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%。     

Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor

The photocatalytic oxidation of methyl orange under weak illumination conditions was carried out in two different types of fluidized bed reactors. TiO2 powder was employed as the photocatalysts and a 15 W low pressure mercury lamp was used as the light source and the reactor volume was 2.5 l. The parametric study of photocatalytic oxidation of methyl orange in two different types of fluidized beds was investigated; effect of catalyst loadings, pH, air flow rate, initial concentration and oxygen concentration on the oxidation reaction rate. The experimental results were analyzed in conjunction with the characteristics of fluidized bed and the reactor geometry effect on the reaction rate was analyzed.     

废印制线路板真空热解渣分选与组成分析的研究

在自行设计制备的真空热解炉中进行了废印制线路板的热解实验，得到固体、液体和气体产物。着重研究了热解固体渣中金属铜和非金属玻璃纤维的物理分选、热解固体渣分析及有氧煅烧对玻璃纤维纯度的影响。结果表明，物理分选效率很高，金属铜的回收率和纯度接近100%；热解固体渣含30.35%的铜、56.21%的玻璃纤维和13.45%的炭黑；有氧煅烧去除炭黑可得到高纯度的玻璃纤维。     

The Autothermal Pyrolysis of Waste Tires

Abstract

The growing amount of rubber waste, such as that from tires and cables, has resulted in serious environmental problems. Since rubber waste is not easily biodegradable even after a long period of landfill treatment, material and energy recovery is the preferable alternative to disposal. The potential offered by waste tire pyrolysis for solving both energy and waste treatment problems is widely recognized. Pyrolysis is one method of inducing thermal decomposition without using any oxidizing agent, or using such a limited supply of the agent that oxidization does not proceed to an appreciable extent. The latter may be described as autothermal pyrolysis and will be studied in the present work.

The main objective of this research was to study the operating parameters of autothermal pyrolysis of scrap tires in a laboratory-scale fluidized bed reactor with a 100-cm bed height (10 cm I.D.) and a 100-cm freeboard (25 cm I.D.). Scrap tires were pyrolyzed in a limited oxygen supply, so that the heat for pyrolysis of the scrap tires was provided by combustion of some portion of the scrap tires. The operating parameters evaluated included the effect on the pyrolysis oil products and their relative proportions of (1) the air factor (O.O7–O35); (2) the pyrolysis temperature (370–570 °C); and (3) the catalyst added (zeolite and calcium carbonate). The results show that: (1) the composition of the liquid hydrocarbon obtained is affected significantly by the air factor; (2) the higher operating temperature caused a higher yield of gasoline and diesel; (3) the yield of gasoline increased due to the catalyst zeolite added, and the yield of diesel increased due to the addition of the catalyst calcium carbonate; (4) the principal constituents of gasoline included dipentene and diprene.     

Combustion characteristics of spent catalyst and paper sludge in an internally circulating fluidized-bed combustor

Combustion of spent vacuum residue hydrodesulfurization catalyst and incineration of paper sludge were carried out in thermo-gravimetric analyzer and an internally circulating fluidized-bed (ICFB) reactor. From the thermo-gravimetric analyzer-differential thermo-gravimetric curves, the pre-exponential factors and activation energies are determined at the divided temperature regions, and the thermo-gravimetric analysis patterns can be predicted by the kinetic equations. The effects of bed temperature, gas velocity in the draft tube and annulus, solid circulation rate, and waste feed rate on combustion efficiency of the wastes have been determined in an ICFB from the experiments and the model studies. The ICFB combustor exhibits uniform temperature distribution along the bed height with high combustion efficiency (>90%). The combustion efficiency increases with increasing reaction temperature, gas velocity in the annulus region, and solid circulation rate and decreases with increasing waste feed rate and gas velocity in the draft tube. The simulated data from the kinetic equation and the hydrodynamic models predict the experimental data reasonably well.     

Stabilization of Heavy Metal Containing Hazardous Wastes with Byproducts from Advanced Clean Coal Technology Systems

ABSTRACT

The purpose of this investigation was to evaluate the success of residues from advanced Clean Coal Technology (CCT) systems as stabilization agents for heavy metal containing hazardous wastes. In the context examined here, stabilization refers to techniques that reduce the toxicity of a waste by converting the hazardous constituents to a less soluble, mobile, or toxic form.¹ Three advanced CCT byproducts were used: coal waste-fired circulating fluidized bed combustor residue, pressurized fluidized bed combustor residue, and spray drier residue. Seven metal-laden hazardous wastes were treated: three contaminated soils, two air pollution control dusts, wastewater treatment plant sludge, and sandblast waste. Each of the seven hazardous wastes was treated with each of the three CCT byproducts at dosages of 10, 30, and 50% by weight (byproduct:waste). The treatment effectiveness of each mixture was evaluated by the Toxicity Characteristic Leaching Procedure. Of the 63 mixtures evaluated, 21 produced non-hazardous residues. Treatment effectiveness can likely be attributed to mechanisms such as precipitation and encapsulation due to the formation of hydrated calcium silicates and calcium sulfo-alu-minates. Results indicate that these residues have potential beneficial uses to the hazardous waste treatment community, possibly substituting for costly treatment chemicals.     

Combustion Characteristics of Spent Catalyst and Paper Sludge in an Internally Circulating Fluidized-Bed Combustor

Abstract

Combustion of spent vacuum residue hydrodesulfurization catalyst and incineration of paper sludge were carried out in thermo-gravimetric analyzer and an internally circulating fluidized-bed (ICFB) reactor. From the thermogravimetric analyzer-differential thermo-gravimetric curves, the pre-exponential factors and activation energies are determined at the divided temperature regions, and the thermo-gravimetric analysis patterns can be predicted by the kinetic equations. The effects of bed temperature, gas velocity in the draft tube and annulus, solid circulation rate, and waste feed rate on combustion efficiency of the wastes have been determined in an ICFB from the experiments and the model studies. The ICFB combustor exhibits uniform temperature distribution along the bed height with high combustion efficiency (>90%). The combustion efficiency increases with increasing reaction temperature, gas velocity in the annulus region, and solid circulation rate and decreases with increasing waste feed rate and gas velocity in the draft tube. The simulated data from the kinetic equation and the hydrodynamic models predict the experimental data reasonably well.     

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%。     

Evolution and kinetics of volatile organic compounds generated during low-temperature polymer degradation

A method using direct flame ionization detector (FID) measurement was developed to study total volatile organic compound (VOC) emissions during thermal degradation of polymers. This method was used to estimate organic emissions from different polymers, such as low-density polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and commingled postconsumer streams, such as recycled carpet residue and auto shredder residue (ASR). The effects of process parameters, such as temperature, heating rate, and residence time, were also studied. Significant VOC emissions were observed at normal processing temperatures, particularly from recycled polymers. Each polymer showed a distinct evolution pattern during its thermal degradation. The kinetics of VOC emissions were also studied using a nonisothermal technique. The kinetic parameters were in agreement with data from the literature.     

两段式热解厨余垃圾实验研究

通过厨余垃圾的工业分析，发现其挥发分比例较高，适合热解利用；采用热重分析方法分析了不同条件下厨余垃圾的热解特性，提出了厨余垃圾两段式热解转化利用的思路，得出了厨余垃圾热解的合适工艺条件。在自行设计建造的一段回转炉、二段焦化罐中对厨余垃圾热解，并分析了产物的组成和性质。     

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。     

Thermogravimetric kinetic analysis and pollutant evolution during the pyrolysis and combustion of mobile phone case

The increase in electronic waste, including cellular telephones, worldwide is a worrying reality. For this reason, urgent action on the management of these wastes is necessary within a framework that respects the environment and human health. Mobile phone components can be physically segregated through grinding at the dismantling sites, in order to reuse or reprocess (via chemical or physical recycling) the recovered plastics and valuable metals. A kinetic study of the thermal decomposition of a mobile phone case has been carried out under different conditions by thermogravimetry. Several experiments were performed in a nitrogen atmosphere (pyrolysis runs) and also in an oxidative atmosphere with two different oxygen concentrations (10% and 20% oxygen in nitrogen). Dynamic runs and dynamic+isothermal runs have been carried out to obtain much decomposition data under different operating conditions. Moreover some TG-MS runs were performed in order to better understand the thermal decomposition of a mobile phone case and identify some compounds emitted during the controlled heating of this material. A scheme of two independent reactions for pseudocomponents has been proposed for the pyrolysis process. For the combustion runs, the scheme proposed includes two pyrolytic reactions competing with other two reactions with formation of an intermediate residue, and finally the reaction of oxidation/burning of the intermediate residue. Furthermore, pyrolysis and combustion runs at 500 °C in a horizontal laboratory furnace were carried out. More than 50 compounds, including carbon oxides, light hydrocarbons, and polycyclic aromatic hydrocarbons (PAHs) have been identified and quantified. The main semivolatile compounds detected were phenol and styrene. Furthermore, polychlorodibenzo-p-dioxin and polychlorodibenzofurans (PCDD/Fs) and dioxin-like PCBs produced were analyzed. In the combustion run, PCDDs were obtained in higher amounts than PCDFs and HxCDD was the most emitted homologue.     

Influence of Fiber Diameter on Pressure Drop and Filtration Efficiency of Glass Fiber Mats

Abstract

A method using direct flame ionization detector (FID) measurement was developed to study total volatile organic compound (VOC) emissions during thermal degradation of polymers. This method was used to estimate organic emissions from different polymers, such as low-density polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), and commingled postconsumer streams, such as recycled carpet residue and auto shredder residue (ASR). The effects of process parameters, such as temperature, heating rate, and residence time, were also studied. Significant VOC emissions were observed at normal processing temperatures, particularly from recycled polymers. Each polymer showed a distinct evolution pattern during its thermal degradation. The kinetics of VOC emissions were also studied using a nonisothermal technique. The kinetic parameters were in agreement with data from the literature.     

两相厌氧流化床中优势菌种降解硝基苯废水的特性

构建了从强化传质与优势菌相结合的两相厌氧流化床生物降解体系,考察了水力停留时间(HRT)与上流速度2种水力特征以及共基质、pH、进水浓度等主要过程因素对优势菌种降解硝基苯的影响.结果显示,反应器在HRT为36h、上流速度为4 m/h时获得较好的处理效果;菌种需要pH 7.5的条件下以葡萄糖为共基质降解硝基苯,且两者的最佳质量比约为6;当进水硝基苯浓度为50～345 mg/L时,对硝基苯平均降解率和降解速率分别达到91.1%和120.9 mg/(L·d),且可耐受2.5倍以内的浓度负荷冲击.由此表明良好的反应器水力条件及优势菌种的结合可使高毒性的硝基苯在厌氧条件下有效地降解.     

Study of the transference rules for bromine in waste printed circuit boards during microwave-induced pyrolysis

The production of waste printed circuit boards (WPCBs) has drawn increasing global concern, especially because the high bromine (Br) content (5-15%) places obstacles in the way of simple disposal techniques. Microwave-induced pyrolysis of WPCBs provides a promising way to dispose of these hazardous and resource-filled wastes. The transference rules for Br during microwave-induced pyrolysis have been investigated experimentally. It was found that the microwave energy could be used more efficiently to accelerate the heating rate and improve the final pyrolysis temperature by adding some activated carbon (AC) as microwave absorbents. The high temperature and rapid pyrolysis process promoted the yields of gaseous products and the decomposition of brominated compounds into hydrogen bromide and then benefited the capture of Br and the debromination of byproducts. The application of a calcium carbonate (CaCO3) layer overhead led to over 95% debromination of the liquid products and over 50% capture of the total Br. It can be concluded that the presented method is suitable for the control of Br transference in the recycling of WPCBs. This method can also be extended to the disposal of the electronic scraps.     

低浓度废水厌氧处理的研究进展

本文展望了国内外厌氧处理低浓度废水的研究进展状况。着重介绍了厌氧滤池（AF）、厌氧流化床（AFB）、上流式厌氧污泥床（UASB）、厌氧颗粒污泥膨胀床（EGSB）、厌氧折流板反应器（ABR）和厌氧序批式活性污泥法（ASBR）等。     

基于膨胀特性的厌氧流化床反应器的设计和运行控制

生物流化床的床层膨胀行为直接与生化反应区的水动力学和效率相关 ,床层膨胀特性是进行合理设计和运行的重要依据。目前流化床设计一般没有考虑生物膜的影响 ,但生物颗粒的流化行为有别于光滑载体 ,因此需要对曳力系数Cd 和膨胀特性方程中的ui 进行必要的修正。在综合分析基础上 ,探讨了优化两相流化床设计和运行的程序和方法     

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.     

Classification and comparison of municipal solid waste based on thermochemical characteristics

Municipal solid waste (MSW) has been normally sorted into six categories, namely, food residue, wood waste, paper, textiles, plastics, and rubber. In each category, materials could be classified further into subgroups. Based on proximate and ultimate analysis and heating value, statistical methods such as analysis of variance (ANOVA) and cluster analysis were applied to analyze the characteristics of MSW in every subgroup and to try to distinguish their relative properties. The chemical characteristics analysis of MSW showed that polyethylene (PE), polypropylene (PP), and polystyrene (PS) had the highest volatile matter content, with almost no ash and fixed carbon, while polyethylene terephthalate (PET) had high carbon content but low hydrogen content. Bones and vegetables had the highest ash content, while nutshells and rubber had the highest fixed carbon content. Paper and starch food had the highest oxygen content, and wool and bones had the highest nitrogen and sulfur content. Polyvinyl chloride (PVC) had the highest chlorine content at about 55%. PE, PP, and PS had the highest heating value, followed by chemical products such as rubber and chemical fiber. Conversely, paper, vegetables and bones had the lowest heating value. The results of cluster analysis of MSW components showed that fruit peel, weeds, wood, bamboo, leaves and nutshells could be classified as the lignocellulose category; starch food, cotton, toilet paper, printing paper and cardboard could be classified as the glucose monomer category; wood and chemical fiber could be classified as the high nitrogen and sulfur category; and PE, PP, and PS could be cluster as the polyolefin category.

Implications: The yield of municipal solid waste (MSW) is constantly increasing and waste to energy (WTE) has been used extensively all over the world. During the processes of incineration, pyrolysis, or gasification, the impact of physical and chemical properties of MSW is of great significance. However, the traditional classification of MSW is too general to provide more detailed information in many investigations. It is necessary to perform the investigation of characteristics of combustible MSW to distinguish different categories of MSW and find out their subclassification.     

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。