Modeling and model performance evaluation of sewage sludge gasification in fluidized-bed gasifiers using Aspen Plus

A model was developed to simulate the sewage sludge gasification in an atmospheric fluidised bed gasifier using Aspen Plus. The model here presented was based on the Gibbs free energy minimisation and the restricted equilibrium method was used to calibrate it against previously published experimental data obtained in a lab-scale gasification plant. A sensitivity analysis of the model was carried out by modifying parameters such as the temperature, equivalence ratio (ER) and the steam-to-biomass ratio. The modeled results were in good agreement with the experimental data (especially when air was used as gasifying agent) and reproduced satisfactorily the experimental trends found for the gas composition, the carbon conversion (Xc) and the cold gas efficiency (CGE) under different gasification conditions. Operating at higher temperatures increased the production of H₂ and CO, as well as the Xc and the CGE. The increase in ER produced higher Xc, yet the CGE experienced slight changes due to a decrease in the lower heating value of the resulting syngas, as well as the oxidation of combustible gases. The use of air+steam as gasifying agent increased the H₂ content of the produced gases but decreased the accuracy of the model.

Implications: Gasification is an available alternative to produce energy as well as several raw materials from sewage sludge. The syngas obtained from this technology totally depends on the type of gasifier and the operation conditions, which can be optimized with the help of models. In this work, a relatively simple model was built using ASPEN PLUS. Despite its simplicity, the outputs of the model are in good agreement with experimental results what makes its use interesting for assessing scaling-up possibilities from lab-scale to pilot-scale gasification processes.     

Development of a chemical kinetic model for a biosolids fluidized-bed gasifier and the effects of operating parameters on syngas quality

In an effort to decrease the land disposal of sewage sludge biosolids and to recover energy, gasification has become a viable option for the treatment of waste biosolids. The process of gasification involves the drying and devolatilization and partial oxidation of biosolids, followed closely by the reduction of the organic gases and char in a single vessel. The products of gasification include a gaseous fuel composed largely of N₂, H₂O, CO₂, CO, H₂, CH₄, and tars, as well as ash and unburned solid carbon. A mathematical model was developed using published devolatilization, oxidation, and reduction reactions, and calibrated using data from three different experimental studies of laboratory-scale fluidized-bed sewage sludge gasifiers reported in the literature. The model predicts syngas production rate, composition, and temperature as functions of the biosolids composition and feed rate, the air input rate, and gasifier bottom temperature. Several data sets from the three independent literature sources were reserved for model validation, with a focus placed on five species of interest (CO, CO₂, H₂, CH₄, and C₆H₆). The syngas composition predictions from the model compared well with experimental results from the literature. A sensitivity analysis on the most important operating parameters of a gasifier (bed temperature and equivalence ratio) was performed as well, with the results of the analysis offering insight into the operations of a biosolids gasifier.

Implications:

As gasification becomes a more prominent waste disposal option, understanding the effects of feedstock composition and gasifier parameters on the production of syngas (rate and quality) becomes increasingly important. A model has been developed for the gasification of dried sewage sludge that will allow for prediction of changes in syngas quality (and energy recovery from the waste), and should be helpful in assessing the benefits of new gasification projects.     

Optimising the preparation of activated carbon from digested sewage sludge and coconut husk.

Preparation of activated carbon from sewage sludge is a promising way to dispose of sewage sludge as well as to produce a low-cost adsorbent for pollutant removal. This research work aimed to optimise the condition for activated carbon preparation from anaerobically digested sewage sludge with the additive coconut husk. The sewage sludge sample was mixed with the additive coconut husk. The preparation condition variables investigated involved the concentration of the ZnCl2 solutions, heating temperature, dwell time and heating rate in pyrolysis and the mixing ratio of coconut husk to sewage sludge. Surface area, pore size distribution, aqueous phenol adsorption capacity and the production yield of the final products were determined and compared. Experimental results revealed that low concentrations of ZnCl2 solution tended to improve the microporosity of the final product. Heating temperature had a considerable impact on the surface area, pore size distribution and phenol adsorption capacity of the final products, whereas dwell time and heating rate performed comparatively insignificantly. The effect of increasing the mixing ratio of coconut husk to sewage sludge was principally to increase the microporosity of the final products. The activated carbon with the highest BET surface area was produced with the activation of 5 M ZnCl2 solution and, thereafter, pyrolysis at a heating temperature of 500 degrees C for 2 h with a heating rate of 10 degrees C/min. The mixing ratio of 1:4 in terms of coconut husk to sewage sludge based on their dried weights was found to be most cost effective.     

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。     

油田含油污泥热解制备烟气脱硫剂

为实现油田含油污泥深度资源化,针对高含油的孤岛采油厂含油污泥采用热解处理,回收油气资源的同时将热解残渣制备成烟气脱硫剂。以苯吸附值和热解残渣含油率为基准对热解工艺进行了优化,对热解油品和残渣进行分析,热解残渣经过后续处理进行了烟气脱硫性能评价。通过正交实验得到热解最佳工艺条件为:氮气保护下,热解温度550℃,热解时间4h,升温速率10℃/min。此时苯吸附值为60.12mg/g,热解残渣含油率为0.29%。最佳工艺条件下,热解油品产率可达10%左右,回收率大于65%,热裂解作用明显,热解油品的品质较好,产生的不凝气体可以作为洁净燃料气;热解残渣经过后续处理,可用于脱除烟气中的SO2,吸附脱硫能力较好,穿透硫容达到3%以上。     

Experimental research of oily sawdust air gasification

This article shows oily sawdust gasification research on countercurrent installation. Experimental research was on a laboratory scale. The main purpose of the experiment was combustible gas production with higher CH₄ concentration. Gas concentrations like CO, CO₂, CH₄, H₂, and C_nH_m determine syngas composition. The technological parameter’s value defines experimental conditions. Value of this was fuel to air ratio. With fuel to air ratio change, syngas composition was a differential phenomenon where it depended on the process parameters like temperature. Additionally, evaluation of methane formation from CO, H₂, and CO₂ was done. Methanization coefficients were based on CO and CO₂ hydrogenation reactions. Component’s activity was in analogs way to syngas components changed.

     

Pyrolysis of humic acids from digested and composted sewage sludge

Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

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。     

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。     

Performance of a semi-industrial scale gasification process for the destruction of polychlorinated biphenyls

A semi-industrial scale test was conducted to thermally treat mixtures of spent oil and askarels at a concentration of 50,000 ppm and 100,000 ppm of polychlorinated biphenyls (PCBs) under a reductive atmosphere. In average, the dry-basis composition of the synthesis gas (syngas) obtained from the gasification process was: hydrogen 46%, CO 34%, CO2 18%, and CH4 0.8%. PCBs, polychlorinated dibenzo-p-dioxins, and polychlorinated dibenzofurans (PCDDs/PCDFs) in the gas stream were analyzed by high-resolution gas chromatography (GC)-mass spectrometry. The coplanar PCBs congeners 77, 105, 118, 156/ 157, and 167 were detected in the syngas at concentrations < 2 x 10(-7) mg/m3 (at 298 K, 1 atm, dry basis, 7% O2). The chlorine released in the destruction of the PCBs was transformed to hydrogen chloride and separated from the gas by an alkaline wet scrubber. The concentration of PCBs in the water leaving the scrubber was below the detection limit of 0.002 mg/L, whereas the destruction and removal efficiency was > 99.9999% for both tests conducted. The concentration of PCDDs/PCDFs in the syngas were 8.1 x 10(-6) ng-toxic equivalent (TEQ)/m3 and 7.1 x 10(-6) ng-TEQ/m3 (at 298 K, 1 atm, dry basis, 7% O2) for the tests at 50,000 ppm and 100,000 ppm PCBs, respectively. The only PCDD/F congener detected in the gas was the octachloro-dibenzo-p-dioxin, which has a toxic equivalent factor of 0.001. The results obtained for other pollutants (e.g., metals and particulate matter) meet the maximum allowed emission limits according to Mexican, U.S., and European regulations for the thermal treatment of hazardous waste (excluding CO, which is a major component of the syngas, and total hydrocarbons, which mainly represent the presence of CH4).     

Urban energy mining from sewage sludge

This work showed that sewage sludge could be a strong candidate for biodiesel production. High lipid content (18–20%) with C_16?18-carbon range was experimentally identified and measured. These lipids from sewage sludge were converted into biodiesel via the transesterification reaction with MgO–CaO/Al₂O₃ derived from magnesium slag, and biodiesel conversion was ～98%. The experimental work enabled explaining that temperature is the main driving force for the transesterification reaction, which can be enhanced in the presence of CO₂. This also enables combination of esterification of free fatty acids and transesterification of triglycerides into a single process within 1 min in the temperature range of 350–500 °C. Sewage sludge residue after extracting lipids was also a good feedstock for recovering energy via thermo-chemical processes. The impact of CO₂ co-feed on the pyrolysis/gasification process of SS residue was also investigated in this work. The CO₂ injected into the thermo-chemical process remarkably increased the generation of CO by a factor of 2. Moreover, the introduction of CO₂ into the pyrolysis/gasification process enabled reducing condensable hydrocarbons (tar) by expediting cracking; thus, utilizing CO₂ as chemical feedstock for the gasification process not only leads to higher thermal efficiency but also has environmental benefits.     

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.     

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.     

Pyrolysis of wastewater sludge and composted organic fines from municipal solid waste: laboratory reactor characterisation and product distribution

Sludge from municipal wastewater treatment plants and organic fines from mechanical sorting of municipal solid waste (MSW) are two common widespread waste streams that are becoming increasingly difficult to utilise. Changing perceptions of risk in food production has limited the appeal of sludge use on agricultural land, and outlets via landfilling are diminishing rapidly. These factors have led to interest in thermal conversion technologies whose aim is to recover energy and nutrients from waste while reducing health and environmental risks associated with material re-use. Pyrolysis yields three output products: solid char, liquid oils and gas. Their relative distribution depends on process parameters which can be somewhat optimised depending on the end use of product. The potential of pyrolysis for the conversion of wastewater sludge (SS) and organic fines of MSW (OF) to a combustion gas and a carbon-rich char has been investigated. Pyrolysis of SS and OF was done using a laboratory fixed-bed reactor. Herein, the physical characterisation of the reactor is described, and results on pyrolysis yields are presented. Feedstock and chars have been characterised using standard laboratory methods, and the composition of pyrolysis gases was analysed using micro gas chromatography. Product distribution (char/liquid/gas) from the pyrolysis of sewage sludge and composted MSW fines at 700°C for 10 min were 45/26/29 and 53/14/33%, respectively. The combustible fractions of pyrolysis gases range from 36 to 54% for SS feedstock and 62 to 72% from OF. The corresponding lower heating value range of sampled gases were 11.8–19.1 and 18.2–21.0 MJ m^?3, respectively.     

Bench-scale gasification of cedar wood – Part I: Effect of operational conditions on product gas characteristics

The present study was conducted within the framework of R&D activities on the development of gasification and reforming technologies for energy and chemical recovery from biomass resources. Gasification of the Japanese cedar wood has been investigated under various operating conditions in a bench-scale externally heated updraft gasifier; this was followed by thermal reforming. Parametric tests by varying the residence times, gasification temperatures, equivalence ratios (ERs) and steam-to-carbon (S/C) ratios were performed to determine their effects on the product gas characteristics. Thermodynamic equilibrium calculations were preformed to predict the equilibrium gas composition and compared with the experimental value.We found that the product gas characteristics in terms of the H₂/CO ratio, CO₂/CO ratio, and CH₄ and lighter hydrocarbons concentrations are significantly affected by the operating conditions used. Increasing the residence time decreased the CO₂/CO ratio; however, a nominal effect was noticed on H₂ concentration as a function of the residence time. At sufficient residence time, increasing the temperature led to higher H₂ yields, CO efficiency and higher heating value (HHV) of the product gas. The presence of steam during gasification effectively enhanced the proportion of H₂ in the product gas. However, higher S/C ratio reduced the HHV of the product gas. Increasing the ER from 0 to 0.3 increased the H₂ yields and CO efficiency and decreased the HHV of the product gas.The evolution of CH₄ and lighter hydrocarbons at low gasification temperatures was relatively higher than that at high temperature gasification. The evolution of CH₄ and lighter hydrocarbons at high gasification temperatures hardly varied over the investigated operating conditions.     

Carbon capture of biochar produced by microwave co-pyrolysis: adsorption capacity,kinetics, and benefits

Environmental Science and Pollution Research - Microwave co-pyrolysis of sewage sludge and leucaena wood was conducted to produce biochar as an adsorbent for CO2 capture. Both microwave power level...     

Thermal detoxification of hazardous metal sludge by applied electromagnetic energy

Industrial wastewater sludge was treated by microwave processes to enhance the stabilization of laden copper. The effects of additives, processing time, microwave adsorbents, moisture content, reaction atmosphere, and cooling gas were investigated. The stabilization results were significantly enhanced by metal powder additives, prolonged microwave processing time, proper moisture content, the addition of carbonaceous materials, and a reaction environment with inert gas. It was also found that the moisture content would increase the homogeneity of applied microwave energy, and thus achieve a better overall efficiency between stabilizing agents and copper. The added metal powders may reduce Cu(II) to Cu(0) in the sludge or TCLP. The resulting thermal energy of microwave radiation, and microarcing process and the oxidation heat of Al powder may also assist the transformation of Cu(II) into CuO and CuAl2O4 phases. Part of the sludge was vitrified within inert gas environment when the processing time was longer than 18 min and active carbon dosage was more than 3g. Reduction reactions also occurred in the hybrid microwave processes, leading to the reduction of sulfates and metal ions, and the formation of Cu2S and FeS. Moreover, the microwave radiation can also enhance the feasibility of co-treating of inorganic and organic solid waste.     

热解含油污泥制备吸附剂及热解过程的优化

为资源化利用油田含油污泥,对高含油的孤岛采油厂含油污泥进行热解处理研究,以苯酚吸附值为基准对热解工艺过程进行优化,并采用ICP-MS、元素分析仪、气相色谱质谱仪和SEM对热解油品和残渣性质进行分析;正交实验和单因素实验结果相一致,热解最佳工艺条件为:N2保护下,热解温度550℃,热解时间4 h,升温速率10℃/min,此时苯酚吸附值为29.26 mg/g。通过对热解残渣苯酚吸附值为基准进行正交实验极差分析,热解温度的影响最大,其次是热解时间,最后是加热速率。SEM结果显示,热解含油污泥制备的固体残渣具有丰富的微米孔,可将其制备成多孔固体吸附剂。初步研究结果表明,含油污泥热解处理实现了无害化和资源化目的,满足国家节能减排的战略要求和农用污泥排放标准。     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

微波炉快速测定城市污泥湿度的探讨

用额定电压为220 V、振荡频率为2 450 MHz、输出功率为800 W的微波炉对5～30 g城市污泥辐照2～30 min。由不同时间对城市污泥进行微波辐照后的质量损失率、残余湿度以及挥发性固体（VS）含量的变化表明：用微波炉可简便、快速地测定城市污泥的湿度。为提高微波炉测定湿度的准确性,应减少取样量,进行重复辐照,并根据相邻2次辐照导致的质量变化幅度逐次缩短辐照时间;在辐照过程中应避免引起样品突然释放大量VS,辐照至恒重为止。