Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.     

The evolution and present status of the study on peak oil in China

Peak oil theory is a theory concerning long-term oil reserves and the rate of oil production. Peak oil refers to the maximum rate of the production of oil or gas in any area under consideration. Its inevitability is analyzed from three aspects. The factors that influence peak oil and their mechanisms are discussed. These include the amount of resources, the discovery maturity of resources, the depletion rate of reserves and the demand for oil. The advance in the study of peak oil in China is divided into three stages. The main characteristics, main researchers, forecast results and research methods are described in each stage. The progress of the study of peak oil in China is summarized and the present problems are analyzed. Finally three development trends of peak oil study in China are presented.     

Contents and Abstracts

The development course, the structure and performance of various types of double- layer tank in gas station are introduced. The research results on oil corrosion and the application status of double- layer tank in North America and Eu~ rope are presented. The advantages of FRP tank about the aspects of corrosion resistance, safety and environment protection are described. Based on the upgrading process of oil product quality in China, the double - layer FRP tank is considered to have broad application prospects in China.     

Contents and Abstracts

STORAGE TECHNOLOGIES 1. Discussion on Transforming Option for a 10 x 104 m3 Floating Roof Tank. Zhang Yi, Li Jian- rain. Abstract： According to the requirement of a en- terprise, a 10 ~ 104 m3 floating roof tank built in 2001 for storage of crude oil needed to be trans- formed into a vault tank with internal floating roof for storage of diesel. The status of the tank needs to be transformed and the main transformation items are introduced, and the feasibility of trans- forming option is discussed from the aspects of technology, construction period and investment.     

Influence of separator control on the characteristics of severe slugging flow

Due to the special structure of offshore multiphase pipes, it is easy for severe slugging to occur in the riser at low gas-liquid velocity. Violent pressure fluctuations and dramatic changes of flow rate are the main characteristics of severe slugging, leading to the risk of serious damage. In this paper, the separator control is adopted to accurately control the separator liquid level and pressure under severe slugging flow conditions. This indicates that the separator liquid level control alone does not have a significant impact on the upstream flow, but it is beneficial for normal operation and pressure control of the separator. As the separator pressure increases, the peak pressure in the riser apparently diminishes, and the amplitude of pressure fluctuation gradually decreases, which means that severe slugging is inhibited. During the slug blowing out, the gas/liquid slipping in the riser intensifies. The long gas plug quickly flows through the riser, and then tends to morph into short and slowly flowing gas bubbles. The elimination effect of the pressure control strategy on severe slugging is related to the relative rate of the superficial gas/liquid flow.     

Technology for Coking of Heavy Crude Oil with High Acid Number

Sudan Khartoum Refinery Co. has selected a unique route featuring delayed coking of crude in connection with the highly sour and high-calcium heavy crude extracted from Sudanese oil block No. 6.The crude oil after pretreatment for calcium removal is subjected to coking for removal of acids and metals with the coker products being further processed. The crude oil extracted from Sudanese oil block No. 6 contains as high as 13 mg KOI-Jdg of crude in addition to a calcium content of 1600 ppm. This article makes an analysis on problems related with the operation of commercial delayed coking unit for processing of highly sour crude and bring forth measures to solve these problems. The liquid yield resulted from coking of crude oil can reach 82 m%, and the petroleum coke can meet the quality requirement for class 3B petroleum coke.     

Formation and distribution characteristics of Proterozoic–Lower Paleozoic marine giant oil and gas fields worldwide

There are rich oil and gas resources in marine carbonate strata worldwide.Although most of the oil and gas reserves discovered so far are mainly distributed in Mesozoic,Cenozoic,and upper Paleozoic strata,oil and gas exploration in the Proterozoic–Lower Paleozoic(PLP)strata—the oldest marine strata—has been very limited.To more clearly understand the oil and gas formation conditions and distributions in the PLP marine carbonate strata,we analyzed and characterized the petroleum geological conditions,oil and gas reservoir types,and their distributions in thirteen giant oil and gas fields worldwide.This study reveals the main factors controlling their formation and distribution.Our analyses show that the source rocks for these giant oil and gas fields are mainly shale with a great abundance of type I–II organic matter and a high thermal evolution extent.The reservoirs are mainly gas reservoirs,and the reservoir rocks are dominated by dolomite.The reservoir types are mainly karst and reef–shoal bodies with well-developed dissolved pores and cavities,intercrystalline pores,and fractures.These reservoirs arehighly heterogeneous.The burial depth of the reservoirs is highly variable and somewhat negatively correlated to the porosity.The cap rocks are mainly thick evaporites and shales,with the thickness of the cap rocks positively correlated to the oil and gas reserves.The development of high-quality evaporite cap rock is highly favorable for oil and gas preservation.We identified four hydrocarbon generation models,and that the major source rocks have undergone a long period of burial and thermal evolution and are characterized by early and long periods of hydrocarbon generation.These giant oil and gas fields have diverse types of reservoirs and are mainly distributed in paleo-uplifts,slope zones,and platform margin reef-shoal bodies.The main factors that control their formation and distribution were identified,enabling the prediction of new favorable areas for oil and gas exploration.     

Influence of Wind Deviation Angle on n-Hexane Evaporation Loss of Internal Floating-Roof Tanks

With the increasing attention to environmental protection, it is still necessary to strictly control the oil evaporation loss from the IFRT(internal floating-roof tank) to the atmosphere. Upon using n-hexane as a representative of light oil, the effects of the WDAs(wind deviation angles) on airflow distribution, the wind speed, the n-hexane vapor concentration, and the evaporation loss rate in the IFRT were investigated, and the mass transfer of the vapor-air was analyzed. The results are shown as follows: when the WDA is 0°, the vapor concentration in the gas space above the floating deck is the lowest; when the WDA is 22.5°, the oil evaporation loss rate is the largest; when the WDA is 45°, the vapor concentration is the highest, but the evaporation loss rate is the smallest. It is recommended to arrange the vent to the wind direction with an angle of 45° to reduce the evaporation loss and protect the atmospheric environment.     

Pretreatment of super viscous oil wastewater and its application in refinery

Wastewater from super viscous oil processing cannot be effectively treated by conventional wastewater treatment plants in refineries because of its high concentration of various organic pollutants. In order to resolve this problem, a number of investigations were conducted in our work to understand the physicochemical properties, sedimentation, demulsification and pretreatment of such super viscous oil refinery wastewater. The results showed that the key issues for pretreatment of this wastewater were： （1） Optimized process parameters were used in the sedimentation and demulsification processes for oil removal to effectively recover oil and remove scum from wastewater; （2） A suitable flocculation process was selected to minimize oil, suspended solids （SS） and chemical oxygen demand （CODcr）. A pretreatment process including three continuous steps： oil removal by sedimentation, oil removal by demulsification, and flotation separation, was proposed and applied in Liaohe Petrochemical Company, PetroChina and the oil content in effluents was less than 200 mg/L and CODcr less than 2,500 mg/L, which completely met the requirement for influent of the conventional wastewater treatment plant, and the recovered super viscous oil reached 5,873 tons in the initial year in Liaohe Petrochemical Company, PetroChina.     

Further Recognition of Petroleum Exploration Potential of Marine Carbonates in Western Tarim Basin

A series of significant discoveries in marine carbonate rocks show great petroleum exploration potential in the Tarim Basin. However, the oil and gas fields discovered in the carbonate rocks are mainly distributed around the Manjiaer Sag in the eastern Tarim Basin. Some explorations occurred and no oil or gas field was discovered around the Awati Sag in the western Tarim Basin. Information from wells and outcrops reveals that there are excellent oil and gas source rock conditions around the Awati Sag. Transformed reef-shoal reservoirs could be formed in the Ordovician carbonate rocks with paleo-geographic background and hydrothermal conditions. Therefore, it is necessary to make a systematical study and overall evaluation of the potential of the periphery of the Awati Sag in terms of source rock evolution, resource potential, high-grade reservoir formation and distribution, and main factors controlling hydrocarbon migration and accumulation.     

炼油污水处理场挥发性有机物和恶臭废气处理技术

炼油污水处理场挥发性有机物（VOCs）和恶臭废气可分为高浓度、低浓度两类：高浓度废气来自提升池、均质罐、隔油池、气浮池（浮选池）、污油罐（池）等,非甲烷总烃浓度为500～40 000 mg/m3,总气量为1 000～10 000 m3/h（标准状态）;低浓度废气来自曝气池、氧化沟、污泥脱水间,非甲烷总烃浓度为10～300 mg/m3,总气量为20 000～50 000 m3/h（标准状态）。中国石化抚顺石油化工研究院开发了适用于炼油污水处理场高浓度与低浓度废气联合处理的SWAT-1、SWAT-2工艺技术,在SWAT-1工艺中,高浓度废气采用“脱硫及总烃浓度均化-催化燃烧（氧化）”工艺处理,曝气池等低浓度废气采用“洗涤-吸附”工艺处理,低浓度废气饱和吸附剂用催化氧化排放的热气再生并返回催化氧化处理系统;而在SWAT-2工艺中,高浓度废气采用“低温柴油吸收-脱硫及总烃浓度均化-催化氧化”工艺处理。应用SWAT-1、SWAT-2工艺处理污水处理场废气,净化气非甲烷总烃浓度可小于50 mg/m3,最低小于10 mg/m3,苯、甲苯、二甲苯浓度低于检出限,臭气浓度小于20（无量纲）。     

生物法净化石化企业污水处理场恶臭废气的中型试验

采用生物法净化石化企业污水处理场曝气池逸散恶臭废气。中试结果表明，在恶臭废气中H2S人口平均浓度为4．34mg／m^3，有机硫化物浓度为6．33mg／m^3，苯系物浓度为300．0mg／m^3的条件下，H2S、有机硫化物、苯系物浓度的平均去除率分别为100％，95．6％，97．2％，臭气的去除率为99．2％。生物填料塔运行稳定，适应性强，有较强的耐H2S负荷冲击能力。     

酸性水汽提装置恶臭气体治理问题及对策

分析了酸性水汽提装置恶臭气体治理过程中出现的脱臭罐压降过大及酸性水原料罐抽空等问题的原因,并提出了相应的解决措施。结果表明,脱臭罐压降过大是由于恶臭气体携带的汽、油类、固体颗粒等物质在吸附剂间的空隙积聚,造成床层空隙率下降所致;酸性水原料罐抽空是由于该罐与水封罐间的气相连接管道存在"U形弯",气体所携带的水分在"U形弯"管道中形成"液阻"所致。建议增设1台脱臭罐,当床层压降超过1.8 kPa时,将该罐切除,进行氮气、蒸汽吹扫等再生处理;水原料罐与水封罐之间的联通管线应尽可能短并畅通。针对恶臭气体治理,还可采取尽量将恶臭气体自酸性水脱气罐中密闭排出,将富含H2S和NH3的循环液返至酸性水原料罐出口,增加酸性水原料罐中油层厚度等措施。     

炼厂酸性水罐区气体减排和治理新技术

酸性水罐区是炼油厂最大的污水罐区,排放气中含有高浓度H2S,NH3,有机硫化物、油气、水蒸气和空气,直接排放导致空气恶臭污染严重且浪费油气资源。采用来水脱气罐、罐顶气连通管网、减少罐内气相空间体积、将排水高峰安排在夜间等措施,可减排气体50%以上。采用罐内气相空间惰性气保护,可防止硫化亚铁自燃引发火灾事故。罐区排放气采用"低温粗柴油吸收-碱液吸收"工艺,粗柴油来自催化裂化分馏塔或常压塔,富吸收油进加氢装置处理;采用氢氧化钠或氨水吸收H2S时,废吸收液进酸性水罐处理;采用醇胺吸收液时,富吸收液进再生系统。该工艺的H2S、有机硫化物回收率接近100%;NH3回收率60%～90%;油气回收率可达95%以上;净化气体中的油气质量浓度小于25 g/m3;H2S,NH3、甲硫醇、甲硫醚、二甲二硫排放量小于GB 14554—93《恶臭污染物排放标准》。     

JK-010金属钝化剂的工业应用

介绍了JK-010型金属钝化剂在呼和浩特炼油厂重油催化裂化装置的使用情况，该装置所加工的原料镍含量高达14～20μg/g，平衡催化剂镍含量达15000μg/g以上。在使用该钝化剂后，干气中H2体积分数由56.88%下降至39.26%，H2/CH4由5.33降至2.18，总轻收提高1.2个百分点，经济效益十分明显。     

泥炭生物过滤器脱除复合恶臭气中的H_2S

在实验室以配制的含H2 S复合恶臭气为对象 ,研究H2 S的生物脱除工艺及二甲基二硫化物、甲苯的存在对H2 S脱除的影响。结果表明 ,H2 S入口负荷在 45g/ (m3 ·h)以下时 ,H2 S脱除率可接近 10 0 % ,并保持长时间的恒定 ,负荷波动幅度可达到 30 .3g/ (m3 ·h)。反应温度对H2 S脱除有较大影响 ,适宜的反应温度为 2 0℃以上 ;甲苯、二甲基二硫化物的存在对H2 S的生物脱除基本没有影响。该工艺可用于净化污水处理场排放的恶臭气体     

膜法分离技术在废气治理中的应用

烯烃部B罐区有10座内浮顶储罐,其中石脑油储罐6座、混合苯储罐2座、粗芳烃储罐2座,10座储罐的罐顶呼吸气直排大气环境。2017年采用“膜分离+吸附工艺”对B罐区罐顶气进行了治理,通过膜分离技术回收了其中有效组分,对于未透过膜的废气通过吸附技术满足排放标准后排放,从而减少了罐顶气对大气环境的影响。     

生物滤床工艺处理含硫恶臭废气的现场小型试验

应用生物滤床工艺，对炼油厂含硫恶臭废气进行了现场小型侧流试验研究并取得成功。试验表明该技术处理含硫恶臭废气是可行的：在废气成分较简单、浓度较低时，可采用单级生物滤床；在废气成分较复杂、污染物浓度较高时，可采用两级生物滤床串联工艺或适当的组合工艺。主要恶臭污染物的去除率较高：H2S不小于97．2％，有机硫化物不小于87．2％。苯系物不小于93．7％；在一定浓度范围内，对废气浓度变化的适应性好。在总结试验结果的基础上。分析了影响生物滤床污染物去除率的主要因素。     

0.60 Mt/a重油催化裂化装置技术改造

对中国石油化工股份有限公司沧州分公司重油催化裂化装置分馏塔、再生器主风分布系统、旋风分离系统和主风机组进行了一系列挖潜改造。改造后烧焦罐主风分布管压力降由25～30kPa下降到5～10kPa,主风机入口流量由1050m     

二级气浮+二段生化处理炼油废水

通过对石油化工企业炼油废水水质特性的分析,采用隔油—浮选—曝气—A/O生化工艺处理锦西石化的炼油废水。实践表明,二级气浮+二段生化处理工艺对炼油废水COD和NH3-N的平均去除率为96.7%和99.2%。,使外排水水质远优于辽宁省《污水综合排放标准》中规定的CODcr<50 mg/L,NH3-N<8 mg/L的标准。