碳中和目标下石油与化学工业绿色低碳发展路径分析

石油与化工行业是高耗能、高污染、高碳排的“三高”行业,在碳达峰、碳中和的目标下,促进石油与化学工业和生态环境的协调可持续发展成为亟需解决的热点问题。本文从国家层面和企业层面总结典型国家及其石油与化学工业面对“双碳”目标采取的措施行动,对乙烯、成品油等石油与化工产品不同生产路径的能耗及二氧化碳排放情况进行比较分析,概述中国的区域能源分布特点、各省份的石油与化学工业产值及二氧化碳排放情况,明确提出作为碳排放的大户,石油与化工行业有可能在“十四五”期间被纳入全国碳市场。文中指出石油与化工行业必须在借鉴发达国家先进碳减排经验的基础上,立足本国国情,综合考虑本国的能源分布情况和石油与化工产品生产的能耗及二氧化碳排放情况,建构清洁低碳、节能高效的工艺流程体系,促进石油与化学工业的高质量发展。石油与化学工业二氧化碳减排的核心是区域能源结构的调整和工艺流程的优化,并以此为前提建设绿色集成化工园区,辅之以可再生能源如风能、太阳能等的综合利用,研发碳捕集、利用与封存技术进行碳固定。还提出值得注意的是,由于其他温室气体如甲烷等的减排已经提上日程,我国也应加快相关技术储备。     

Interfacial tension and density measurement of the system corn germ oil – carbon dioxide at low temperatures

In this article, the physical properties of corn germ oil at high pressures of up to 30 MPa and at low temperatures from ?10 °C to 22 °C are presented. We measured the interfacial tension of the commercially available corn germ oil Mazola® and of unrefined corn germ oil in contact with carbon dioxide, as well as the density of carbon dioxide‐saturated corn germ oil. The interfacial tension of refined and unrefined corn germ oil in contact with gaseous carbon dioxide at temperatures above ?10 °C depends on time, while at higher pressures the equilibrium value of the interfacial tension is reached immediately after the formation of the drops or bubbles. The interfacial tension of unrefined corn germ oil in contact with carbon dioxide is higher than the interfacial tension of refined corn germ oil. This fact is explained in this article. The interfacial tension of refined and of unrefined corn germ oil in contact with carbon dioxide decrease with rising pressure and can be described as a function of the carbon dioxide density for the examined temperature range. The density of carbon dioxide‐saturated corn germ oil is linearly dependent on pressure, with a high slope if carbon dioxide is gaseous and with a low slope if carbon dioxide is liquid.     

Measurement and modelling of the interfacial tension of triglyceride mixtures in contact with dense gases

The interfacial tension of various triglyceride mixtures in contact with carbon dioxide is compared. The interfacial tension of these triglyceride mixtures is similar. The interfacial tension in contact with carbon dioxide and nitrogen decreases with increasing pressure. Concerning the interfacial tension in contact with carbon dioxide, the interfacial tension increases at higher pressure with rising temperature. The interfacial tension of triglyceride mixtures and of many other liquids in contact with carbon dioxide can be described as a function of the carbon dioxide density.The modelling of the interfacial tension of triglycerides in contact with carbon dioxide or nitrogen using the density gradient theory (Macromolecules 14 (1981) 361) and the Sanchez-Lacombe equation of state (J. Phys. Chem. 80 (1976a/b) 2352 and 2568) is successful if one parameter for nitrogen and two parameters for carbon dioxide are employed. Nevertheless, an appropriate equation of state must be utilized for modelling the interfacial tension of a system. For complex systems, e.g. for triglyceride mixtures, it is indispensable to check the equation of state by means of experimental equilibrium data (e.g. density, volume, or mole fraction).     

Interfacial tensions of ethanol-carbon dioxide and ethanol-nitrogen. Dependence of the interfacial tension on the fluid density—prerequisites and physical reasoning

Interfacial tensions in the systems ethanol-carbon dioxide and ethanol-nitrogen are measured. In both systems the interfacial tension decreases with increasing pressure. The interfacial tension in the system ethanol-nitrogen decreases with increasing temperature. In contrast to this, in the system ethanol-carbon dioxide at high pressures an isobaric increase in temperature provokes an increase in interfacial tension. In the system ethanol-carbon dioxide at elevated pressure the density of the carbon dioxide phase is the only influence parameter concerning the interfacial tension. This phenomena can be observed for various other systems with one near critical or supercritical component and a high solubility of this component in the liquid phase and at temperatures above the critical temperature of the gas. For this fact a physical reasoning, which is based on a new concept of partial interfacial tensions, is given. Furthermore, it is stated that the interfacial tension of fatty systems in contact with carbon dioxide has approximately the same dependence on the reduced density (ρ_r=ρ/ρ_c) of the supercritical phase as the interfacial tension of the same systems in contact with ethane. The knowledge of this fact can help to avoid experiments with ethane, which is flammable.     

Interfacial tension of edible oils in supercritical carbon dioxide

Interfacial properties essentially influence fluid‐liquid separation processes. Thereby, interfacial tension is an important parameter that is associated with mass transfer and mutual solubility of participating compounds. For this reason, interfacial tension of a virgin olive oil with a known amount of free fatty acids was measured in supercritical carbon dioxide atmosphere at 313 K and 353 K and pressures up to 40 MPa. The obtained values were compared to different oils some of which contain appreciable amounts of volatile components. In general, interfacial tension behaviour is dominated by the effect of pressure, whereas differences between oil compositions are secondary. Besides mutual solubility interfacial tension is supposed to be associated with the compressibility of the dense fluid phase. For predicting mass transfer area some general comments on the colloidal behaviour of systems containing supercritical CO₂ are made     

Evaluation of aqueous chemical systems for heavy oil recovery processes

The effects of temperature and certain chemical additives on the interfacial tension behaviour of a heavy oil (from Lloydminster, Alberta) with petroleum sulphonate surfactant solutions and alkaline solutions are investigated experimentally. Corresponding data for a light Canadian oil are included for comparison purposes. It is concluded that alkaline solutions are effective only in the recovery of heavy oils, while petroleum sulphonate surfactants are effective only for light oils. The effect of temperature on the minimum attainable interfacial tension is marginal in all cases. However, for alkaline solutions, temperature has a significant effect on the rate of rise of interfacial tension with time after attainment of the minimum value.     

Process intensification in vapor–liquid mass transfer: The state-of-the-art

The concept of process intensification(PI) has absorbed diverse definitions and stays true to the mission—"do more with less", which is an approach purposed by chemical engineers to solve the global energy environment problems. To date, the focus of PI has been on processes mainly involving vapor/liquid systems. Based on the fundamental principles of vapor–liquid mass transfer process like distillation and absorption, there are three strategies to intensify interphase mass transfer: enhancing the overall driving force, improving the mass transfer coefficient and enlarging the vapor–liquid interfacial area. More specifically, this article herein provides an overview of various technologies to strengthen the vapor–liquid mass transfer, including application of external fields, addition of third substances, micro-chemical technology and usage of solid foam, with the objective to contribute to the future developments and potential applications of PI in scientific research and industrial sectors.     

超临界二氧化碳萃取在石油工业中的应用探究

随着化工工程的发展,超临界技术得以发展并被广泛的应用到了各个领域之中,尤其是石油化工行业。二氧化碳、乙醇、丙烯等气体都可作为流体萃取的溶剂,而在石油工业中,二氧化碳萃取具有独特的优势。对以二氧化碳为溶剂的超临界流体萃取技术在石油工业中的应用情况进行分析与探究。     

Interfacial tension measurements between α-tocopherol and carbon dioxide at high pressures

The interfacial tension of the binary system α-tocopherol/carbon dioxide was measured using the pendant drop method in the pressure range between 10 and 37 MPa at nine different temperatures: 313, 333, 343, 353, 363, 373, 383, 393, and 402 K. At every interfacial tension measurement, densities of both the liquid and the supercritical gas phase were also determined as the knowledge of these values is essential for calculating interfacial tension from the shape and size of drops. The interfacial tension decrease with rising pressure at a constant temperature and increases with increasing temperature at a constant pressure. The interfacial tension was found to be mainly a function of the mutual solubility of the two system components and of the density of pure carbon dioxide.     

Interfacial phenomena of aqueous systems in dense carbon dioxide

The interfacial tensions of initially pure liquids (water, ethanol and corn germ oil) and water–ethanol mixtures against dense carbon dioxide as well as against dense carbon dioxide mixtures with water and ethanol at 313 K and at pressures up to 27 MPa are measured. The wettabilities of ethanol and water on PTFE, glass and steel surrounded by pressurized carbon dioxide are also included in this paper. The interfacial tension results reported are the static values as well as the values which are measured during mass transfer.Generally, it is known that the interfacial tension depends on the composition of the coexisting phases. However, up to now, it is not clear whether only the composition of the interface does have an influence on the interfacial tension or if the composition of the bulk phase also affects this property. The detail discussion on this issue can be found in this paper. In this regard, the estimated pressure difference over the meniscus of a water drop with a diameter of 5 mm is reported.During mass transfer some interesting but scarcely reported drop phenomena such as drop kicking, upwards motion of the continuous phase around the drop, rising bubbles and intense mixing in the drop phase are observed. They are closely related to the interfacial turbulence, free convection, diffusion and stranding of the carbon dioxide molecules.The contact angle of ethanol and water drop over a pressure range of 27 MPa on PTFE, stainless steel and glass surfaces in the presence of dense carbon dioxide are included.     

Studies on petroleum sulphonates: Correlation between their chemical structure and the oil—Water emulsion stability characteristics

The average molecular weight distribution, emulsion stability of oil—water emulsion, the chemical structure of the hydrocarbon portions of petroleum sulphonates, and surface active properties have been determined with a view to establishing a correlation between the chemical structure of petroleum sulphonates and their emulsion stability characteristics. It has been found that the emulsion stability of oil—water emulsions imparted by sodium petroleum sulphonates depends on: (i) average molecular weight of sodium petroleum sulphonates; (ii) their molecular weight distribution; (iii) oil—water interfacial tension; (iv) hydrophile—lipophile balance values. The structural parameters which predominantly effect the emulsion stability are the ratio of the percentage distribution of carbon atoms in paraffin side chains to the percentage distribution of carbon atoms, the aromatic rings (C_P/C_A), the relative proportions of long chain mono-aromatics and the orientation of the sulphonate group relative to the paraffin alkyl chains in the molecules.     

表(界)面张力测定方法的研究进展

综述了表(界)面张力的测量原理和方法;详细分析了适合高温、高压、不同气氛影响以及动态表面张力的测量方法、表面张力仪器建立时需要注意的问题和影响测量结果准确度的因素以及其发展趋势;指出了在煤液化工艺和石油加氢工艺中考察气氛对表面张力影响时最好采用最大气泡法和悬滴法。     

Interfacial tension measurements and modelling of (carbon dioxide + n-alkane) and (carbon dioxide + water) binary mixtures at elevated pressures and temperatures

Supercritical carbon dioxide (CO₂) is often used as a process fluid for enhanced oil recovery. The storage of carbon dioxide in underground formations is a potential way of mitigating climate change during a transition period to more sustainable energy sources. Combining injection with subsequent trapping of the non-wetting supercritical carbon dioxide phase in the pores of a depleted reservoir is a promising scheme for allowing the continued use of fossil fuels with minimal environmental consequences. The design of such processes is ultimately linked to the confined behaviour of the fluids in question at reservoir conditions, which is largely controlled by interfacial forces. Measurements of the relevant interfacial tensions for systems containing alkanes, carbon dioxide and water are currently limited and inconsistent while models usually fail to capture the pressure dependence of the interfacial tension. In this work, a density functional theory based on the SAFT-VR equation of state was used to predict the interfacial tension of (H₂O + CO₂ + n-alkane) binary systems over wide ranges of temperature and pressure. The comparison with a new set of reported experimental data of three (n-alkane + CO₂) systems at pressures up to the critical points, as well as with the (H₂O + CO₂) system at pressures up to 60 MPa, for a temperature range of (298-443) K, is discussed.     

石油磺酸盐合成技术进展

石油磺酸盐是一种以石油馏分为原料的合成阴离子表面活性剂,主要用作驱油剂,具有界面活性强,与原油配伍性好以及水溶性好等优点,一直受到广泛重视。石油磺酸盐因原料油组分及分子结构复杂,结构和性能差异大,使得三次采油应用的表面活性剂应满足低界面张力和低吸附量才能达到提高采收率的目的,故开发具有高界面活性和低吸附损失的石油磺酸盐具有重要意义。     

Influence of oxide dopants on the wetting of doped graphite by cryolite/alumina melts

In the aluminium smelting industry, the wetting of the electrolyte on the carbon anode is an important property associated with the onset of the anode effect. The effect of dopants on the wettability of the anode was investigated in this study. The carbon material selected was graphite. The composition of the cryolite/alumina melts varied between a very low alumina content and 6 wt.% alumina. The sessile drop approach was adopted to measure the contact angle between the melt and the graphite at 1030 °C. The influence of oxide dopants, chromium III oxide and alumina, in the graphite on the wettability was studied. The wettability on a pure graphite surface depends to a small extent on the liquid surface tension but mostly on the liquid–solid interfacial tension that varies with the concentration of alumina in the liquid. The wettability on an oxide doped graphite surface depends on the dissolution of the oxide in the melt that changes the liquid–solid interfacial tension. The alumina dissolution has a double effect on the liquid–solid interfacial tension: the chemical reaction as well as the change in the oxy-anions concentration at the interface decrease the interfacial tension.     

Directed Valve Trays

1 INTRODUCTIONValve tray columns are one of the most important mass transfer equipment for vapor-liquidoperations and are widely used in the petroleum and chemical industries.They have good op-erating performances with floatable parts on the trays.There are various of valve trays,andType V1(F1-type)valve trays are used very common in industry.Though Type V1 valvetrays have a number of advantages,it has been found in recent years that there are also cer-tain drawbacks,for example,higher hydraulic gradient on the tray,more backmixing of     

Determination of dynamic contact angles in solid–liquid–liquid systems using the Wilhelmy plate apparatus

The purpose of this work was to carry out a systematic study of the effects of brine composition and rock mineralogy on rock-oil-brine interactions taking place in petroleum reservoirs. These terms are generally lumped into a single term called wettability in petroleum engineering. The extent of wetting of the rock surface by water or oil depends on the dynamic contact angles measured in such a mode as to enable movements of the three-phase contact line. The Wilhelmy plate technique has been used in this study to measure adhesion tension (which is the product of interfacial tension and cosine of the contact angle) at the solid-liquid interface. The water-advancing and water-receding contact angles have been calculated from the adhesion tensions by making independent measurements of the liquid-liquid interfacial tensions using a du Noüy ring tensiometer. The water-advancing and receding angles have been measured in this study for pure hydrocarbons against synthetic brines of different concentrations. Polished surfaces of glass slides and dolomite have been used to simulate the reservoir rock surfaces. A nonionic surfactant (ethoxy alcohol), which is being used in Yates reservoir in West Texas for enhancing oil recovery, was used to quantify its wettability effects. The results of the systematic experimental investigation of the effects of practical variables on wettability are presented. It is found that interactions between surface-active agents at the interface of two liquids have an effect on wettability alteration. The composition and concentrations of different organic and inorganic chemical species have a major effect in making a reservoir oil-wet or water-wet.     

离子液体介质中绿色催化研究新进展

综述了近年来离子液体在超临界CO2、生物催化、不对称催化3个方面的应用进展,阐明离子液体具有独特的物理化学性质,在许多化工过程中能代替传统的有机溶剂,真正实现环境友好及“绿色催化”,展望了离子液体的发展方向。     

超临界CO_2流体特性及其在材料加工中的应用

介绍了超临界CO2的溶解度、密度、表面张力、扩散能力等特性;并着重阐述了超临界CO2在材料清洗、染色、涂料、粒子制备等材料加工方面的应用。     

超临界二氧化碳和醇类体系的相平衡计算

应用Peng-Robinson(P-R)状态方程对超临界CO2系统进行了相平衡模拟。对超临界CO2和醇类二元系统进行了汽液相平衡计算,结果表明,P-R状态方程模拟高压下CO2系统的相平衡具有较高的精度。