4.陕汽集团商用车有限公司,宝鸡 721013
2.Key Laboratory of Subsurface Hydrology and Ecological Effect in Arid Region Key Laboratory of Subsurface Hydrology and Ecological Effect in Arid Region (Chang′an University), Ministry of Education, Xi′an 710054, China
3.Haiwei Environmental Technology Company, Chang′an University, Xi′an 710054, China
4.Shaanxi Automobile Group Commercial Vehicle Co. Ltd., Baoji 721013, China
为了实现市政脱水污泥的资源化,以污泥快速热解制备富氢燃气剩余半焦作为吸附材料,对刚果红(CR)模拟染料废水进行了吸附研究。采用响应曲面法的Box-Behnken实验设计原理探究了吸附剂投加量、CR初始浓度、温度和溶液pH对CR去除率的影响,并分析了剩余半焦对CR的吸附机理。结果表明:各因素对CR去除率的影响顺序为吸附剂投加量>CR初始浓度>溶液pH>温度;最佳吸附条件下CR的去除率为98.97%,与预测值(99.61%)基本吻合;由交互作用响应曲面分析结果得出,适当的增加吸附剂投加量,降低CR初始浓度和溶液pH均有助于提高CR的去除率;污泥热解剩余半焦的XRD和FT-IR表征结果显示,其主要成分为含硅无机物,BET结果显示孔隙结构发达,可提供较多的吸附位点;吸附CR后,没有新的官能团产生,表明剩余半焦对CR的吸附主要为物理吸附。
As for the resource utilization of municipal sewage sludge, the semicoke residuals from sludge rapid pyrolysis for hydrogen-rich gas production was used to absorb the Congo red (CR) simulated dye wastewater. Box-Behnken design of response surface methodology was used to explore the effects of adsorbent dosage, initial concentration of CR, temperature and pH on CR removal rate. Furthermore, the CR adsorption mechanism by the semicoke residuals was analyzed. The results showed that the effect order of above factors on CR removal rate was following: the dosage of adsorbent > CR initial concentration > pH > temperature; the CR removal rate under the optimal adsorption conditions reached 98.97%, which was basically consistent with the predicted value of 99.61%. Through the analysis of the response surface interactions, increasing the amount of adsorbent to a certain extent, reducing the initial concentration of CR and the pH could improve the CR removal rate. The characterization results of XRD and FT-IR showed that the main components of semicoke residuals were silicon-containing inorganics, BET results demonstrated that the semicoke residuals had developed pore structure and provided many adsorption sites. No new functional groups were found after CR adsorption, which indicating that physical adsorption dominated CR adsorption on semicoke residuals.
.
Comparison of experimental and predicted values of CR removal rate
Normal probability of residual
吸附剂投加量和CR初始浓度对剩余半焦吸附CR的响应曲面图
Response surface map of adsorbent dosage and initial concentration on CR adsorption on semicoke residuals
CR初始浓度和pH对剩余半焦吸附CR的响应曲面图
Response surface map of CR initial concentration and pH on CR adsorption on semicoke residuals
吸附剂投加量和溶液pH对剩余半焦吸附CR的响应曲面图
Response surface map of adsorbent dosage and pH on CR adsorption on semicoke residuals
污泥热解剩余半焦孔容积和孔比表面积微分分布
Differential distribution of volume and pore specific surface area of sludge pyrolysis semicoke residuals
FT-IR spectra of sludge pyrolysis semicoke residuals
X-ray diffraction pattern of sludge pyrolysis semicoke residuals
[1] | DU Q, SUN J, LI Y, et al. Highly enhanced adsorption of Congo red onto graphene oxide/chitosan fibers by wet-chemical etching off silica nanoparticles[J]. Chemical Engineering Journal, 2014, 245: 99-106. doi: 10.1016/j.cej.2014.02.006 |
[2] | 张丽, 罗汉金, 方伟, 等. 改性氧化石墨烯/壳聚糖功能材料对刚果红的吸附研究[J]. 环境科学学报, 2016, 36(11): 3977-3985. |
[3] | ZHENG L, WANG C, SHU Y, et al. Utilization of diatomite/chitosan Fe(III) composite for the removal of anionic azo dyes from wastewater: Equilibrium, kinetics and thermodynamics[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 468: 129-139. |
[4] | GAO H, ZHAO S, CHENG X, et al. Removal of anionic azo dyes from aqueous solution using magnetic polymer multi-wall carbon nanotube nanocomposite as adsorbent[J]. Chemical Engineering Journal, 2013, 223: 84-90. doi: 10.1016/j.cej.2013.03.004 |
[5] | CHAKRABORTY S, BASAK B, DUTTA S, et al. Decolorization and biodegradation of congo red dye by a novel white rot fungus Alternariaalternata CMERI F6[J]. Bioresource Technology, 2013, 147: 662-666. doi: 10.1016/j.biortech.2013.08.117 |
[6] | PENG H H, CHEN J, JIANG D Y, et al. Merging of memory effect and anion intercalation: MnOx-decorated MgAl-LDO as a high-performance nano-adsorbent for the removal of methyl orange[J]. Dalton Transactions, 2016, 45(26): 10530-10538. doi: 10.1039/C6DT00335D |
[7] | CHENG Z, ZHANG L, GUO X, et al. Adsorption behavior of direct red 80 and congo red onto activated carbon/surfactant: process optimization, kinetics and equilibrium[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 137: 1126-1143. doi: 10.1016/j.saa.2014.08.138 |
[8] | RAFI M, SAMIEY B, CHENG C H. Study of adsorption mechanism of congo red on graphene oxide/PAMAM nanocomposite[J]. Materials, 2018, 11(4): 496-520. doi: 10.3390/ma11040496 |
[9] | KIM K H, KIM J Y, CHO T S, et al. Influence of pyrolysis temperature on physicochemical properties of biochar obtained from the fast pyrolysis of pitch pine (Pinusrigida)[J]. Bioresource Technology, 2012, 118: 158-162. doi: 10.1016/j.biortech.2012.04.094 |
[10] | LIAN L, GUO L, GUO C. Adsorption of congo red from aqueous solutions onto Ca-bentonite[J]. Journal of Hazardous Materials, 2009, 161(1): 126-131. doi: 10.1016/j.jhazmat.2008.03.063 |
[11] | ZHANG F, YIN X, ZHANG W. Development of magnetic Sr5(PO4)3(OH)/Fe3O4, nanorod for adsorption of congo red from solution[J]. Journal of Alloys & Compounds, 2016, 657: 809-817. |
[12] | LUO S, FENG Y. The production of hydrogen-rich gas by wet sludge pyrolysis using waste heat from blast-furnace slag[J]. Energy, 2016, 113: 845-851. doi: 10.1016/j.energy.2016.07.130 |
[13] | 韩融, 刘晋文, 赵晨曦, 等. 生物物理干化污泥快速热解半焦特性研究[J]. 中国给水排水, 2016, 32(15): 70-74. |
[14] | LIU C, TANG Z, CHEN Y, et al. Characterization of mesoporous activated carbons prepared by pyrolysis of sewage sludge with pyrolusite[J]. Bioresource Technology, 2010, 101(3): 1097-1101. doi: 10.1016/j.biortech.2009.09.012 |
[15] | 彭峰, 何丕文. 亚甲基蓝在污泥微波热解半焦上的吸附[J]. 水处理技术, 2011, 37(5): 51-54. |
[16] | FAN S, JIE T, YI W, et al. Biochar prepared from co-pyrolysis of municipal sewage sludge and tea waste for the adsorption of methylene blue from aqueous solutions: Kinetics, isotherm, thermodynamic and mechanism[J]. Journal of Molecular Liquids, 2016, 220: 432-441. doi: 10.1016/j.molliq.2016.04.107 |
[17] | MAHAPATRAK, RAMTEKE D S, PALIWAL L J. Production of activated carbon from sludge of food processing industry under controlled pyrolysis and its application for methylene blue removal[J]. Journal of Analytical & Applied Pyrolysis, 2012, 95: 79-86. |
[18] | 王格格, 李刚, 陆江银, 等. 热解工艺对污泥制备生物炭物理结构的影响[J]. 环境工程学报, 2016, 10(12): 7289-7293. doi: 10.12030/j.cjee.201507124 |
[19] | 李晋. 污泥经机械化预处理在不同条件下快速热解制氢研究[D]. 西安: 长安大学, 2018. |
[20] | 王雅辉, 邹雪刚, 舒冉君, 等. 胡敏素对Pb2+吸附的响应面优化及机理[J]. 中国环境科学, 2017, 37(5): 1814-1822. doi: 10.3969/j.issn.1000-6923.2017.05.026 |
[21] | 王利平, 刘静静, 沈肖龙, 等. 响应面法优化凹凸棒土吸附水中亚甲基蓝[J]. 环境工程学报, 2016, 10(9): 4912-4918. doi: 10.12030/j.cjee.201503263 |
[22] | 李柳柳, 闫伯骏, 崔建升, 等. 基于响应曲面法优化H2O2/Fe3+脱除烧结烟气中的Hg0[J]. 环境工程学报, 2018, 12(4): 1083-1091. doi: 10.12030/j.cjee.201708060 |
[23] | SEN K, MONDAL N K, CHATTORAJ S, et al. Statistical optimization study of adsorption parameters for the removal of glyphosate on forest soil using the response surface methodology[J]. Environmental Earth Sciences, 2017, 76(1): 22-37. doi: 10.1007/s12665-016-6333-7 |
[24] | 姜春红, 赵研, 王鹏. 基于响应面法的改性玉米芯吸附水中Zn2+的工艺条件优化及机理研究[J]. 环境保护科学, 2017, 43(2): 76-80. |
[25] | 唐方云, 银媛媛. 污水处理效果评价的一点思考[J]. 环境科学导刊, 2012, 31(2): 84-85. doi: 10.3969/j.issn.1673-9655.2012.02.022 |
[26] | 安强, 蒋韵秋, 吴丹青, 等. 响应面法探究花生壳炭吸附水中镍离子的最优改性条件[J]. 重庆大学学报, 2018, 41(12): 46-54. |
[27] | 王泽怿, 赵斌, 沈伯雄, 等. 热改性废茶叶吸附刚果红性能的研究[J]. 工业水处理, 2017, 37(4): 78-82. doi: 10.11894/1005-829x.2017.37(4).019 |
[28] | NAUTIYAL P, SUBRAMANIAN K A, DASTIDAR M G. Adsorptive removal of dye using biochar derived from residual algae after in-situ transesterification: Alternate use of waste of biodiesel industry[J]. Journal of Environmental Management, 2016, 182: 187-197. doi: 10.1016/j.jenvman.2016.07.063 |
[29] | 赵伟, 白云翔, 张春芳, 等. 水葫芦生物质炭的制备与染料吸附性能研究[J]. 应用化工, 2017, 46(10): 95-98. |
[30] | MANE V S, VIJAY BABU P. Kinetic and equilibrium studies on the removal of congo red from aqueous solution using Eucalyptus wood (Eucalyptus globulus) saw dust[J]. Journal of the Taiwan Institute of Chemical Engineers, 2013, 44(1): 81-88. doi: 10.1016/j.jtice.2012.09.013 |
[31] | 闻辂, 矿物红外光谱学[M]. 重庆: 重庆大学出版社, 1988. |
[32] | PANEK P, KOSTURA B, CEPELAKOVA I, et al. Pyrolysis of oil sludge with calcium-containing additive[J]. Journal of Analytical and Applied Pyrolysis, 2014, 108: 274-283. doi: 10.1016/j.jaap.2014.04.005 |
[33] | 徐阳. 硅藻土基吸附剂的制备及其吸附性能的研究[D]. 吉林: 吉林化工学院, 2018. |
[34] | VIMONSES V, LEI S, JIN B, et al. Kinetic study and equilibrium isotherm analysis of congo red adsorption by clay materials[J]. Chemical Engineering Journal, 2009, 148(2/3): 354-364. |
[35] | 段小月, 曹红丽, 刘伟, 等. 粉煤灰的改性及对刚果红的吸附[J]. 化工环保, 2013, 33(4): 294-298. doi: 10.3969/j.issn.1006-1878.2013.04.003 |
[36] | 徐姗姗, 魏刚, 张晓丰, 等. 陶土-粉煤灰基吸附性陶瓷基体的制备及其吸附性能[J]. 北京化工大学学报(自然科学版), 2012, 39(4): 42-46. doi: 10.3969/j.issn.1671-4628.2012.04.009 |