SLAB View软件在含硫天然气井井喷泄漏扩散模拟中的应用

介绍了SLAB重气泄漏扩散模型,并运用SLAB View软件模拟了某含硫气井发生井喷事故H2S云团的扩散过程和危害区域,得出了H2S云团在指定浓度平均时间下的影响范围,以及指定浓度H2S云团出现在最远距离的时间和最远下风向扩散距离。结果表明,SLAB View软件能方便、快速地模拟平坦地形下含硫天然气井喷泄漏扩散过程,预测事故泄漏扩散后果和影响范围。     

TiO_2基硫磺回收催化剂表面化学特性研究

随着炼油工业和天然气工业的快速发展,针对SO2排放的环保要求日益严格。对于炼油加工和天然气净化过程所产生的含硫酸性气体,硫磺回收加尾气处理工艺是主要的治理方式,其中TiO2基硫磺回收催化剂逐步得到广泛应用。通过一系列的XPS、XRD、TEM、FT-IR、CO2-TPD、NH3-TPD和吡啶红外分析表征手段,进一步认识到钛基催化剂的表面化学特性,其活性组分为锐钛矿相TiO2,晶粒为纳米级晶粒,具有弱碱性位和中强碱性位。     

Prediction of the conditions for sour gas hydrate formation in the presence of methanol inhibitor

In this work a new thermodynamic model for accurate prediction of H₂S and CO₂ containing sour gas hydrate equilibrium dissociation temperatures in the presence of a gas hydrate thermodynamic inhibitor (methanol) is presented. The average absolute deviation between the predicted and measured sour gas hydrates dissociation temperatures (AADT%) considering pure and mixed acid gases in the presence of methanol inhibitor is about 0.274% which is much lower than those obtained by the other available thermodynamic models. The proposed approach is quite reliable over wide ranges of methanol and acid gases concentrations and can be used for performance evaluation of other gas hydrate inhibitors regarding the design of sour natural gas flow assurance systems in oil and gas industries.     

CT系列催化剂在大型天然气净化厂的应用效果分析及活性预测技术研究

硫磺回收装置是含硫天然气开发生产的配套处理装置,对酸气中H 2S进行催化转化,能起到资源回收、降低SO2排放的重要作用,而装置所用催化剂的性能很大程度上决定其硫回收率的高低,对装置整体运行效率有重要影响。分析评价了CT系列催化剂在某大型天然气净化厂硫磺回收装置的应用效果情况,并以催化剂反应热力学平衡为基础,结合催化剂性能变化研究,对在运催化剂的活性进行预测。结果表明,通过活性预测技术的应用,可为装置的平稳、安全、高效运行提供科学客观的性能参数,也能为CT系列催化剂的持续改进与优化提供参考。     

Modelling of CO2 capture and separation from different gas mixtures using semiclathrate hydrates

In this work we present a model for predicting hydrate formation condition to separate carbon dioxide (CO₂) from different gas mixtures such as fuel gas (H₂+CO₂), flue gas (N₂+CO₂), and biogas gas (CH₄+CO₂) in the presence of different promoters such as tetra-n-butylammonium bromide (TBAB), tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium fluoride (TBAF), tetra-n-butyl ammonium nitrate (TBANO₃), and tetra-n-butylphosphonium bromide (TBPB). The proposed method was optimized by genetic algorithm. In the proposed model, hydrate formation pressure is a function of temperature and a new variable in term of Z, which used to cover different concentrations of studied systems. The study shows experimental data and predicted values are in acceptable agreement.     

GB 17820对硫化物气体标准物质的影响探讨

介绍了强制性标准GB 17820-2018《天然气》实施后对我国硫化物气体标准物质的需求和影响。结合天然气质量控制领域的重大变化,分析国际、国内的H_2S和SO_2气体标准物质的现状和标准物质的溯源性,提出相对应的硫化物尤其是H_2S和SO_2气体标准物质的研发和生产需求。标准中规定进入长输管道的天然气应符合一类气的质量要求,一类商品天然气中H_2S质量浓度应不超过6 mg/m~3。为了实现对一类天然气中H_2S含量的准确分析和溯源,满足管输天然气现场微量H_2S的分析,应有相应摩尔分数的H_2S气体标准物质,完善一类天然气中H_2S的分析溯源链。     

Enhanced Natural Gas and Condensate Recovery by Carbon Dioxide and Methane Flooding

Abstract

The authors quantitatively investigates the recovery efficiency, pattern behavior, and relative permeability of (a) condensate following supercritical carbon dioxide (CO₂) injection, methane (CH₄) injection, and the injection of their mixtures; and (b) natural gas of various compositions following pure supercritical CO₂ injection. A high-pressure high-temperature experimental laboratory was established to simulate reservoir conditions and to perform relative permeability measurements on sandstone cores. This work is part of an integrated enhanced natural gas and condensate recovery project conducted for a local reservoir in Western Australia. This data will help the operators develop operational and design strategies for their present and future EOR projects.     

Laboratory investigation of carbon dioxide separation from methane using a PES/Pebax 1657 composite membrane

Removal of carbon dioxide from methane is a critical issue in the gas sweetening and treatment units. The aim of this study is to investigate the capability of PES/Pebax composite membrane in order to CO₂ removal from the CH₄. In this regard, permeability values of both carbon dioxide and methane have been measured. The ranges of temperature and pressure used for pure gases experiments were 20–50°C and 2.5–10 bar, respectively. Moreover, influence of CO₂ concentration on the CH₄ permeability and its selectivity was studied. Results indicated that the pressure and temperature have significant influence on permeability and selectivity. In addition, for the gas mixtures, experiments were carried out at 5 bar and 35°C. Results also indicated that at higher CO₂ concentrations the CO₂ permeability increased significantly.     

H6P2W18O62/MCM-48催化剂的制备、表征及催化绿色合成己二酸

以MCM-48为载体,通过浸渍法制备了H6P2W18O62/MCM-48催化剂,并采用FT-IR、XRD、SEM、EDS对催化剂进行表征。以微波促进30%(质量分数)H2O2氧化环己酮合成己二酸反应为探针,考察了H6P2W18O62/MCM-48的催化性能,并通过正交实验确定了优化的工艺条件。结果表明,采用H6P2W18O62负载量40%的H6P2W18O62/MCM-48催化剂,在优化的合成己二酸的工艺条件下,即催化剂质量分数(以环己酮质量计)5.1%、n(C6H10O)∶n(H2O2)∶n(H2C2O4.2H2O)=100∶450∶1.88、反应温度95℃、微波功率300 W、反应时间3.5h,己二酸收率可达81.3%;催化剂重复使用5次,己二酸收率仍可达到64.6%。     

Hydrogen production by catalytic gasification of petroleum residue

The liquid fuel gasification to obtain a clean flue gas for power generation and produce chemicals such as methanol is a most promising attempt to reduce the greenhouse gas emissions and air pollutants. In this paper, an equilibrium model of liquid fuel gasification was developed by the method of Gibbs free energy minimization. Two kinds of catalysts: Ni/CeO₂/Al₂O₃ and Ni/Al₂O₃ were used to explore the influence of catalysts and operating conditions on hydrogen yield and char conversion. Over the ranges of operating conditions studied, the maximum hydrogen yield reached 52.47 vol%, whereas the char conversion varied between 45.2% and 98.5%. The results indicated that an appropriate reaction temperature is favorable for higher hydrogen production and char conversion. The model was validated with experimental data obtained from a fluidized bed gasifier.     

The Evaluation of Variable-Injection Rate Waterflooding,Immiscible CO2 Flooding,and Water-alternating-CO2 Injection for Heavy Oil Recovery

Abstract

Despite the existence of studies for separate evaluation of waterflooding, immiscible CO₂ flooding, and CO₂ water-alternating gas (WAG) for heavy oil recovery, there is a lack of an experimental, comparative evaluation of these three methods. The authors conducted tests for comparative evaluation of variable-injection rate waterflood (VIWF), immiscible CO₂ flood, and CO₂ WAG. The results illustrate the (a) effectiveness of VIWF, immiscible CO₂ flood, and CO₂ WAG; (b) effect of permeability and oil viscosity on VIWF, immiscible CO₂ flood, and CO₂ WAG; (c) effect of injection rate on VIWF; and (d) effect of slug ratio on CO₂ WAG.     

Application of LS-SVM strategy to estimate H2S loading capacity in different ionic liquids and alkanolamines

Favorable properties of aqueous solutions are improved with the addition of different materials for separation of hydrogen sulfide (H₂S). Also, equilibrium data and available equations for solubility estimation of this gas are only valid for specific solutions and limited ranges of temperature and pressure. In this regard, a machine learning model based on Support vector machine (SVM) algorithm is proposed and developed with mixtures containing different amines and ionic liquids to predict H₂S solubility over wide ranges of temperature (298–434.5 K), pressure (13–9319 kPa), overall mass concentration (3.82–100%) and mixture's apparent molecular weight (18.39–556.17 g/mol). The accuracy of the performance of this network was evaluated by regression analysis on calculated and experimental data, which had not been used in network training.     

Design of Catalyst Support for Deep Hydrodesulfurization of Gas Oil

Abstract

Alumina-silica (Al₂O₃-SiO₂) composite supports were examined to find the optimum state of support (i.e., composition and morphology). SiO₂ content in the Al₂O₃-SiO₂ support induced a shift of the main peak to higher frequency ascribed to an increased amount of Mo₈O₂₆ ^4?. A 75 wt% Al₂O₃-25 wt% SiO₂ support had homogeneously dispersed alumina particles of smaller size with high crystallinity. Hydrodesulfurization (HDS) of straight-run gas oil and its conventionally hydrotreated straight-run gas oil was performed over NiMo sulfides supported on Al₂O₃-SiO₂ composites. The high crystallinity of NMASA2-27 may be related to the high HDS and hydrogenation activity of NiMo sulfides due to its moderate interaction with the alumina surface.     

H2S废气反应炉燃烧数值模拟

针对某炼油化工厂H_2S反应炉设计的不同结构的燃烧器进行三维数值模拟,研究了不同燃烧器结构参数、燃料气成分与分配比例、反应炉花墙结构等因素对炉内流动与燃烧的影响,并确定了合理的燃烧器结构。结果表明:原始燃烧器结构下,单烧酸性气工况时,降低内圈酸性气比例有利于H_2S的完全燃烧,炉膛出口烟温有所提高;优化后的燃烧器结构较原始结构下,增强了内圈酸性气与空气的混合,更有利于H_2S气体的燃烧;反应炉内花墙结构能造成炉膛内烟气回流,提高了烟气的停留时间,有利于H_2S气体的燃烧完全;掺烧天然气工况较单烧酸性气工况,炉内燃烧变差。     

CO2 Adsorption Isotherm on Modified Calcite,Quartz, and Kaolinite Surfaces: Surface Energy Analysis

Interaction of CO₂ with mineral surfaces is of increasing importance to the activities related to CO₂ sequestration and enhanced oil recovery. Adsorption/interaction of CO₂ with mineral powder surfaces is addressed using microcalorimetric method coupled with gas chromatograph as a detector. Calcite powder surface is modified with stearic acid (SA) and asphaltene, while the silicate mineral powder surfaces (quartz and kaolinite) are modified with N,N-dimethyldodecylamine (NN-DMDA) and asphaltene. Unmodified calcite in presence of humidity has shown to have the highest capacity for CO₂ adsorption among the tested minerals, where a reaction may occur at the calcite surface. The adsorption capacity of calcite is reduced upon modification with SA and asphaltene. Similar observation is also shown with the modified silicate minerals with asphaltene. In contrast, for the modified silicate with NN-DMDA, the adsorption capacity of CO₂ increased, which may be explained by the interaction of CO₂ with the amine group of NN-DMDA.     

Origin, migration, and accumulation of carbon dioxide in the East Changde Gas Field, Songliao Basin, northeastern China

CO₂ reservoirs are widely distributed within the Yingcheng Formation in the Songliao Basin, but the extreme horizontal heterogeneity of CO₂ content causes difficulties in the exploration and exploitation of methane. Former studies have fully covered the lithology, structure, and distribution of the reservoirs high in CO₂ content, but few are reported about migration and accumulation of CO₂. Using the East Changde Gas Field as an example, we studied the accumulation mechanisms of CO₂ gas. Two original types of accumulation model are proposed in this study. The fault-controlled accumulation model refers to gas accumulation in the reservoir body that is cut by a basement fault (the West Xu Fault), allowing the hydrocarbon gas generated in the lower formation to migrate into the reservoir body through the fault, which results in a relatively lower CO₂ content. The volcanic conduit-controlled accumulation model refers to a reservoir body that is not cut by the basement fault, which prevents the hydrocarbon gas from being mixed in and leads to higher CO₂ contents. This conclusion provides useful theories for prediction of CO₂ distribution in similar basins and reservoirs.     

大型天然气净化厂硫磺回收加氢尾气深度脱硫技术研究及工业应用

针对硫磺回收加氢尾气脱硫溶剂在低压下脱硫效果不理想导致排放尾气中SO_2质量浓度较高的问题,研究开发出了CT8-26加氢尾气深度脱硫溶剂,并在遂宁龙王庙天然气净化厂尾气处理装置上得到工业应用。应用结果表明,在天然气净化厂气质条件下,可使脱硫后加氢尾气中的H2S质量浓度20mg/m~3,能显著降低排放尾气中的SO_2质量浓度。     

炼油厂燃料气中C_(3)+及H_(2)优化回收利用北大核心CSCD

目的回收利用炼厂燃料气中的C_(3)+及H_(2),提高经济效益。方法通过对不同来源的燃料气分析对比,找出其中富H_(2)、高C_(3)+燃料气。优化H_(2)利用及回收流程,增加脱氢膜面积,提高H_(2)回收量。利用催化装置和焦化装置的吸收稳定系统回收燃料气中的C_(3)+。结果技改总投资320万元,可回收C_(3)+1.23×10^(4) t/a,增效3000万元/年;H_(2)回收量可增加1050×10^(4) m^(3)/a,降低制氢成本1200万元/年。结论该方案充分利用炼厂现有吸收稳定系统及现有脱氢系统扩容,具有投资少、效益好、见效快的优点,对玉门炼化总厂高质量发展具有重要意义。     

Implementation of CPA EoS for simultaneous solubility modeling of CO2 and H2S in ionic liquid [OMIM][Tf2N]

In this study, solubility of pure CO₂ and H₂S and their mixture in [OMIM][Tf₂N] modeled applying CPA EoS. CPA combines the SRK equation with an advanced association term, which is similar to that of SAFT. From a practical point of view, the target in the CPA project was to develop a thermodynamic model capable of describing complex equilibria of mixtures containing polar/associating chemicals through a simple procedure with respect to the SAFT.

The AAD% for binary systems, including H₂S+ IL and CO₂+ IL are 6.81, 5.21 respectively. Moreover, AAD% equal to 13.89 was achieved for the ternary system.