite catalyst with enhanced heterogeneous photo-Fenton reactivity via electron transfer from Ag/AgBr to ferrihydrite.Appl.Catal.B:Environ.239,280-289.
Amin,S.K.,Abdel Hamid,E.M.,El-Sherbiny,S.A.,Sibak,H.A.,Abadir,M.F.,2018.The use of sewage sludge in the production of ceramic floor tiles.HBRC J.14,309-315.
Babuponnusami,A.,Muthukumar,K.,2014.A review on Fenton and improvements to the Fenton process for wastewater treatment.J.Environ.Chem.Eng.2,557-572.
Banerjee,K.,Amy,G.L.,Prevost,M.,Nour,S.,Jekel,M.,Gallagher,P.M.,et al.,2008.Kinetic and thermodynamic aspects of adsorption of arsenic onto granular ferric hydroxide(GFH).Water Res.42,3371-3378.
Bautista,P.,Mohedano,A.F.,Casas,J.A.,Zazo,J.A.,Rodriguez,J.J.,2008.An overview of the application of Fenton oxidation to industrial wastewaters treatment.J.Chem.Tech.&Biotechnol.83,1323-1338.
Bigham,J.M.,Schwertmann,U.,Carlson,L.,Murad,E.,1990.Apoorly crystallized oxyhydroxysulfate of iron formed by bacterial oxidation of Fe(II)in acid mine waters.Geochim.Cosmochim.Acta 54,2743-2758.
Bigham,J.M.,Schwertmann,U.,Traina,S.,Winland,R.L.,Wolf,M.,1996.Schwertmannite and chemical modeling of iron in acid sulfate waters.Geochim.Cosmochim.Acta 60,2111-2121.
Burton,E.D.,Bush,R.T.,Sullivan,L.A.,2006.Sedimentary iron geochemistry in acidic waterways associated with coastal lowland acid sulfate soils.Geochim.Cosmochim.Acta 70,5455-5468.
Campos,A.,López,C.M.,Blanco,A.,Aguado,A.,2018.Effects of an internal sulfate attack and an alkali-aggregate reaction in a concrete dam.Constr.Build.Mater.166,668-683.
Cao,G.M.,Sheng,M.,Niu,W.F.,Fei,Y.L.,Li,D.,2009.Regeneration and reuse of iron catalyst for Fenton-like reactions.J.Hazard.Mater.172,1446-1449.
Caraballo,M.A.,Rimstidt,J.D.,Macías,F.,Nieto,J.M.,Hochella,M.F.,2013.Metastability,nanocrystallinity and pseudo-solid solution effects on the understanding of schwertmannite solubility.Chem.Geol.360-361,22-31.
Collins,R.N.,Jones,A.M.,Waite,T.D.,2010.Schwertmannite stability in acidified coastal environments.Geochim.Cosmochim.Acta 74,482-496.
Debieb,F.,Courard,L.,Kenai,S.,Degeimbre,R.,2010.Mechanical and durability properties of concrete using contaminated recycled aggregates.Cem.Concr.Compos.32,421-426.
Dold,B.,2003.Dissolution kinetics of schwertmannite and ferrihydrite in oxidized mine samples and their detection by differential X-ray diffraction(DXRD).Appl.Geochem.18,1531-1540.
Elmoaty,A.E.M.A.,2018.Four-years carbonation and chloride induced steel corrosion of sulfate-contaminated aggregates concrete.Constr.Build.Mater.163,539-556.
Fitzpatrick,R.W.,Mosley,L.M.,Raven,M.D.,Shand,P.,2017.Schwertmannite formation and properties in acidic drain environments following exposure and oxidation of acid sulfate soils in irrigation areas during extreme drought.Geoderma308,235-251.
Gamaralalage,D.,Sawai,O.,Nunoura,T.,2018.Reusing the generated sludge as Fe source in Fenton process for treating crepe rubber wastewater.J.Mater.Cycl.Waste Manag.https://doi.org/10.1007/s10163-018-0784-8.
Gypser,S.,Hirsch,F.,Schleicher,A.M.,Freese,D.,2018.Impact of crystalline and amorphous iron-and aluminum hydroxides on mechanisms of phosphate adsorption and desorption.J.Environ.Sci.70,175-189.
Kartashevsky,M.,Semiat,R.,Dosoretz,C.G.,2015.Phosphate adsorption on granular ferric hydroxide to increase product water recovery in reverse osmosis-desalination of secondary effluents.Desalination 364,53-61.
Kattel,E.,Trapido,M.,Dulova,N.,2016.Treatment of landfill leachate by continuously reused ferric oxyhydroxide sludgeactivated hydrogen peroxide.Chem.Eng.J.304,646-654.
Li,X.,Zhang,Y.,Xie,Y.,Zeng,Y.,Li,P.,Xie,T.,et al.,2018.Ultrasonic-enhancedFenton-like degradation of bisphenol Ausing a bio-synthesized schwertmannite catalyst.J.Hazard.Mater.344,689-697.
Liao,Y.,Zhou,L.,Bai,S.,Liang,J.,Wang,S.,2009.Occurrence of biogenic schwertmannite in sludge bioleaching environments and its adverse effect on solubilization of sludge-borne metals.Appl.Geochem.24,1739-1746.
Liao,Y.,Liang,J.,Zhou,L.,2011.Adsorptive removal of As(III)by biogenic schwertmannite from simulated As-contaminated groundwater.Chemosphere 83,295-301.
Liu,H.,Li,P.,Zhu,M.,Wei,Y.,Sun,Y.,2007.Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite.J.Solid State Chem.180,2121-2128.
Magnone,E.,Kim,S.D.,Park,J.H.,2018.A systematic study of the iron hydroxide-based adsorbent for removal of hydrogen sulphide from biogas.Microporous Mesoporous Mater.270,155-160.
Mahmood,T.,Din,S.U.,Naeem,A.,Tasleem,S.,Alum,A.,Mustafa,S.,2014.Kinetics,equilibrium and thermodynamics studies of arsenate adsorption from aqueous solutions onto iron hydroxide.J.Ind.Eng.Chem.20,3234-3242.
Mezenner,N.Y.,Bensmaili,A.,2009.Kinetics and thermodynamic study of phosphate adsorption on iron hydroxide-eggshell waste.Chem.Eng.J.147,87-96.
Neyens,E.,Baeyens,J.,2003.A review of classic Fenton's peroxidation as an advanced oxidation technique.J.Hazard.Mater.98,33-50.
Paikaray,S.,Schr?der,C.,Peiffer,S.,2017.Schwertmannite stability in anoxic Fe(II)-rich aqueous solution.Geochim.Cosmochim.Acta 217,292-305.
Ponomar,V.P.,2018.Thermomagnetic properties of the goethite transformation during high-temperature treatment.Miner.Eng.127,143-152.
Regenspurg,S.,Brand,A.,Peiffer,S.,2004.Formation and stability of schwertmannite in acidic mining lakes 1 1 Associate editor:C.M.Eggleston.Geochim.Cosmochim.Acta 68,1185-1197.
Rezaee,F.,Danesh,S.,Tavakkolizadeh,M.,Mohammadi-Khatami,M.,2019.Investigating chemical,physical and mechanical properties of eco-cement produced using dry sewage sludge and traditional raw materials.J.Clean.Prod.214,749-757.
Sánchez Espa?a,J.,López Pamo,E.,Santofimia Pastor,E.,2007.The oxidation of ferrous iron in acidic mine effluents from the Iberian Pyrite Belt(Odiel Basin,Huelva,Spain):field and laboratory rates.J.Geochem.Explor.92,120-132.
?wierczek,L.,Cie?lik,B.M.,Konieczka,P.,2018.The potential of raw sewage sludge in construction industry-a review.J.Clean.Prod.200,342-356.
Xie,Y.,Lu,G.,Ye,H.,Yang,C.,Xia,D.,Yi,X.,et al.,2017.Fulvic acid induced the liberation of chromium from CrO42--substituted schwertmannite.Chem.Geol.475,52-61.
Xiong,Y.,Tong,Q.,Shan,W.,Xing,Z.,Wang,Y.,Wen,S.,et al.,2017.Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon.Appl.Surf.Sci.416,618-627.
Yu,J.-Y.,Park,M.,Kim,J.,2002.Solubilities of synthetic schwertmannite and ferrihydrite.Geochem.J.36,119-132.
Zhang,K.,Dwivedi,V.,Chi,C.,Wu,J.,2010.Graphene oxide/ferric hydroxide composites for efficient arsenate removal from drinking water.J.Hazard.Mater.182,162-168.
Zhao,X.,Su,Y.,Li,S.,Bi,Y.,Han,X.,2018.A green method to synthesize flowerlike Fe(OH)3 microspheres for enhanced adsorption performance toward organic and heavy metal pollutants.J.Environ.Sci.73,47-57.
Zhu,Y.,Zhu,R.,Yan,L.,Fu,H.,Xi,Y.,Zhou,H.,et al.,2018.Visiblelight Ag/AgBr/ferrihydrite catalyst with enhanced heterogeneous photo-Fenton reactivity via electron transfer from Ag/AgBr to ferrihydrite.Appl.Catal.B:Environ.239,280-289.