污水污泥裂解技术研究进展

污水污泥是污水进行生物处理过程中不可避免的副产物,具有环境污染严重、产量大的特点,对污水污泥进行裂解是对污泥实现无害化、减量化、资源化的一种有效手段。总结了近年来机理研究、污水污泥裂解技术与方法的最新进展,并对污泥裂解产物裂解油、裂解气和残渣的组成资源化利用进行了综述,指出了污泥裂解技术要实现工业化亟需解决的问题。     

含油污泥热处置技术研究

对几种含油污泥热处置技术进行了研究,包括干燥、焚烧、热解和气化技术。干燥技术可以实现含油污泥的初步脱水;焚烧技术是一种高效的含油污泥减量化技术,可以将含油污泥中的石油资源转化为热能;热解技术可以使含油污泥所含的石油烃类在高温环境中裂解,进而回收热解油气;气化技术是以生产可燃性气体为导向的,可以回收更多可燃气体。在综合运用各种热处置技术之后,提出了一种含油污泥综合处置工艺,将几种含油污泥热处置技术进行对比,分析了不同热处置技术的特点和不足,指出开展含油污泥热处置技术的综合利用有很强的可行性。     

国内外石油污泥处理技术研究进展

针对国内外石油企业由于污泥问题难以持续发展的现状,介绍了石油污泥的特性以及石油污泥处理技术,包括萃取、焦化、焚烧、调剖、生物等方法,并提出我国石油污泥研究的发展以无害化、资源化为方向的建议.     

裂解色谱在石油和化工领域的应用现状

综述了裂解色谱法在国内外石油和化工领域的应用进展,介绍了直接裂解色谱法、裂解色谱-质谱法、指纹图谱技术在石油地质、油页岩工艺评价、分析硫化物、润滑油、橡胶领域和烟草化学方面的巨大作用。阐述了裂解色谱技术的局限性,并提出了未来发展的趋势。     

大庆油田含油污泥对环境的影响及其处理技术

含油污泥是石油企业开发过程中产生的重要污染源之一,也是制约油田环境质量持续提高的一大因素。以含油污泥为主的废弃物对大庆地区的土壤、大气环境、水生态环境造成了不容忽视的影响。采取有效措施妥善处理含油污泥,已成为石油企业面临的重大的环境保护问题。目前,国内外甘油污泥处理方法主要有焚烧处理技术、回注与调剖技术以及土地耕作法的生物处理技术。采用土地耕作生物法处理含油污泥技术最大的有点就是能通过廉价的天然过程将石油烃类等污染物转化成无害的土壤成分。     

长庆油田超低渗透油藏含油污泥处理技术研究

含油污泥是石油开采过程中的主要污染物之一,如何使其实现无害化处理一直困扰着石油开采企业。本文在国内外含油污泥处理现状大量调研基础上,通过对长庆油田超低渗透油藏含油污泥组分分析和室内实验,优选出一种有效的含油污泥热解技术,为下步研制含油污泥处理装置提供了依据。     

热载气体直接加热石油烃裂解研究进展?I. 裂解装置和技术

概述了以气体为热载体的石油烃直接加热裂解技术及其应用;介绍了热载气体直接加热石油烃裂解的装置组成、运行条件、产物产率、技术改进及发展状况,分析了裂解反应机理和反应动力学;指出热载气体直接加热裂解具有原料适用性广、产物分布灵活、热效率较高和受结焦影响小等优点,但同时也有裂解装置结构较复杂、缺乏系统性研究数据等不足. 最后对热载气体直接加热石油烃裂解的研究进行了展望,指出以氢氧燃烧产生的过热水蒸汽作为热载气体的直接加热裂解技术,在提高换热效率、降低碳排放、扩大原料范围和耦合制取合成气等方面有很大优势,发展前景广阔.     

催化裂解制低碳烯烃技术研究进展

对以石油路线生产低碳烯烃的催化裂解工艺进行了综述。催化裂解结合了传统蒸汽裂解和流化催化裂化的优势,表现出良好的原料适应性和较高的低碳烯烃产率,针对不同的石油裂解原料已经开展了相应工艺技术的研究。本文总结了目前催化裂解制低碳烯烃技术的研究进展,指出ZSM-5分子筛催化剂、热力学平衡限制和动力学反应条件是催化裂解反应过程中的重要影响因素和研究内容。催化剂研究仍是催化裂解工艺开发的重点,而热力学和动力学是研究反应规律的有效方法,这是今后实现石油烃类定向转化的研究方向。     

重质石油烃利用技术-重质烃气化-裂解集成工艺的模拟研究

我国是一个石油资源紧缺的发展中国家,石油供给高度依赖于世界石油市场. 世界原油资源的重质化和对轻质产品需求的增加,使重质石油烃利用技术成为我国能源和石化工业的一个重要课题. 现有的重质石油烃利用技术中,减粘裂化、焦化、催化裂化和加氢转化仍然是最主要的技术手段. 同时,气化和裂解制烯烃也显示出良好的技术潜力. 本工作提出的重质石油烃气化-裂解集成工艺利用燃烧裂解结焦为气化和裂解过程提供热量,同时产出合成气和部分低碳烯烃. 模拟研究显示,通过调整O2和水蒸汽流量可实现对气化-裂解温度的控制,在近零焦炭添加量的情况下可同时获得合成气和低碳烯烃,可在控制反应停留时间的条件下获得产物中烯烃的最大组成.     

砂子沸腾床裂解石油的工艺

一、前言建立和发展石油化学工业,首先遇到而必需解决的技术问题,是用何种方法制取大量的廉价的烯烃。除从石油炼制工业副产气中分得一定量的丙烯和丁烯外,烯烃的主要来源,是依靠裂解低级烷烃、轻油、重油或原油而取得。所以裂解技术是发展石油化学工业道路上的第一关。裂解方法随着石油化学工业的发展而不断演变;也随着各国的资源条件而采用不同的方式。制取乙烯、丙烯的主要而常用的裂解方法,是管式裂解和流化裂解。从给热的方式来说,前者是靠外部加热,热量是通过管壁间接传递的;后者是以固体作热载体,热量是直接传递的。管式裂解法中,有美、日等国普遍采用的斯东-韦勃斯脱(Stone and Webster)式管式炉,和英     

Resources recovery of oil sludge by pyrolysis: kinetics study

Oil sludge, if unused, is one of the major industrial wastes requiring treatment from petroleum refinery plants or the petrochemical industry. It contains a large amount of combustibles with high heating values. The treatment of waste oil sludge by burning has certain benefits; however, it cannot provide the useful resource efficiently. On the other hand, the conversion of oil sludge to lower molecular weight organic compounds by pyrolysis not only solves the disposal problem but also has the appeal of resource utilization. The major sources of oil sludge include the oil storage tank sludge, the biological sludge, the dissolve air flotation (DAF) scum, the American Petroleum Institute (API) separator sludge and the chemical sludge. In this study, the oil sludge from the oil storage tank of a typical petroleum refinery plant located in northern Taiwan is used as the raw material of pyrolysis. Its heating value of dry basis and low heating value of wet basis are about 10681 kcal kg⁻¹ and 5870 kcal kg⁻¹, respectively. The removal of the moisture from oil sludge significantly increases its heating value. The pyrolysis of oil sludge is conducted by the use of nitrogen as the carrier gas in the temperature range of 380–1073 K and at various constant heating rates of 5.2, 12.8 and 21.8 K min⁻¹. The pyrolytic reaction is significant at 450–800 K and complex. For the sake of simplicity and engineering use, a one‐reaction kinetic model is proposed for the pyrolysis of oil sludge, and is found to satisfactorily fit the experimental data. The activation energy, reaction order and frequency factor of the corresponding pyrolysis reaction in nitrogen for oil sludge are 78.22 kJ mol⁻¹, 2.92 and 9.48 × 10⁵ min⁻¹, respectively. For precise use, the two‐ and three‐reaction models are proposed to describe the pyrolysis results. Among the three models proposed, the three‐reaction model gives the best fit. These results are very useful for the proper design of the pyrolysis system of the oil sludge under investigation. © 2000 Society of Chemical Industry     

临港含油污泥的热解动力学分析

对含油污泥及其抽提油和热解油的组成进行分析。采用热重分析仪对含油污泥在空气氛下的热重特性进行实验研究, 考察不同升温速率下的热重(TG)和差热分析(DTA)曲线。采用Coats-Redfern积分法, 基于9种不同动力学机制模式函数分别对200～600℃之间的热重分析数据就ln[g (a)/T²]对1/T进行校正决定系数分析, 拟合反应动力学活化能和指前因子。实验结果表明:随着升温速率的增加, 油泥的TG和DTA曲线都向高温方向移动。含油污泥的热解阶段分为200～400℃和400～600℃两个阶段, 第一个阶段符合三维扩散反应动力学机制;第二个阶段含油污泥的热解反应符合一级反应规律。     

不同来源污泥热解油中多环芳烃分布特征

分析了4种不同来源污泥的热解油中16种EPA-PAHs生成分布,并探讨了污泥原样中自由赋存PAHs和污泥泥质特性（碳含量、H/C摩尔比、O/C摩尔比及挥发分含量等）的影响。结果表明,4种来源污泥热解油中均不同程度包含16种EPA-PAHs,∑EPA-PAHs含量分布次序为：工业印染污泥热解油（21.72 mg·kg^-1）>生活污泥热解油（14.10 mg·kg^-1）>造纸污泥热解油（13.72 mg·kg^-1）>食品污泥热解油（5.48 mg·kg^-1）,且以低环（2R）和中环（3R和4R）PAHs为主,其总量占∑EPA-PAHs的95%以上。热解油中PAHs含量高低与污泥自身赋存的自由PAHs含量具有一定关联;泥质特性对热解油中EPA-PAHs含量分布也呈现了不同程度影响,随着污泥泥质特性变化,3R和4R-PAHs含量变化规律较相似,均在碳含量为30.96%、H/C摩尔比为1.1、O/C摩尔比为0.33和挥发分为35.5%时达到最高水平;2R-PAHs含量在碳含量为20.75%、H/C摩尔比为1.44、O/C摩尔比为0.6和挥发分为46.3%时达到最高水平。     

污泥热解过程中多环芳烃排放规律

研究了不同温度（350~1050℃）下污泥热解过程液、气、固三相产物中16种多环芳烃（PAHs）排放规律。结果表明,PAHs趋向富集于液相产物中,其次为气相产物,在液相产物中检测到所有16种PAHs,650℃液相产物中16种PAHs（∑₁₆PAHs）总质量比最高,为96%;750℃气相产物中∑₁₆PAHs质量比最高,为21.3%以上;固相产物中PAHs含量极少,仅在650℃时达1%。所有温度下液相产物中2、3和4环PAHs均占据主导地位,∑_2,3,4环PAHs质量比达95%以上,850℃时液相产物中∑EPA-PAHs含量最高,达15.25 mg·kg^-1。气相产物主要以萘（NaP）、苊烯（Acp）、芴（Flu）和蒽（Ant）PAHs为主,未检测到高环PAHs。在高温热解阶段,污泥大分子结构裂解到达高峰,伴随产物的二次断裂、合成、环化等反应,气相产物中∑_低PAHs生成含量达到最高7.248 mg·kg^-1。不同温度下污泥热解产物中PAHs的毒性当量（TEQ）变化规律与其生成量变化基本一致,在850℃时液相产物中PAHs的TEQ最高达1.129。     

储运含油污泥慢速热解特性分析

采用精确控温的固定床反应装置研究了罐底油泥和清罐油泥在不同升温速率下热解产物特性。结果发现当升温速率为5℃·min^-1和2℃·min^-1时,两种油泥样品的油品回收率均高于65%。提高升温速率有利于促进气相产物的生成,同时得到的油相产物中环状有机物含量提高而链状有机物含量减少,这说明提高升温速率有助于C-H键断裂和环化反应的发生。借助于TG分析和Doyle方程得到两种油泥的热解反应动力学参数。发现随着升温速率加快,表观反应活化能增大了20%~37%。     

焦化厂土壤中PAHs的累积、垂向分布特征及来源分析

引言多环芳烃(polycyclic aromatic hydrocarbons,PAHs)在环境中普遍存在,由于具有强烈的诱变、致癌和致畸作用而受到越来越多的关注。以煤为主要原料的焦化行业,是环境中人类活动产生PAHs的主要来源之一,其各个生产车间内化石燃料的不完全燃烧及焦油、煤气等化工产品的加工过程都可能导致PAHs的排放。土壤是PAHs累积和迁移的重要介质,环境中的PAHs可由大气     

Investigations into the control of odour and viscosity of biomass oil derived from pyrolysis of sewage sludge

Biomass oil derived from the pyrolysis of sewage sludge has good commercial value as a fuel to power diesel engines. However, the properties of the oil, such as its bad odour, high viscosity and its instability can be a disadvantage for marketing the oil. This paper examines the possibilities of improving the characteristics of biomass oil that was derived from sludge using oil from sludge (OFS) technology. Esterification of the pyrolysis oil with ethanol and sulphuric acid (as a catalyst) was found to improve the odour characteristics significantly. Detailed analysis using gas chromatography-mass spectrometer (GC-MS) suggested conversion of fatty acids in the pyrolysis oil into esters. Among the alcohols tested, ethanol was found to produce the best smelling oil. An attempt has been made to determine the optimum parameters for the esterification process. The optimisation included the quantity of ethanol and catalyst required, in addition to the required time and temperature for the reaction. The method was found to improve the odour of the oil from an extremely annoying level to a not annoying level, reduce the viscosity of the oil by four times and increase the heating value of the oil up to 9%. Another improvement observed was improved stability of the oil, making it more suitable to be stored for long-term use.     

Investigations into the characteristics of oils produced from microwave pyrolysis of sewage sludge

GC–MS was used to determine the main components of high temperature oils obtained from the microwave pyrolysis of sewage sludge under different conditions. The effect of a multimode and a singlemode microwave oven and graphite and char as microwave absorbers on the pyrolysis process was investigated. The pyrolysis of sewage sludge was rapid with both absorbers, temperatures of up to 1000 °C being reached within a few minutes. Although the qualitative composition of the pyrolysis oils was the same for both microwave ovens and absorbers, certain quantitative differences were observed. For example, the use of graphite instead of char produced more cracking in the large aliphatic chains, a higher proportion of 1-alkenes than alkanes and an increase in the proportion of monoaromatics. The multimode microwave oven also favoured cracking and dehydrogenation reactions to a greater extent than the singlemode microwave oven. Compared with the electrical furnace, microwave-assisted heating required shorter times for pyrolysis. Moreover, the microwave pyrolysis oils were more aliphatic and oxygenated and did not contain environmentally harmful compounds such as heavy PAHs. Conversely, the pyrolysis of the sludge at high temperatures using conventional methods gave rise to an oil rich in PAHs including compounds such as benzo[e] and benzo[a]pyrene and benzo[ghi]perylene with 5 or 6 aromatic rings.     

程序升温下页岩油泥热解机理

采用热重分析仪,进行了桦甸和汪清页岩油泥在不同升温速率（5 ℃/min,10 ℃/min,20 ℃/min,40 ℃/min）下热失重实验,并通过瓦斯气析出情况研究页岩油泥热解机理。结果表明,页岩油泥热解分为3个阶段：第一阶段（20～180 ℃）为水分和轻质组分析出;第二阶段（180～360 ℃）重质组分稳定析出,是动力学研究的重点;第三阶段（360～600 ℃）为半焦炭化及矿物质失重过程。研究发现,催化剂K2CO3能有效降低油泥热解温度及其残渣率,而Al2O3对油泥热解催化不明显甚至起抑制作用。在页岩油泥热解过程中,生成的有机大分子侧链发生C—C键断链,生成小分子的烷烃和不饱和烃,在低压高温条件下,其断链位置倾向于碳链端部,使得小分子烃含量较多。     

Levels of Some Persistent Organic Pollutants (PCBs and PAHs) in Jordanian Oil Shale Ash after Direct Heating at Different Temperature Ranges

The levels of 13 polycyclic aromatic hydrocarbons (PAHs) and 12 polychlorinated biphenyls (PCBs) were studied in oil shale ash samples gathered after heating oil shale samples collected from major deposit sites in Jordan. All analyses were carried out using GC/MS instrument. The results showed that the total concentration of the studied polycyclic aromatic hydrocarbon (PAHs) was the highest (75.99–317.53 μg /kg) at the lowest temperature range (200–400°C) and it decreased as the temperature increased. For the heating temperature range 400–600°C the concentrations were all decreased to below the limit of quantification while none of the samples contained any of the studied PAHs at the highest temperature range 600–800°C. While all the analyzed samples did not contain any of the studied 13 compounds of PCBs at different temperature ranges.

Recoveries of PAHs and PCBs were found between 82–106% and 91–114%, respectively. Precision of the analytical method for both PAHs and PCBs, calculated as relative standard deviation (RSD), ranged from 0.95–7.08% and 0.78–9.03%, respectively. The limit of detection values for PAHs and PCBs were between 0.006–0.070 μg/kg and 0.149–0.330 μg/kg, respectively.

The total estimated cancer risks of exposure to PAHs in the soil samples were ranged from 9.13 × 10^?7 to 2.15 × 10^?6. By multiplying these numbers of cancer risks of exposure to oil shale ash sample-PAHs by 10⁶, it is possible to determine the maximum theoretical number of cancer cases per million of people. The maximum estimated cancer risks cases determined in this study (2 out of 1 million) are well within the acceptable range of excess cancer risk specified by the US Environmental Protection Agency.