A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons.

Disposal of sewage sludge is an increasingly expensive and environmentally sensitive problem throughout the world. Preparation of activated carbon from sewage sludge offers an attractive re-use alternative to the traditional disposal routes. The objective of this research work was to compare anaerobically digested sewage sludge (DS) and undigested sewage sludge (US) as source materials in the preparation of activated carbons. Prior to the preparation the properties of the two types of sewage sludges were determined and compared. Subsequently the sludge samples were activated with 5 M ZnCl2 solution and thereafter pyrolysed at heating temperature of 650 degrees C for 2 h with the heating rate of 15 degrees C/min under a nitrogen atmosphere. The produced activated carbons were characterised by surface area and porosity analysis, CHN elemental composition and ash contents determination, and aqueous phase phenol adsorption tests. The results indicate that in comparison with the DS, the US had a higher carbon content and lower ash content, and accordingly yielded a better activated carbon with a higher BET surface area, pore volume, carbon content and phenol adsorption capacity.     

玉米芯掺杂对污泥基活性炭性能的影响

针对以城市污水厂剩余污泥为原料制备的污泥基活性炭微孔性差、比表面积低的缺陷,将一定比例玉米芯掺杂到污泥中以期改善活性炭性质。通过对活性炭的比表面积、孔结构、碘值、表面官能团测定以及表面电镜分析,探讨了不同比例玉米芯掺杂对活性炭物理化学性质的影响,并以苯酚和硝基苯为目标物,对比考察所制活性炭对有机物的吸附性能。实验结果表明,随着玉米芯掺杂比例的提高,活性炭微孔体积及比表面积明显增大,但活性炭表面官能团种类及数量变化不明显。所制活性炭表面都以酸性基团为主。结果显示苯酚和硝基苯吸附值与活性炭表面酸性基团含量关系密切,因此,玉米芯的掺杂对苯酚和硝基苯的吸附没有明显的促进作用。     

Low-cost adsorbent prepared from sewage sludge and corn stalk for the removal of COD in leachate

Sewage sludge (SS) with corn stalk (CS) was used to prepare SS-based activated carbon (SAC) by pyrolysis with ZnCl₂. The effects of mixing ratio on surface area and pore size distribution, elemental composition, surface chemistry, and morphology were investigated. The results demonstrated that the addition of CS into SS samples improved the surface area (from 92 to 902 m²/g) and the microporosity (from 1.2 to 4.1 %) of the adsorbents and, therefore, enhancing the adsorption performance. The removal of leachate chemical oxygen demand (COD) was also determined. It was found that the COD removal rate reached 85 % at pH 4 with the SAC (90 wt% CS) dosage of 2 % (g/mL) and an adsorption time of 40 min. The adsorption experimental data were fitted by both Langmuir and Freundlich adsorption isotherms. Long-chain alkanes and refractory organics were found in raw leachate, but could be removed by SAC largely.     

Characterization of activated carbons prepared from sugarcane bagasse by ZnCl2 activation.

Activated carbons were prepared from the agricultural waste of sugarcane bagasse by the chemical activation with zinc chloride (ZnCl2) at the activation temperature of 500 degrees C with soaking time of 0.5 hour. The influence of activation parameters on the final carbon products was examined by varying the impregnation ratio (i.e., mass ratio of added ZnCl2 to bagasse) and bagasse size. The physical properties of carbon products were characterized by nitrogen adsorption/desorption isotherms (at 77 K) and helium displacement method. The surface area and pore volume of carbons were thus obtained by the BET equation and t-plot method. Also, the particle density and porosity of carbons were estimated by the total pore volume and true density. The increases of the values of surface area and pore volume are approximately proportional to the impregnation ratio. The microporous carbon product with the BET surface area of 905 m2/g and total pore volume of 0.44 cm3/g was obtained in the present study. Further, the adsorption isotherms of two acid dyes from aqueous solutions onto the carbon products were performed at 30 degrees C. The results show that the adsorption isotherms of acid dyes with high molecular weight or large molecular size on the microporous adsorbents of activated carbons are plateau forms, indicating multilayer adsorptions, which may be attributed to the steric hindrance of the adsorbate molecules.     

微波法污水厂污泥制备活性炭的研究

研究了以污水厂污泥为原料、微波辐照下磷酸活化法制备污泥活性炭的工艺条件,探讨了微波功率、辐照时间以及磷酸浓度对活性炭碘值的影响.结果表明,微波功率480 W、辐照时间315 s、磷酸浓度40%～45%的条件下,制备的污泥活性炭碘值为301 mg/g,总孔孔容是0.37 mL/g,平均孔径8.8 nm,比表面积168 m2/g.将该污泥活性炭用于处理TNT红水,吸附效果良好.     

微波法污水厂污泥制备活性炭的研究

研究了以污水厂污泥为原料、微波辐照下磷酸活化法制备污泥活性炭的工艺条件,探讨了微波功率、辐照时间以及磷酸浓度对活性炭碘值的影响.结果表明,微波功率480 W、辐照时间315 s、磷酸浓度40%～45%的条件下,制备的污泥活性炭碘值为301 mg/g,总孔孔容是0.37 mL/g,平均孔径8.8 nm,比表面积168 m2/g.将该污泥活性炭用于处理TNT红水,吸附效果良好.     

微波法制备污泥活性炭研究

采用微波加热法,以污水厂剩余污泥为原料,磷酸为污泥活化剂制备污泥活性炭.微波功率、辐照时间和磷酸浓度对污泥活性炭吸附性能具有显著影响,在最佳工艺条件微波功率480 W、辐照时间315 s和磷酸浓度40%条件下制得的活性炭碘值301 mg/g,比表面积168 m2/g,污泥中重金属绝大部分被固化.与传统商品炭相比,污泥炭孔隙结构以中孔为主.利用该活性炭处理城市生活污水处理厂出水,COD去除率可达87%以上,污泥炭的吸附等温线用Langmuir等温吸附模型进行描述.     

工业废水污泥的热解及升温速率对热解的影响

利用热重分析法对印染、中药和废水处理厂3种典型工业废水污泥进行了热解动力学实验研究。结果表明,工业污泥是一种高挥发分、低固定碳和低热值的劣质燃料。经过消化处理的污泥灰分含量较高,挥发分含量变小。热解过程中有3个失重速率较高的阶段,以挥发分的析出为主。升温速率对热解的最终失重率有重要影响。升温速率增加,热解更剧烈,但最终失重率的变化趋势与污泥种类有关;为使热解效果更好,不同种类的污泥应选择不同的升温速率。不同种类的污泥具有不同的热解特性,印染污泥挥发分析出阶段有2次热解。中药污泥活化能最小,印染污泥挥发分第2次热解的活化能比第1次大幅增加。     

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of its Brunauer–Emmett–Teller (BET) surface area. Two simulated flue gas conditions, (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, that is, more than 87%, regardless of their BET surface area.

Implications: We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had mercury adsorption efficiency comparable to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.     

污泥活性炭的表征及其对Cr（Ⅵ）的吸附特性

以城市污水处理厂污泥为原料，采用磷酸活化一微波热解法制备得到污泥活性炭，并将其用于吸附水溶液中的Cr（Ⅵ）。分别采用元素分析仪（VarioELcube）、比表面积孔径分布测定仪（ASAP2020）、扫描电镜（SEM）和傅里叶红外光谱（FT—IR）等仪器对原污泥及污泥活性炭的表面组成和结构进行表征，探讨污泥活性炭的孔隙结构参数和表面化学性能。通过静态吸附实验，考察了溶液初始pH，接触时间，初始Cr（Ⅵ）浓度对污泥活性炭吸附Cr（Ⅵ）效果的影响，并探讨了污泥活性炭去除Cr（Ⅵ）的机理。实验结果表明，pH越低吸附效果越好，吸附平衡时间为100h。不同温度下吸附过程均符合Langmuir等温吸附模型，30℃时最大吸附容量为27．55mg／g；吸附动力学过程符合准二级速率方程（R2〉0．99）；污泥活性炭对Cr（Ⅵ）的去除是一个吸附-还原耦合的过程。     

Preparation of activated carbons from raw and biotreated agricultural residues for removal of volatile organic compounds

Activated carbons with diverse physical and chemical properties were produced from four agriculture residues, including raw barley husk, biotreated barley husk, rice husk, and pistachio shell. Results showed that with adequate steam activation (30-90 min, 50% H2O(g),/50% N2), activated carbons with surface areas between 360 and 950 m2 g(-1) were developed. Further increases in the activation time destroyed the pore structure of activated carbons, which resulted in a decrease in the surface area and pore volume. Biotreated agricultural residues were found to be suitable precursors for producing mesoporous activated carbons. The oxygen content of activated carbons increased with increasing activation time. Results from X-ray photoelectron spectroscopy examination further suggested that H2O molecules react with the carbon surface, enhancing the deconvoluted peak area of carbonyl and carboxyl groups. Equilibrium adsorption of toluene indicated that the adsorption capacities increased with an increase in the inlet toluene concentration and a decrease in temperature. The adsorption isotherms were successfully fitted with Freundlich, Langmuir, and Dubinin-Radushkevich equations. Activated carbons derived from agricultural residues appear to be more applicable to adsorb volatile organic compounds at a low concentration and high-temperature environment.     

Optimization of preparation process of activated carbon from chestnut burs assisted by microwave and pore structural characterization analysis

In this study, activated carbon was prepared from Chinese chestnut burs assisted by microwave irradiation with potassium hydroxide (KOH) as activator, and the process conditions were optimized employing Box-Behnken design (BBD) and response surface methodology (RSM). The optimized variables were irradiation time, impregnation time, and mass ratio of alkali-to-carbon, and the iodine adsorption value was used to evaluate the adsorption property of activated carbon. The optimal preparation conditions were determined as follows: irradiation time 17 min, impregnation time 240 min, and mass ratio of alkali-to-char 1.5:1. Meanwhile, the relatively high iodine adsorption value (1141.4 mg/g) was also obtained. Furthermore, the pore structural characterization of activated carbon was analyzed. The analyzed results showed a larger Brunauer-Emmett-Teller (BET) specific surface area (1254.5 m²/g) and a higher microporosity ratio (87.2%), a bigger total pore volume (0.6565 m³/g), but a smaller average pore size (2.093 nm), which demonstrated the obtained activated carbon possessed strong adsorption capacity and well-developed microporous structure. This research could not only establish the foundation of utilizing chestnut burs to prepare activated carbon, but also provide the basis for exploitation of Chinese chestnut by-products.

Implications: Because Chinese chestnut burs are the by-products and usually discarded upon harvesting subsequently, the utilization of chestnut burs as a potential source of activated carbon is of great profit to the chestnut processing industries.     

不同升温速率下城市污水污泥热解特性及动力学研究

利用差热-热重分析法和Coats-Redfern积分法,对杭州某污水处理厂污泥在不同升温速率下的热解特性及反应动力学特征进行研究。实验结果表明,热解温度从室温升至900℃时,污泥热解过程可分为4个失重阶段;升温速率对污泥热解转化率、挥发分析出温度以及最大失重率等热解特性参数都有显著影响。升温速率越高污泥最大失重率越大;而较低的升温速率延迟了污泥热解反应时间,导致污泥失重量相对较大。根据Coats-Redfern积分法计算结果,污泥在氮气氛围下的热解反应为二级反应模式。提高升温速率可显著增加污泥热解的表观活化能和频率因子。     

Experimental design methodology for the preparation of carbonaceous sorbents from sewage sludge by chemical activation--application to air and water treatments

The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18 and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to experimental conditions, copper adsorption capacity varies from 77 to 83 mg g(-1), phenol adsorption capacity varies between 41 and 53 mg g(-1) and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g(-1). Each response has been described by a second-order model that was found to be appropriate to predict most of the responses in every experimental region. The most influential factors on each experimental design response have been identified. Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in wastewater and gas treatments have been determined using response surfaces methodology. In order to have a high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2SO4 g(-1) of sludge, 700 degrees C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.     

城市污泥热解中试系统集成一体化研究及运行效果评估

为了促进城市污泥热解工艺的工程化应用,组建了污泥热解系统、热解产物分离回收利用系统、废气净化排放系统于一体较完整的热解中试装置,在实现污泥有效处置的同时也实现了高值能源回收利用。中试工况优化,较好工况为：热解时间30-40 min,热解终温450-500℃,在此条件下,干化污泥（含水率5%）减量率为50%;热值为33.8 MJ/kg的热解油产率为17.1%左右。通过对中试运行效果的评估,得出热解油和热解气两者能量或污泥炭自身能量可供干化污泥热解本身所需能量,从而为推动污水污泥热解工艺的工程化利用提供了支持。     

Utilization of Arachis hypogaea hull,an agricultural waste for the production of activated carbons to remove phenol from aqueous solutions

Arachis hypogaea hulls, an agricultural waste, were used to prepare activated carbon by chemical activation with zinc chloride under four different activation atmospheres. The most important parameter in chemical activation was found to be the chemical ratio (activating agent/precursor). Carbonization temperature and time are the other two important variables, which had significant effect on the pore structure of carbon. The maximum Brunquer-Emmett-Teller (BET) surface area and micropore volume of the activated carbon was found to be 418 m²/g and 0.28 cm³/g, respectively. The activated carbon developed shows substantial capability to adsorb phenol from aqueous solutions. The kinetic data were fitted to the models of intraparticle diffusion, pseudo-second-order, and Lagergren, and followed more closely the pseudo-second-order chemisorption model. The isotherm equilibrium data were well fitted by the Langmuir and Freundlich models. Solution pH has significant effect on adsorption and the maximum uptake of phenol was reported at pH 3.5.     

Preparation of activated carbon using low temperature carbonisation and physical activation of high ash raw bagasse for acid dye adsorption

Activated carbons were prepared from bagasse through a low temperature (160 degrees C) chemical carbonisation treatment and gasification with carbon dioxide at 900 degrees C. The merit of low temperature chemical carbonisation in preparing chars for activation was assessed by comparing the physical and chemical properties of activated carbons developed by this technique to conventional methods involving the use of thermal and vacuum pyrolysis of bagasse. In addition, the adsorption properties (acid blue dye) of these bagasse activated carbons were also compared with a commercial activated carbon. The results suggest that despite the high ash content of the precursor, high surface areas (614-1433 m2 g(-1)) and microporous (median pore size from 0.45 to 1.2 nm) activated carbons can be generated through chemical carbonisation and gasification. The micropore area of the activated carbon developed from chars prepared by the low temperature chemical carbonisation provides favourable adsorption sites to acid blue dye (391 mg g(-1) of carbon). The alkalinity of the carbon surface and total surface area were shown to have complementary effects in promoting the adsorption of acid blue dye. Adsorption of the anionic coloured component of the acid dye was shown to be promoted in carbon exhibiting alkaline or positively charged surfaces. This study demonstrates that activated carbons with high acid dye adsorption capacities can be prepared from high ash bagasse based on low temperature chemical carbonisation and gasification.     

Effects of production conditions on yield and physicochemical properties of biochars produced from rice husk and oil palm empty fruit bunches

Biochar is the bio-solid material produced by pyrolysis. The biochar properties are controlled by feedstock and pyrolysis variables. In this study, the impacts of these production variables on biochar yield and physicochemical properties including pH, cation exchange capacity (CEC), total organic carbon (TOC) content, surface area, and pore volume and size were investigated. Rice husk (RH) and oil palm empty fruit bunches (EFB) were used as biomass. The biochars were produced at temperature range of 300 to 700 °C, heating rate of 3 to 10 °C/min and retention time of 1 to 3 h. The pyrolysis conditions were optimized using response surface methodology (RSM) technique to maximize the values of the responses. Analysis of variance (ANOVA) of the results demonstrated that the data fitted well to the linear and quadratic equations. Temperature was found to be the most effective parameter on the responses followed by retention time and heating rate, sequentially. CEC, TOC, surface area, and pore characteristics were evaluated as biochar properties determining their sorption potential. The optimum conditions for the maximum values of the properties were temperatures of 700 and 493.44 °C and time of 3 and 1 h for RH and EFB biochars, respectively. Heating rate at 3 °C/min was found to be the best rate for both biochars. The structure of EFB biomass was more sensitive to heating than rice husk. The biomass type and the production variables were demonstrated as the direct effective factors on biochar yield and physicochemical properties.     

The reuse of biosludge as an adsorbent from a petrochemical wastewater treatment plant

Biosludge was obtained from a petrochemical industry's biological wastewater treatment plant. Zinc chloride (ZnCl2) was used as a sludge activation agent during the pyrolytic process. Scanning electron microscope (SEM) image photographs, element composition, surface functional group, and pore structure were analyzed for the sludge adsorbent characteristics. Results indicated the proper ZnCl2-immersed concentration, pyrolytic temperature, and time could produce adsorbent from the biosludge. The optimal conditions for a larger surface area adsorbent were 3 M ZnCl2-immersed sludge pyrolyzed at 600 degrees C for 30 min and washed with 3 N hydrochloric acid (HCl) solution and distilled water. The predominant pore size of the sludge adsorbent was the mesopore.     

Effect of potassium hydroxide activation in the desulfurization process of activated carbon prepared by sewage sludge and corn straw

Series sludge straw–based activated carbons were prepared by sewage sludge and corn straw with potassium hydroxide (KOH) activation, and the desulfurization performance of activated carbons was studied. To obtain the best desulfurization performance, the optimum ratio between the raw materials and the activator was investigated. The results showed that when the mass ratio of sewage sludge, corn straw, and KOH was 3:7:2, the activated carbon obtained the best breakthrough and saturation sulfur sorption capacities, which were 12.38 and 5.74 times, respectively, those of samples prepared by the nonactivated raw materials. The appropriate KOH could improve the microporosity and alkaline groups, meanwhile reducing the lactone groups, which were all beneficial to desulfurization performance. The chemical adsorption process of desulfurization can be simplified to four main steps, and the main desulfurization products are elemental sulfur and sulfate.

Implications: Sewage sludge (SS) and corn straw (CS) both have great production and wide distribution and are readily available in China. Much attention has been paid on how to deal with them effectively. Based on the environment protection idea of waste treatment with waste and resource recycling, low-cost adsorbents were prepared by these processes. The proposed method can be expanded to the municipal solid waste recycling programs and renewable energy plan. Thus, proceeding with the study of preparing activated carbon by SS and straw as a carbon-based dry desulfurization agent could obtain huge social, economic, and environmental benefits.