改性污泥基生物炭的性质与重金属吸附效果
|
摘要
为提高污泥基生物炭在高钙溶液体系中对重金属阳离子的吸附能力,将Fe_2O_3、MnO_2、ZnO与市政污泥以质量比1∶10(以过渡金属元素质量计)混合共热解,制备改性生物炭;表征改性生物炭的组成、官能团分布和表面性质,考察其对典型重金属阳离子Cd~(2+)的吸附效果.过渡金属氧化物可促进污泥的热解,改性生物炭的H/C原子比均低于0. 31,碳链裂解脱氢更彻底.改性生物炭中Fe、Mn保留较好,分别主要以单质和氧化物形态存在;而Zn流失较多.改性生物炭中的孔隙以介孔为主,平均孔径约3. 8 nm,比表面积在50 m~2·g~(-1)以上.初始浓度约200 mg·L~(-1)的Cd~(2+)溶液中,Ca~(2+)初始浓度从0 mg·L~(-1)升高到约200 mg·L~(-1),Fe改性生物炭对Cd~(2+)的吸附容量从43. 17 mg·g~(-1)降至27. 88 mg·g~(-1),但仍较未改性生物炭高10 mg·g~(-1)以上,在含钙溶液体系中表现出了对Cd~(2+)更强的吸附性能. Fe_2O_3较MnO_2和ZnO对市政污泥基生物炭吸附重金属的强化效果更好.
To enhance the heavy metal cation adsorption capacity of sewage sludge-derived biochar in an aqueous medium with a high concentration of Ca~(2+),modified biochars were obtained from co-pyrolysis of sewage sludge and transition metal oxides( with a sewage sludge∶ transition metal mass ratio of 10∶ 1),such as Fe_2 O_3,MnO_2,and ZnO. The properties of the modified biochars were characterized,and the Cd~(2+)adsorption effect of the modified biochars was determined as well. The H/C atom ratios of the modified biochars were all lower than 0. 31,indicating that the transition metal oxides catalyzed the decomposition and volatilization of organic matter in sewage sludge. The majority of the added Fe and Mn remained in the modified biochars,and existed as a simple substance and oxide,respectively; while significant loss of Zn occurred. The pores of the modified biochars were mainly mesopores with an average pore size of approximately 3. 8 nm,and the specific surface area of the modified biochars was larger than 50 m~2·g~(-1). When the initial Cd~(2+)concentration was increased from 0 mg·L~(-1) to approximately 200 mg·L~(-1),the Cd~(2+)adsorption capacity of the Fe-modified biochar declined from 43. 17 mg·g~(-1) to 27. 88 mg·g~(-1),which was still higher than that of the unmodified biochar by at least 10 mg·g~(-1). In aqueous media with a high concentration of Ca~(2+),the Fe-modified biochar showed better Cd~(2+)adsorption performance;thus,compared to MnO_2 and ZnO,Fe_2 O_3 was the best choice to enhance the heavy metal adsorption performance of the sewage sludgederived biochar.
To enhance the heavy metal cation adsorption capacity of sewage sludge-derived biochar in an aqueous medium with a high concentration of Ca~(2+),modified biochars were obtained from co-pyrolysis of sewage sludge and transition metal oxides( with a sewage sludge∶ transition metal mass ratio of 10∶ 1),such as Fe_2 O_3,MnO_2,and ZnO. The properties of the modified biochars were characterized,and the Cd~(2+)adsorption effect of the modified biochars was determined as well. The H/C atom ratios of the modified biochars were all lower than 0. 31,indicating that the transition metal oxides catalyzed the decomposition and volatilization of organic matter in sewage sludge. The majority of the added Fe and Mn remained in the modified biochars,and existed as a simple substance and oxide,respectively; while significant loss of Zn occurred. The pores of the modified biochars were mainly mesopores with an average pore size of approximately 3. 8 nm,and the specific surface area of the modified biochars was larger than 50 m~2·g~(-1). When the initial Cd~(2+)concentration was increased from 0 mg·L~(-1) to approximately 200 mg·L~(-1),the Cd~(2+)adsorption capacity of the Fe-modified biochar declined from 43. 17 mg·g~(-1) to 27. 88 mg·g~(-1),which was still higher than that of the unmodified biochar by at least 10 mg·g~(-1). In aqueous media with a high concentration of Ca~(2+),the Fe-modified biochar showed better Cd~(2+)adsorption performance;thus,compared to MnO_2 and ZnO,Fe_2 O_3 was the best choice to enhance the heavy metal adsorption performance of the sewage sludgederived biochar.
引文
[1] Ren J Z,Liang H W,Dong L,et al. Sustainable development of sewage sludge-to-energy in China:Barriers identification and technologies prioritization[J]. Renewable and Sustainable Energy Reviews,2017,67:384-396.
[2] Yang G,Zhang G M,Wang H C. Current state of sludge production,management,treatment and disposal in China[J].Water Research,2015,78:60-73.
[3] Ignatowicz K. The impact of sewage sludge treatment on the content of selected heavy metals and their fractions[J].Environmental Research,2017,156:19-22.
[4] Zhang W,Alvarez-Gaitan J P,Dastyar W,et al. Value-added products derived from waste activated sludge:a biorefinery perspective[J]. Water,2018,10(5):545.
[5] Raheem A,Sikarwar V S,He J,et al. Opportunities and challenges in sustainable treatment and resource reuse of sewage sludge:a review[J]. Chemical Engineering Journal,2018,337:616-641.
[6] Wu H Y,Zhou Z Y,Zhang Y X,et al. Fluorescence-based rapid assessment of the biological stability of landfilled municipal solid waste[J]. Bioresource Technology,2012,110:174-183.
[7] Han R,Zhao C X,Liu J W,et al. Thermal characterization and syngas production from the pyrolysis of biophysical dried and traditional thermal dried sewage sludge[J]. Bioresource Technology,2015,198:276-282.
[8] Kwon E E,Lee T,Ok Y S,et al. Effects of calcium carbonate on pyrolysis of sewage sludge[J]. Energy,2018,153:726-731.
[9] Ifthikar J,Wang J,Wang Q L,et al. Highly efficient lead distribution by magnetic sewage sludge biochar:sorption mechanisms and bench applications[J]. Bioresource Technology,2017,238:399-406.
[10]李锦,祖艳群,李刚,等.载镧或铈生物炭吸附水体中As(V)的作用机制[J].环境科学,2018,39(5):2211-2218.Li J,Zu Y Q,Li G,et al. Mechanism of As(V)removal from water by lanthanum and cerium modified biochars[J].Environmental Science,2018,39(5):2211-2218.
[11]赵华轩,郎印海.磁性生物炭对水中CIP和OFL的吸附行为和机制[J].环境科学,2018,39(8):3729-3735.Zhao H X,Lang Y H. Behaviors and mechanisms of CIP and OFL adsorption by magnetic biochar[J]. Environmental Science,2018,39(5):3729-3735.
[12]于长江,董心雨,王苗,等.海藻酸钙/生物炭复合材料的制备及其对Pb(Ⅱ)的吸附性能和机制[J].环境科学,2018,39(8):3719-3728.Yu C J, Dong X Y, Wang M, et al. Preparation and characterization of a calcium alginate/biochar microsphere and its adsorption characteristics and mechanisms for pb(Ⅱ)[J].Environmental Science,2018,39(8):3719-3728.
[13]陈友媛,惠红霞,卢爽,等.浒苔生物炭的特征及其对Cr(Ⅵ)的吸附特点和吸附机制[J].环境科学,2017,38(9):3953-3961.Chen Y Y, Hui H X, Lu S, et al. Characteristics of Enteromorpha prolifera biochars and their adsorption performance and mechanisms for Cr(Ⅵ)[J]. Environmental Science,2017,38(9):3953-3961.
[14]王红,夏雯,卢平,等.生物炭对土壤中重金属铅和锌的吸附特性[J].环境科学,2017,38(9):3944-3952.Wang H,Xia W,Lu P,et al. Adsorption characteristics of biochar on heavy metals(Pb and Zn)in soil[J]. Environmental Science,2017,38(9):3944-3952.
[15]郑晓青,韦安磊,张一璇,等.铁锰氧化物/生物炭复合材料对水中硝酸根的吸附特性[J].环境科学,2018,39(3):1220-1232.Zheng X Q,Wei A L,Zhang Y X,et al. Characteristic of nitrate adsorption in aqueous solution by iron and manganese oxide/biochar composites[J]. Environmental Science,2018,39(3):1220-1232.
[16] Bogusz A,Oleszczuk P. Sequential extraction of nickel and zinc in sewage sludge-or biochar/sewage sludge-amended soil[J].Science of The Total Environment,2018,636:927-935.
[17] Chen T,Zhou Z Y,Xu S,et al. Adsorption behavior comparison of trivalent and hexavalent chromium on biochar derived from municipal sludge[J]. Bioresource Technology,2015,190:388-394.
[18] Chen T,Zhou Z Y,Han R,et al. Adsorption of cadmium by biochar derived from municipal sewage sludge:impact factors and adsorption mechanism[J]. Chemosphere,2015,134:286-293.
[19]陈坦,韩融,王洪涛,等.污泥基生物炭对重金属的吸附作用[J].清华大学学报(自然科学版),2014,54(8):1062-1067.Chen T,Han R,Wang H T,et al. Adsorption of heavy metals by biochar derived from municipal sewage sludge[J]. Journal of Tsinghua University(Science and Technology),2014,54(8):1062-1067.
[20] Chen T,Zhang Y X,Wang H T,et al. Influence of pyrolysis temperature on characteristics and heavy metal adsorptive performance of biochar derived from municipal sewage sludge[J]. Bioresource Technology,2014,164:47-54.
[21] Lu H L,Zhang W H,Yang U X,et al. Relative distribution of Pb2+sorption mechanisms by sludge-derived biochar[J]. Water Research,2012,46(3):854-862.
[22] Song Z G,Lian F,Yu Z H,et al. Synthesis and characterization of a novel MnOx-loaded biochar and its adsorption properties for Cu2+in aqueous solution[J]. Chemical Engineering Journal,2014,242:36-42.
[23] Rietra R P J J,Hiemstra T,van Riemsdijk W H. Interaction between calcium and phosphate adsorption on goethite[J].Enviromental Science and Technology,2001,35(16):3369-3374.
[24] Tonkin J W,Balistrieri L S,Murray J W. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model[J]. Applied Geochemistry,2004,19(1):29-53.
[25] Han R,Liu J W,Zhang Y C,et al. Dewatering and granulation of sewage sludge by biophysical drying and thermo-degradation performance of prepared sludge particles during succedent fast pyrolysis[J]. Bioresource Technology,2012,107:429-436.
[26]范晓倩,韩融,徐东耀,等. HCl气体对污泥热解产物性质影响的试验研究[J].环境科学与技术,2014,37(1):38-42.Fan X Q,Han R,Xu D Y,et al. Impact of feeding HCl on properties of products from sewage sludge pyrolyzing[J].Evironmental Science and Technology,2014,37(1):38-42.
[27] Zhang B P,Xiong S J,Xiao B,et al. Mechanism of wet sewage sludge pyrolysis in a tubular furnace[J]. International Journal of Hydrogen Energy,2011,36(1):355-363.
[28] Uchimiya M,Wartelle L H,Klasson K T,et al. Influence of pyrolysis temperature on biochar property and function as a heavy metal sorbent in soil[J]. Journal of Agricultural and Food Chemistry,2011,59(6):2501-2510.
[29] Liu Y N,Guo Z H,Sun Y,et al. Stabilization of heavy metals in biochar pyrolyzed from phytoremediated giant reed(Arundo donax)biomass[J]. Transactions of Nonferrous Metals Society of China,2017,27(3):656-665.
[30] Sing K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity(Recommendations 1984)[J]. Pure and Applied Chemistry,1985,57(4):603-619.
[2] Yang G,Zhang G M,Wang H C. Current state of sludge production,management,treatment and disposal in China[J].Water Research,2015,78:60-73.
[3] Ignatowicz K. The impact of sewage sludge treatment on the content of selected heavy metals and their fractions[J].Environmental Research,2017,156:19-22.
[4] Zhang W,Alvarez-Gaitan J P,Dastyar W,et al. Value-added products derived from waste activated sludge:a biorefinery perspective[J]. Water,2018,10(5):545.
[5] Raheem A,Sikarwar V S,He J,et al. Opportunities and challenges in sustainable treatment and resource reuse of sewage sludge:a review[J]. Chemical Engineering Journal,2018,337:616-641.
[6] Wu H Y,Zhou Z Y,Zhang Y X,et al. Fluorescence-based rapid assessment of the biological stability of landfilled municipal solid waste[J]. Bioresource Technology,2012,110:174-183.
[7] Han R,Zhao C X,Liu J W,et al. Thermal characterization and syngas production from the pyrolysis of biophysical dried and traditional thermal dried sewage sludge[J]. Bioresource Technology,2015,198:276-282.
[8] Kwon E E,Lee T,Ok Y S,et al. Effects of calcium carbonate on pyrolysis of sewage sludge[J]. Energy,2018,153:726-731.
[9] Ifthikar J,Wang J,Wang Q L,et al. Highly efficient lead distribution by magnetic sewage sludge biochar:sorption mechanisms and bench applications[J]. Bioresource Technology,2017,238:399-406.
[10]李锦,祖艳群,李刚,等.载镧或铈生物炭吸附水体中As(V)的作用机制[J].环境科学,2018,39(5):2211-2218.Li J,Zu Y Q,Li G,et al. Mechanism of As(V)removal from water by lanthanum and cerium modified biochars[J].Environmental Science,2018,39(5):2211-2218.
[11]赵华轩,郎印海.磁性生物炭对水中CIP和OFL的吸附行为和机制[J].环境科学,2018,39(8):3729-3735.Zhao H X,Lang Y H. Behaviors and mechanisms of CIP and OFL adsorption by magnetic biochar[J]. Environmental Science,2018,39(5):3729-3735.
[12]于长江,董心雨,王苗,等.海藻酸钙/生物炭复合材料的制备及其对Pb(Ⅱ)的吸附性能和机制[J].环境科学,2018,39(8):3719-3728.Yu C J, Dong X Y, Wang M, et al. Preparation and characterization of a calcium alginate/biochar microsphere and its adsorption characteristics and mechanisms for pb(Ⅱ)[J].Environmental Science,2018,39(8):3719-3728.
[13]陈友媛,惠红霞,卢爽,等.浒苔生物炭的特征及其对Cr(Ⅵ)的吸附特点和吸附机制[J].环境科学,2017,38(9):3953-3961.Chen Y Y, Hui H X, Lu S, et al. Characteristics of Enteromorpha prolifera biochars and their adsorption performance and mechanisms for Cr(Ⅵ)[J]. Environmental Science,2017,38(9):3953-3961.
[14]王红,夏雯,卢平,等.生物炭对土壤中重金属铅和锌的吸附特性[J].环境科学,2017,38(9):3944-3952.Wang H,Xia W,Lu P,et al. Adsorption characteristics of biochar on heavy metals(Pb and Zn)in soil[J]. Environmental Science,2017,38(9):3944-3952.
[15]郑晓青,韦安磊,张一璇,等.铁锰氧化物/生物炭复合材料对水中硝酸根的吸附特性[J].环境科学,2018,39(3):1220-1232.Zheng X Q,Wei A L,Zhang Y X,et al. Characteristic of nitrate adsorption in aqueous solution by iron and manganese oxide/biochar composites[J]. Environmental Science,2018,39(3):1220-1232.
[16] Bogusz A,Oleszczuk P. Sequential extraction of nickel and zinc in sewage sludge-or biochar/sewage sludge-amended soil[J].Science of The Total Environment,2018,636:927-935.
[17] Chen T,Zhou Z Y,Xu S,et al. Adsorption behavior comparison of trivalent and hexavalent chromium on biochar derived from municipal sludge[J]. Bioresource Technology,2015,190:388-394.
[18] Chen T,Zhou Z Y,Han R,et al. Adsorption of cadmium by biochar derived from municipal sewage sludge:impact factors and adsorption mechanism[J]. Chemosphere,2015,134:286-293.
[19]陈坦,韩融,王洪涛,等.污泥基生物炭对重金属的吸附作用[J].清华大学学报(自然科学版),2014,54(8):1062-1067.Chen T,Han R,Wang H T,et al. Adsorption of heavy metals by biochar derived from municipal sewage sludge[J]. Journal of Tsinghua University(Science and Technology),2014,54(8):1062-1067.
[20] Chen T,Zhang Y X,Wang H T,et al. Influence of pyrolysis temperature on characteristics and heavy metal adsorptive performance of biochar derived from municipal sewage sludge[J]. Bioresource Technology,2014,164:47-54.
[21] Lu H L,Zhang W H,Yang U X,et al. Relative distribution of Pb2+sorption mechanisms by sludge-derived biochar[J]. Water Research,2012,46(3):854-862.
[22] Song Z G,Lian F,Yu Z H,et al. Synthesis and characterization of a novel MnOx-loaded biochar and its adsorption properties for Cu2+in aqueous solution[J]. Chemical Engineering Journal,2014,242:36-42.
[23] Rietra R P J J,Hiemstra T,van Riemsdijk W H. Interaction between calcium and phosphate adsorption on goethite[J].Enviromental Science and Technology,2001,35(16):3369-3374.
[24] Tonkin J W,Balistrieri L S,Murray J W. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model[J]. Applied Geochemistry,2004,19(1):29-53.
[25] Han R,Liu J W,Zhang Y C,et al. Dewatering and granulation of sewage sludge by biophysical drying and thermo-degradation performance of prepared sludge particles during succedent fast pyrolysis[J]. Bioresource Technology,2012,107:429-436.
[26]范晓倩,韩融,徐东耀,等. HCl气体对污泥热解产物性质影响的试验研究[J].环境科学与技术,2014,37(1):38-42.Fan X Q,Han R,Xu D Y,et al. Impact of feeding HCl on properties of products from sewage sludge pyrolyzing[J].Evironmental Science and Technology,2014,37(1):38-42.
[27] Zhang B P,Xiong S J,Xiao B,et al. Mechanism of wet sewage sludge pyrolysis in a tubular furnace[J]. International Journal of Hydrogen Energy,2011,36(1):355-363.
[28] Uchimiya M,Wartelle L H,Klasson K T,et al. Influence of pyrolysis temperature on biochar property and function as a heavy metal sorbent in soil[J]. Journal of Agricultural and Food Chemistry,2011,59(6):2501-2510.
[29] Liu Y N,Guo Z H,Sun Y,et al. Stabilization of heavy metals in biochar pyrolyzed from phytoremediated giant reed(Arundo donax)biomass[J]. Transactions of Nonferrous Metals Society of China,2017,27(3):656-665.
[30] Sing K S W. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity(Recommendations 1984)[J]. Pure and Applied Chemistry,1985,57(4):603-619.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |