改性稻秆阴离子吸附剂的制备及对硝酸根吸附研究
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摘要
NO_3~-对水环境是污染物,对土壤而言则是肥料,因此NO_3~-高效吸附剂的研发对于水环境治理和土壤保肥均有重要意义。以废弃稻秆为原料,结合物理、化学改性手段制备出稻秆(RS)、生物炭稻秆(RS-B)、乙二胺稻秆(DMF-RS)和乙二胺生物炭稻秆(DMF-RS-B) 4种NO_3~-吸附剂,通过SEM和FTIR等方法表征其表面特性和官能团特性确定改性情况,对比4种吸附剂对NO_3~-的去除效果和有机碳源溶出量。结果表明,4种吸附剂中DMF-RS-B对NO_3~-的去除效果最好。在NO_3~-初始质量浓度为30 mg/L,吸附剂投加量为4g/L,pH=2,吸附时间为10 min时,其最大去除率可达61. 22%,表观吸附量达15. 31 mg/g。吸附剂对NO_3~-的吸附过程符合D-R吸附等温方程(R~2> 0. 99),吸附过程为多分子层吸附且是自发放热过程。通过实际水样测试,DMF-RSB对NO_3~-的吸附效果显著,且出水无二次污染。本吸附剂亦可作为缓释固相碳源及土壤保肥(氮肥)材料,是绿色无污染的吸附剂。
The given paper is inclined to present a kind of highly efficient adsorbent for nitrate in helping to improve the water environment control and soil conservation system with the physical and chemical methods( that is by using the rice straw( RS),the biochar-rice straw( RS-B),ethylenediamine-rice straw( DMFRS),and the ethylenediamine-biochar-rice straw( DMF-RS-B).As a matter of fact,nitrate is a pollutant to the water environmentbut a fertilizer to the soil. Therefore,it is necessary to verify the condition of the modified material and the adsorptive mechanism to determine the oxygen functional groups on the adsorbent surface before and after the necessary modification by SEM and FTIR. For the above said purpose,we have investigated the effects of the different modification methods,the solution's dosage and the pH value on the removal of NO_3~- by different modified adsorbents. In so doing,we have examined and identified the mechanism of NO_3~- removal by the adsorbent through the isothermal adsorption equilibrium and adsorption thermodynamics. At the same time,we have also compared the dissolution rates of the organic carbon sources of the 4 adsorbents. The experimental results we have gained in this paper have shown that: DMF-RS-B should be the best adsorbent with 61. 22% of 15. 31 mg/g under the initiating nitrate nitrogen concentration of 30 mg/L,in a dosage of 4 g/L with the pH value of 2 for the 10 minutes. The experimental results also indicate that it is also possible for the removal process of nitrate with the DMF-RS-B to be described properly via the Dubinin-Redushkevich model with its correlation coefficient being over 0. 99 correspondingly. What is more,the main adsorption process can also be described as and categorized into those of chemical reactions,suggesting that it belongs to a multi-molecule layer and self-releasing thermos process,whereas the effect of DMF-RS-B on NO_3~- should be of great significance for the simulated sewage,with no further pollution to be released. In addition,the adsorbent of the modified material may enjoy a wide application prospect in the sewage treatment. The adsorbent of the modified material can be also used as a kind of solid carbon source and soil fertilizer. It can be used as a green adsorbent as well.
The given paper is inclined to present a kind of highly efficient adsorbent for nitrate in helping to improve the water environment control and soil conservation system with the physical and chemical methods( that is by using the rice straw( RS),the biochar-rice straw( RS-B),ethylenediamine-rice straw( DMFRS),and the ethylenediamine-biochar-rice straw( DMF-RS-B).As a matter of fact,nitrate is a pollutant to the water environmentbut a fertilizer to the soil. Therefore,it is necessary to verify the condition of the modified material and the adsorptive mechanism to determine the oxygen functional groups on the adsorbent surface before and after the necessary modification by SEM and FTIR. For the above said purpose,we have investigated the effects of the different modification methods,the solution's dosage and the pH value on the removal of NO_3~- by different modified adsorbents. In so doing,we have examined and identified the mechanism of NO_3~- removal by the adsorbent through the isothermal adsorption equilibrium and adsorption thermodynamics. At the same time,we have also compared the dissolution rates of the organic carbon sources of the 4 adsorbents. The experimental results we have gained in this paper have shown that: DMF-RS-B should be the best adsorbent with 61. 22% of 15. 31 mg/g under the initiating nitrate nitrogen concentration of 30 mg/L,in a dosage of 4 g/L with the pH value of 2 for the 10 minutes. The experimental results also indicate that it is also possible for the removal process of nitrate with the DMF-RS-B to be described properly via the Dubinin-Redushkevich model with its correlation coefficient being over 0. 99 correspondingly. What is more,the main adsorption process can also be described as and categorized into those of chemical reactions,suggesting that it belongs to a multi-molecule layer and self-releasing thermos process,whereas the effect of DMF-RS-B on NO_3~- should be of great significance for the simulated sewage,with no further pollution to be released. In addition,the adsorbent of the modified material may enjoy a wide application prospect in the sewage treatment. The adsorbent of the modified material can be also used as a kind of solid carbon source and soil fertilizer. It can be used as a green adsorbent as well.
引文
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[15] ZHANG Jiqiang(张吉强),ZHENG Ping(郑平). Study on adsorption property of ammonia nitrogen in corn straw treated with different modification[J]. Industrial Water Treatment(工业水处理),2017,37(6):78-81.
[17] ZHOU Pin(周品),GU Lin(谷麟),RAO Shanshan(饶姗姗). Preparation of strain-sludge composite activated carbon and its adsorption characteristics for 1,2,4-acid oxygens[J]. Environmental Chemistry(环境化学),2013,32(1):106-111.
[17] WARTELLE L H,MARSHALL W E. Chromate ion adsorption by agricultural by-products modified with dimethyloldihy droxyethylene urea and choline chloride[J].Water Research,2005,39(13):2869-76.
[18] LIANG Hao(梁昊),LUO Zhaohui(罗朝晖),ZHAO Haiyan(赵海燕). Adsorption of Cd~(2+)in solution by 7 modified rice straws[J]. Chinese Environmental Science(中国环境科学),2018,38(2):596-607.
[19] XU X S,LIN L,PAPELIS C,et al. Sorption of Arsenic from Desalination Concentrate onto Drinking Water Treatment Solids:Operating Conditions and Kinetics[J]. Water-Sui,2018,10(2):96-111
[20] LIANF B,LEHMANN J,SOLOMON D,et al. Black carbon increases cation exchange capacity in soils[J].Soil Science Society of America Journal,2006,70(5):1719-1730.
[21] LI Jihui(李际会),LUGuohua(吕国华),BAI Wenbo(白文波). Adsorption of modified biochar and its effect on nitrate nitrogen and effective phosphorus leaching in soil[J]. Agricultural Meteorology of China(中国农业气象),2012,33(2):220-225.
[22] WANG Yu(王宇),GAO Baoyu(高宝玉),YUE Wenwen(岳文文),et al. Study on adsorption kinetics of nitrate in aqueous solution by modified corn straw[J].Journal of Environmental Science(环境科学学报),2007(9):1458-1462.
[23] MO Weiming(莫蔚明),TANG Qingsong(唐庆松),LI Wang(李旺),et al. Dynamic adsorption and desorption of nitrate on modified cassava straw[J]. Environmental Chemistry(环境化学),2013,32(9):1668-1673.
[24] YUAN Jinhua(袁金华),XU Renkou(徐仁扣). Research progress on the properties of biomass carbon and its effect on soil environmental function[J]. Journal of Ecological Environment(生态环境学报),2011,20(4):779-785.
[25] UCHIMIYA M,CANTRELLK B,HUNTP G,et al. Retention of heavy metals in a typic kandiudult amended with different manure-based biochars[J]. Journal of Environmental Quality,2012,41(4):1138-1149.
[26] WANG Weiping(王未平),DAI Youzhi(戴友芝),JIA Mingchang(贾明畅),et al. The characteristics of magnetic sepiolite surface zero charge point and adsorption Cd~(2+)[J]. Environmental Chemistry(环境化学),2012,31(11):1691-1696.
[27] TAN I A W,AHMAD A L,HAMEED B H. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon[J]. Journal of Hazardous Materials,2009,164(2/3):473-482.
[28] YOUSEF R I,El-ESWED B,ALA’A H. Adsorption characteristics of natural zeolites as solid adsorbents for phenol removal from aqueous solutions:kinetics,mechanism,and thermodynamics studies[J]. Chemical Engineering Journal,2011,171(3):1143-1149.
[29] MILAD R,NAKISA Y,MEHDI H,et al. Adsorption of divalent lead ions from aqueous solution using low silica nano-zeolite X[J]. Journal of Industrial and Engineering Chemistry,2012,18(6):1970-1976.
[30] BAGNIS S,FITZSIMONS M,SNAPE J,et al. Sorption of active pharmaceutical ingredients in untreated wastewater effluent and effect of dilution in freshwater:implications for an"impact zone"environmental risk assessment approach[J]. Science of the Total Environment,2018,624:333-341
[31] XU Jianchun(徐建春),QIU Mei(邱梅),WU Anguo(伍安国). Study on preparation method of modified straw adsorbent[J]. Paper and Paper Making(纸和造纸),2017,36(3):55-57.
[32] HAO Hongying(郝红英),SHAO Ziqiang(邵自强),HE Mengchang(何孟常). Study on physical and chemical modification and adsorption mechanism of plant straw cellulose[J]. Journal of Agro-Environment Science(农业环境科学学报),2007(3):1138-41.
[33] GUNAY A,ARSLANKAYA E,TOSUN I. Lead removal from aqueous solution by natural and pretreated clinoptilolite:adsorption equilibrium and kinetics[J]. Journal of Hazardous Materials,2007,146(1/2):362-371.
[34] INGLEZAKIS V J,STYLIANOU M A,LOIZIDOU M,et al. Experimental studies and modeling of clinoptilolite and vermiculite fixed beds for Mn2+,Zn2+and Cr3+removal[J]. Desalination and Water Treatment,2016,57(25):11610-11622.
[2] XUE D,DE B B,VAN C O,et al. Classification of nitrate polluting activities through clustering of isotope mixing model outputs[J]. Environ Qual,2013,42(5):1486.
[3] ZHANG Daofang(张道方),SHI Lifang(史利芳),XU Zhihua(许智华). Synthesis material of zeolite peat and experimental study of nitrogen and phosphorus removal[J]. Energy Research and Information(能源研究与信息),2011,27(1):1-6.
[4] CHEN Linli(陈琳荔),ZOU Hua(邹华). Removal of nitrogen and phosphorus from water by modified malmaite[J]. Journal of Food Science and Biotechnology(食品与生物技术报),2015,34(3):283-290.
[5] WEN Yonglin(文永林),LIU Pan(刘攀),TANG Qi(汤琪). Research progress on adsorption and removal of heavy metals from agricultural and forestry wastes[J].Chemical Progress(化工进展), 2016, 35(4):1208-1215
[6] YANG D,JING D,GONG H,et al. Biosorption of aquatic cadmium(II)by unmodified rice straw[J]. Bioresource Technol,2012,114:20-25
[7] SUN Liming(孙黎明),XIA Weiqing(夏维清),ZHU Xiaofan(朱晓帆). Preparation of modified straw activated carbon and its adsorption to SO2[J]. Journal of Environmental Engineering(环境工程学报),2017,11(9):5109-5113.
[8] SHEPHERD J G,JOSEPH S,SOHI S P,et al. Biochar and enhanced phosphate capture:mapping mechanisms to functional properties[J]. Chemosphere, 2017, 179:57-74.
[9] ZHANG Lu(张璐),DONG Da(董达),PING Fan(平帆). The effects of carbonization of crop stalks on rice yield and soil nutrients[J]. Journal of Agro-Environment Science(农业环境科学学报), 2018, 37(10):2319-2326.
[10] LOHMANN R,MACFARLANE J K,GSCHWEND P M. Importance of black carbon to sorption of native PAHs,PCBs,and PCDDs in Boston and New York harbor sediment[J]. Environmental Science&Technology,2005,39(1):141-148.
[11] ZHAO Lijian(赵力剑),LIAO Liming(廖黎明),LU Yuxiang(卢宇翔). Progress in research and application of biomass carbon in environmental management[J]. Industrial Water and Wastewater(工业用水与废水),2018,49(4):1-7.
[12] LI R,WANG J J,ZHOU B,et al. Enhancing phospate adsorption by Mg/Al layed double hydroxide functionalized biochar with differernt Mg/Al ratios[J]. Science of Total Environment,2016,559:121-129.
[13] MOHAN D,SARSWAT A,OK Y S,et al. Organic and inorganic contaminants removal from water with biochar,a renewable,low cost and sustainable absorbent-a critical review[J]. Bioresource Technology,2014,160:191-202.
[14] LUO Yugang(罗玉刚). Plant(straw)modified fiber resource utilization[J]. Chinese Engineering(中国工程学),2004,6(6):91-94
[15] ZHANG Jiqiang(张吉强),ZHENG Ping(郑平). Study on adsorption property of ammonia nitrogen in corn straw treated with different modification[J]. Industrial Water Treatment(工业水处理),2017,37(6):78-81.
[17] ZHOU Pin(周品),GU Lin(谷麟),RAO Shanshan(饶姗姗). Preparation of strain-sludge composite activated carbon and its adsorption characteristics for 1,2,4-acid oxygens[J]. Environmental Chemistry(环境化学),2013,32(1):106-111.
[17] WARTELLE L H,MARSHALL W E. Chromate ion adsorption by agricultural by-products modified with dimethyloldihy droxyethylene urea and choline chloride[J].Water Research,2005,39(13):2869-76.
[18] LIANG Hao(梁昊),LUO Zhaohui(罗朝晖),ZHAO Haiyan(赵海燕). Adsorption of Cd~(2+)in solution by 7 modified rice straws[J]. Chinese Environmental Science(中国环境科学),2018,38(2):596-607.
[19] XU X S,LIN L,PAPELIS C,et al. Sorption of Arsenic from Desalination Concentrate onto Drinking Water Treatment Solids:Operating Conditions and Kinetics[J]. Water-Sui,2018,10(2):96-111
[20] LIANF B,LEHMANN J,SOLOMON D,et al. Black carbon increases cation exchange capacity in soils[J].Soil Science Society of America Journal,2006,70(5):1719-1730.
[21] LI Jihui(李际会),LUGuohua(吕国华),BAI Wenbo(白文波). Adsorption of modified biochar and its effect on nitrate nitrogen and effective phosphorus leaching in soil[J]. Agricultural Meteorology of China(中国农业气象),2012,33(2):220-225.
[22] WANG Yu(王宇),GAO Baoyu(高宝玉),YUE Wenwen(岳文文),et al. Study on adsorption kinetics of nitrate in aqueous solution by modified corn straw[J].Journal of Environmental Science(环境科学学报),2007(9):1458-1462.
[23] MO Weiming(莫蔚明),TANG Qingsong(唐庆松),LI Wang(李旺),et al. Dynamic adsorption and desorption of nitrate on modified cassava straw[J]. Environmental Chemistry(环境化学),2013,32(9):1668-1673.
[24] YUAN Jinhua(袁金华),XU Renkou(徐仁扣). Research progress on the properties of biomass carbon and its effect on soil environmental function[J]. Journal of Ecological Environment(生态环境学报),2011,20(4):779-785.
[25] UCHIMIYA M,CANTRELLK B,HUNTP G,et al. Retention of heavy metals in a typic kandiudult amended with different manure-based biochars[J]. Journal of Environmental Quality,2012,41(4):1138-1149.
[26] WANG Weiping(王未平),DAI Youzhi(戴友芝),JIA Mingchang(贾明畅),et al. The characteristics of magnetic sepiolite surface zero charge point and adsorption Cd~(2+)[J]. Environmental Chemistry(环境化学),2012,31(11):1691-1696.
[27] TAN I A W,AHMAD A L,HAMEED B H. Adsorption isotherms, kinetics, thermodynamics and desorption studies of 2,4,6-trichlorophenol on oil palm empty fruit bunch-based activated carbon[J]. Journal of Hazardous Materials,2009,164(2/3):473-482.
[28] YOUSEF R I,El-ESWED B,ALA’A H. Adsorption characteristics of natural zeolites as solid adsorbents for phenol removal from aqueous solutions:kinetics,mechanism,and thermodynamics studies[J]. Chemical Engineering Journal,2011,171(3):1143-1149.
[29] MILAD R,NAKISA Y,MEHDI H,et al. Adsorption of divalent lead ions from aqueous solution using low silica nano-zeolite X[J]. Journal of Industrial and Engineering Chemistry,2012,18(6):1970-1976.
[30] BAGNIS S,FITZSIMONS M,SNAPE J,et al. Sorption of active pharmaceutical ingredients in untreated wastewater effluent and effect of dilution in freshwater:implications for an"impact zone"environmental risk assessment approach[J]. Science of the Total Environment,2018,624:333-341
[31] XU Jianchun(徐建春),QIU Mei(邱梅),WU Anguo(伍安国). Study on preparation method of modified straw adsorbent[J]. Paper and Paper Making(纸和造纸),2017,36(3):55-57.
[32] HAO Hongying(郝红英),SHAO Ziqiang(邵自强),HE Mengchang(何孟常). Study on physical and chemical modification and adsorption mechanism of plant straw cellulose[J]. Journal of Agro-Environment Science(农业环境科学学报),2007(3):1138-41.
[33] GUNAY A,ARSLANKAYA E,TOSUN I. Lead removal from aqueous solution by natural and pretreated clinoptilolite:adsorption equilibrium and kinetics[J]. Journal of Hazardous Materials,2007,146(1/2):362-371.
[34] INGLEZAKIS V J,STYLIANOU M A,LOIZIDOU M,et al. Experimental studies and modeling of clinoptilolite and vermiculite fixed beds for Mn2+,Zn2+and Cr3+removal[J]. Desalination and Water Treatment,2016,57(25):11610-11622.