Pyrolysis Kinetics and Residue Characteristics of Petrochemical Industrial Sludge

ABSTRACT

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene, ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

润滑油废白土的热解处理

以润滑油废白土为原料,利用电热解法,研究了热解终温、加热速率和CaO添加量对热解产物的影响。实验结果表明:热解终温对热解产物的影响最为显著。随着热解终温的升高,不凝气产量和产油率均迅速增加。当热解终温达到600℃时,其增加的速率逐渐缓慢增大。当控制热解终温为800℃、加热速率为16℃/min、CaO添加量为0.5%时,富氢气体产量为189.2 L/kg,气体中主要成分为H2和CH4,其含量分别为27.97%和41.64%;热解残渣含油率和重金属溶出物均低于标准规定值,热解油产率为10.98%,回收率为38.94%,其主要成分为汽油、柴油和重油3部分组成,分别含19.13%、31.35%和49.52%。     

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。     

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。     

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。     

Pyrolytic kinetics of sludge from a petrochemical factory wastewater treatment plant--a transition state theory approach

The pyrolysis of hydrocarbon-rich sludge in an oxygen-free environment can provide useful liquefaction products and residues. When applied to sewage sludge, energy and time costs are the major factors that affect the operation. Therefore, it is important to understand how the process is affected by temperature. The pyrolysis kinetics of sludge from a petrochemical factory wastewater treatment plant was studied to reveal the effects of temperature on the reaction rate and the magnitude of deltaH and deltaS of the reaction barrier. Oven-dried sludge samples were pyrolyzed in an isothermal reactor under six different temperatures. The residues were weighed at frequent intervals within a total 30-min experiment period. Data analysis indicated that a first order reaction model could describe the pyrolysis kinetics, across all experimental temperature ranges. When transition state theory was applied, the results indicated that the major reaction barrier came from the entropy term of the activation free energy. Therefore, increasing the pyrolysis temperature to overcome the reaction barrier yielded no apparent improvement, but strategies that reduced the entropy should significantly improve the reaction.     

罐底含油泥热解动力学参数计算方法的优选

在化学反应设计中反应动力学是较重要的因素。为得到更合理的污泥热解动力学参数计算方法,利用热重分析仪,在氮气气氛下对罐底含油污泥的热解特性进行研究。根据热重实验数据,分别采用Coats-Redfern法、Kissinger法、FWO法和Popescu法计算污泥热解动力学参数,并获取罐底泥热解制油的主要阶段(第2阶段)的反应活化能E、频率因子A并分析各种方法反应机理。通过对比不同计算方法得到动力学参数及拟合曲线与实验曲线的相关性,确定了最佳罐底含油污泥热解动力学参数计算方法。研究表明,Popescu法得到罐底泥的热解过程符合Jander方程,活化能E为101.43 kJ/mol,与FWO法得到的91.20 kJ/mol相近,且预测曲线与实验曲线有较好的相关性(0.9816),说明Popescu法计算罐底泥热解动力学参数更合适。     

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。     

油田采油污泥的热解动力学及其热解效果研究

以新疆克拉玛依油田采油污泥为对象，分别采用热重分析仪和小型流化床热解反应器研究了含油污泥的热解过程及其热解效果。结果表明，油泥热解主要经历了失水、轻质组分挥发、重组分快速热解失重和缓慢失重4个阶段，热解过程基本符合一级动力学方程，提高热解的升温速率，可使油泥的最大失重速率D_max、失重速率峰值温度θ_max、升温终点的最大失重率都随之增加，表现在动力学上，反映出表观活化能和碰撞频率因子的同时升高，即提高油泥热解转化率的同时也影响了热解效率。失水油泥用流化床热解，在热解温度600℃、反应时间3 min时，油泥回收率可达到87%。     

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.     

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.     

餐厨垃圾中典型组分的裂解液化特征研究

利用实验室规模的实验装置管式加热炉进行餐厨垃圾热解实验,实验分析了反应温度对餐厨垃圾热解产物分布的影响,米饭、白菜、猪肉、塑料和纸5种原料在最佳温度下可实现热解油质量产率的最大化,分别为45.02%、24.55%、61.19%、73.77%和24.86%。其中,米饭和白菜热解油含水率较高,可达到30%~40%,将含水率降到15%后,测定热值分别为25.51 MJ/kg和17.75 MJ/kg。塑料和纸混合热解时,塑料热解过程的放热效应可缩小纸的热解温度区间,增加热解油产量。红外光谱分析厨余热解油包含多种含氧有机物。通过气质联用仪(GC-MS)分析塑料热解油和塑料与纸混合热解油在180℃以下蒸馏出的液相产物,主要组分为烷烃和烯烃,从成分和热值分析,与汽油、柴油相近。     

沼渣生物炭基Fenton催化剂的制备及其高效降解吡虫啉农药废水的研究

以废弃物沼渣和含铁剩余污泥为原料,采用一步热解法制备沼渣生物炭基Fenton催化剂(以下简称催化剂),构建了非均相Fenton反应体系处理含吡虫啉模拟废水,考察了H2 O2和催化剂用量对吡虫啉去除率的影响.结果表明,非均相Fenton反应体系中,H2 O2最佳投加量为0.50 g/L,催化剂最佳投加量为1.00 g/L...     

Pyrolysis of oil sludge in a fluidised bed reactor

The oil sludge of tanker cleaning was pyrolysed in fluidised bed reactors. Three experiments were conducted in a laboratory plant and two on a technical plant. Separation of oil from the solids and distribution of the oil products were investigated at temperatures from 460 degrees C to 650 degrees C. Between 70% and 84% of the oil could be separated from the solids. Distribution of the oil products depended on the feed material and the pyrolysis conditions. The higher the temperature the more the oil was cracked into low boiling compounds. Under the conditions of pyrolysis carbon reduced gridiron to iron. Thus some solid fractions were pyrophoric and oxidised with high heat generation. Therefore the solid products have to be turned into inert substances. The fluidised bed pyrolysis is an adequate process to recycle oil sludge with high yields.     

粉煤灰和电石渣对聚丙烯塑料裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响,讨论了加入量对裂解速度和裂解产物的影响.结果表明:粉煤灰和电石渣都使裂解产物中的轻质部分(汽油和裂解气)增加、重油降低;粉煤灰比电石渣更能加快反应的进行,而且加入量越多,反应越快,需时越短;粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果.     

铝塑包装废物热解过程能量平衡分析

热解是实现铝塑包装废物中有机物和金属铝分离的有效方法。利用外热式固定床反应系统对其进行热解实验,研究热解时物质与能量流向的变化趋势。结果表明:(1)铝塑包装废物最佳热解温度为723～773 K;(2)热解产生的可回收能量远大于反应所需能量,可以实现热解系统的自供热;(3)铝塑包装废物热解的净能源回收效率为62%～63%。     

Phosphorus release from ash, dried sludge and sludge residue from supercritical water oxidation by acid or base

Leaching of ash and dried sewage sludge were investigated and compared with the leaching results of sludge residue from supercritical water oxidation (SCWO). This article focuses on how the composition of ash and sludge residues influences the extraction of phosphate and heavy metals and if different treatment temperatures of the sludge effect the leachability. Results showed that acid leaching gave a higher release of phosphate than alkaline leaching for all ash and sludge residue samples. Also, alkaline leaching dissolved phosphate with a lower metal contamination than acid leaching. Furthermore, it was found that iron had a low release at both alkaline and acid leaching from ash and from SCWO residue. The difference in composition of ash and sludge residue samples had no significant influence on release of phosphate at high concentrations of acid. Phosphate release from ash, dried sludge at 300 degrees C and SCWO residue showed similar results at 1M acid leaching. However, it seems to be easier to release phosphate from the SCWO residue than from the ash at low acid concentrations. SCWO residue showed higher release than the other ashes at 0.5M HCl. Results for alkaline leaching showed higher release from ash at 1M NaOH than from SCWO residue or from dried sludge at 300 degrees C. The leaching of phosphate from dried sludge seems to be temperature dependent, as the dried sludge treated at higher temperature showed less release of phosphate. It was found that the pre-treatment of the ash may be important for better release of phosphate.     

Toxicity of crude oil to the mayfly, Hexagenia bilineata (Ephemeroptera: Ephemeridae)

Effects of crude oil on survival and behavior of the mayfly Hexagenia bilineata were evaluated in laboratory studies. Mayfly nymphs were exposed to the water soluble and oil residue fractions of crude oil. Mayfly survival was not reduced by a 96-h exposure to either the water soluble fraction or the oil residue mixed with sediment. However, significant mortality did result from a 21-day exposure to oil residue mixed with sediment at concentrations as low as 500 microg g(-1). Survival was also reduced after a 21-day exposure to oil-contaminated sediments (1905 microg g(-1)) collected 6 weeks after a crude oil spill in the Chariton River, Missouri. In a behavioral test measuring habitat exclusion, organisms did not avoid contact with sediment containing oil residue (50-800 microg g(-1)). Collectively, results from these studies indicate that exposure to oil residue in sediment will reduce survival of H. bilineata in the laboratory and may reduce survival in the environment for 6 weeks or more after an oil spill.     

Pyrolytic characteristics of sewage sludge

In this study, a number of different sewage sludge including sludge samples from industrial and hospital wastewater treatment plants were characterized for pyrolysis behavior by means of thermogravimetric analysis up to 800 degrees C. According to the thermogravimetric results, five different types of mass loss behaviors were observed depending on the nature of the sludge used. Typical main decomposition steps occurred between 250 and 550 degrees C although some still decomposed at higher temperatures. The first group (Types I, II and III) was identified by main decomposition at approximately 300 degrees C and possible second reaction at higher temperature. Differences in the behavior may be due to different components in the sludge both quantitatively and qualitatively. The second group (Types IV and V), which rarely found, has unusual properties. DTG peaks were found at 293, 388 and 481 degrees C for Type IV and 255 and 397 degrees C for Type V. Kinetics of sludge decomposition can be described by either pseudo single or multicomponent overall models (PSOM or PMOM). The activation energy of the first reaction, corresponding to the main pyrolysis typically at 300 degrees C, was rather constant (between 68 and 77 kJ mol(-1)) while those of second and third reactions were varied in the range of 85-185 kJ mol(-1). The typical order of pyrolysis reaction was in the range of 1.1-2.1. The pyrolysis gases were composed of both saturated and unsaturated light hydrocarbons, carbon dioxide, ethanol and chloromethane. Most products, however, evolve at a quite similar temperature regardless of the sludge type.     

市政污泥水热炭化废水组成成分特征

污泥水热炭化处理被认为是极具潜力的污泥安全处置与资源化利用的技术措施之一。为了解废水中碳、氮、磷、钾和重金属含量随水热炭化反应温度和反应时间的变化规律,对市政污泥190℃和260℃水热炭化不同时间（1、6、12、18和24 h）后的废水组成成分进行了研究。结果表明,水热炭化处理后,废水颜色由黑色变成浅黄色;pH由6.40提高到9.14;TOC、COD和BOD5最高分别增加了13 175 mg/L、55 998 O2mg/L和31 723 O2mg/L;氮和钾含量显著提高,但磷含量降低;Cd、Cr含量由未检测到分别增加到0.060 mg/L和2.326 mg/L,As、Pb含量均由0.032 mg/L分别增加到1.408 mg/L和0.590 mg/L,但Cu、Mn及Zn含量降低。比起反应时间,反应温度对废水组成成分的影响更大。