氨基改性吸附剂在低CO2分压下吸附CO2的热力学研究

为了减少温室效应,应采取有效措施减少温室气体CO2的排放。氨基改性吸附剂是捕获烟道气中CO2的重要吸附材料。建立了描述氨基改性MCM-41吸附剂在低CO2压力下吸附等温线的平衡模型,并计算了吸附热力学参数。该模型基于Dual-site Langmuir模型,同时假设CO2吸附具有两种独立的吸附机理,分别是氨基基团的化学吸附和吸附剂表面的物理吸附,提出了一种基于未改性介孔材料吸附容量和比表面积计算改性材料的物理吸附量方法。结果表明,该模型能较好地拟合吸附等温线,计算得到的物理化学吸附热分别为-25.4kJ/mol和-41.9kJ/mol,总吸附热为-67.3kJ/mol,与实验数据一致,且氨基改性MCM-41-TEPA饱和吸附容量可达到7.79mmol/g。     

Operation Parameters on CO2-Foam process

Abstract

Reducing the mobility of CO₂ by means of generating in situ foam is an effective method for improving the oil recovery in CO₂ flooding processes. Implementation of the CO₂-foam technique typically involves the co-injection of CO₂ and surfactant solution into the porous medium. The surfactant molecules form bubble films that trap the flowing CO₂ molecules. The effectiveness of the CO₂-foam process is measured in terms of foam mobility. The mobility of CO₂-foam is affected by different operation parameters, such as pressure, temperature, foam quality, and brine concentration. However, surfactant type governs the overall efficiency of the CO₂-foam process. This paper presents the results of a series of experiments conducted to study the effect of various parameters on the CO₂-foam process. Bottle tests were conducted for four commercially available surfactants and among them, Chaser CD-1045 was found to be the most effective surfactant for CO₂-foam flow under reservoir conditions. It was observed that an increase in pressure from 1, 200 psi to 1, 500 psi leads to increase of the mobility of CO₂-foam, and an increase in temperature from 72 to 122°F reduces the mobility. Also, as the foam quality increases from 20 to 80%, the mobility decreases. It was observed that there was no significant effect on the mobility with an increase in brine concentration from 1 to 3 wt%.     

Influence of pressure and CO2 content on the asphaltene precipitation and oil recovery during CO2 flooding

During CO₂ flooding, the crude oil is treated with CO₂, and meanwhile it is displaced by CO₂. Based on the two processes, the influence of pressure and CO₂ content on the asphaltene precipitation and oil recovery efficiency are systematically investigated by indoor simulation experiment. With the increase of the pressure or CO₂ content during CO₂ treatment, the amount of asphaltene precipitation can be increased to a certain value. Correspondingly, the degrees of the changes of oil-water interface, the compositions of crude oil, and reservoir permeability are positively correlated with the amount of asphaltene precipitation. However, during the process, the oil recovery has an optimal value due to the combined action of asphaltene precipitation and the improvement of flow performance of the crude oil. These conclusions can provide a basis for high efficiency development of low permeability oil reservoirs by CO₂ flooding.     

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.     

Influence of H2S Content on CO2 Corrosion Behaviors of N80 Tubing Steel

Abstract

The corrosion behaviors of N80 steel in pure CO₂ and at different partial pressure ratios of CO₂/H₂S were tested by high-temperature and high-pressure autoclave. At 90°C, with the additional H₂S to pure CO₂, the surface corrosion condition improved greatly and the corrosion rates were lower than in pure CO₂ condition. With the increase of partial pressure ratio, the corrosion rate reached a peak value at pCO₂/pH₂S = 100 and then declined. The corrosion products of the samples in different conditions were analyzed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD) methods. The inner film is finer and denser than the outer scale.     

Economical Evaluation of CO2-EOR Projects in the Middle East

Abstract

Recently, there is a growing interest the in oil industry to utilize carbon dioxide (CO₂) to enhance oil production from mature reservoirs. Conversely, there is a rising global attention to reduce CO₂ emissions from burning fossil fuels due to environmental concerns. Synchronization between these two objectives is promising through CO₂ Capture and Storage (CCS) projects where CO₂ is captured from large emission sources and then storedin safe geological structures. Economical evaluation of CO₂-EOR projects is a crucial measure in order to ensure a project's viability.

In this study, an efficient model was developed to predict the economics of CO₂-EOR projects. The developed model consists of five modules that are linked together to allow for fast prediction of CO₂-EOR economics.

The model was used to predict the economics of a case study where CO₂-EOR application is considered for a Middle Eastern reservoir. Moreover, the case study was subjected to sensitivity analyses to evaluate the effects of several parameters on the various economical components of CO₂-EOR projects.     

Oil recovery and CO2 storage in CO2 flooding

In this study, the interfacial tension (IFT) of crude oil-carbon dioxide mixtures was measured to determine the minimum miscibility pressure. CO₂ flooding with sand packs, long cores, and heterogeneous cores was conducted to investigate the oil recovery and storage efficiency. The experiment results show that the interfacial tension decreases linearly with increasing pressure at two different pressure ranges. Under immiscible condition, the oil recovery and storage efficiency are increased by 30.1% and 52.4% when the injection pressure is increased from 13 to 22 MPa, and improved by 16.3% and 22.04% when the permeability is decreased from 270 to 10 mD, respectively. Under miscible condition, increase of injection pressure can only lead to much slower increase of oil recovery and storage efficiency, and permeability almost has no influence on oil recovery and storage efficiency. The oil recovery and storage efficiency can be remarkably reduced by heterogeneity. Water alternating CO₂ injection can improve the oil recovery and storage efficiency by 35.5% and 13.55%, respectively, compared with continuous injection.     

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.     

Catalytic cracking of isopropylbenzene over hybrid HZSM-12/M41S (M41S = MCM-41 or MCM-48) micro-mesoporous materials

The catalytic cracking of isopropylbenzene was investigaded over hybrid ZSM-12/MCM-41 and HZSM-12/MCM-48 micro-mesoporous materials, in order to verify the effect of the acid site of the accessibility of mesoporous channels combined with the acid sites into the zeolite. The hybrid materials were synthesized by the hydrothermal method using the template mechanism. The obtained materials were characterized by X-ray diffraction and BET isotherms using nitrogen adsorption-desorption at 77 K. The X-ray diffraction patterns presented characteristic peaks of the microporous and mesoporous phases. These analysis revealed the formation of ordered hexagonal MCM-41 or cubic MCM-48 mesoporous phases, associated with the ZSM-12 structure. In order to generate acid sites, the materials were ion exchanged with ammonium chloride solution. The calcined hybrid materials were tested as catalyst for cracking of isopropyl-benzene, using a fixed bed reactor at 450 ^oC and nitrogen gas. The catalytic tests showed that the HZSM-12/AlMCM-41 and HZSM-12/MCM-48 hybrid materials have potential for use in cracking reactions, bening more active than the zeolite or the M41S alone. The catalytic activities of the hybrid materials can be associated with a synergistic effect between the acid sites present on the zeolitic phase and the mesoporous phase. In order to verify how the structure of the hybrid materials may affect and control their catalytic performances, the results were compared with HZSM-12 physically mixed with MCM-41 and MCM-48.     

Screening of Oil Pools on Alaskan North Slope and Phase Behavior Study of Viscous Oil and CO2 System in Conjunction with CO2 Sequestration

Abstract

Carbon dioxide gas, a greenhouse gas (GHG), is released in the atmosphere by combustion of solid waste, wood, and fossil fuels for energy generation. Due to conspicuous absence of CO₂ sequestration studies for Alaska, the study of CO₂ sequestration options on North Slope has a very important role to play. The screening of the oil reservoirs to evaluate the technical feasibility with respect to their CO₂-EOR potential was performed by calculating the rank of the oil reservoirs with parametric approach. CMG-WinProp® simulator was used to predict phase behavior for CO₂ injection in viscous oil by tuning the equation-of-state.     

Experimental Investigation of Miscible CO2 Flooding

Abstract

Management of water alternating gas (WAG) injection projects requires making decisions regarding the WAG ratio, half-cycle-slug size, and ultimate solvent slug size. The impact of these decisions affects the capital cost and ultimate incremental oil recovery. Core flooding runs were conducted on 2 and 4 ft core samples. Injection scheme (continuous gas injection [CGI] vs. WAG), WAG ratio, and slug size were investigated. In addition, miscible WAG flooding as a secondary process was investigated and its efficiency was compared to the conventional tertiary miscible gas flooding. Miscible gas flooding at different miscible WAG parameters (WAG ratio and slug size) indicate that 1:2 WAG ratio at 0.2 PV slug size is the best combination yielding the highest recovery and tertiary recovery factors. Miscible WAG flooding as a secondary process indicated a higher ultimate recovery compared to the conventional tertiary WAG flooding. However, a larger amount of gas injection is consumed particularly in the early stages of the injection process. Miscible CGI mode conducted using n-Decane as oleic phase appears to have better performance than miscible WAG injection in term of recovery. When light Arab crude oil was used as oleic phase, higher recovery was obtained for miscible WAG flooding. The reversal trend seen in is believed to be due to the presence of crude oil, which alters the rock wettability toward an oil-wet condition, preventing the water blockage during the WAG process.     

The Impact of Pore Pressure on CO2-Methane Displacement

Abstract

The intricate behavior of carbon dioxide at supercritical conditions is considered to influence the ultimate recovery of additional hydrocarbon reserves through the application of CO₂-enhanced gas recovery projects. Mixing in such a system is a diffusion-like process, which definitely depends on the physical properties of the displacing and displaced phases and the heterogeneity of the medium. The authors' aim was to experimentally investigate the consequence of pore pressure on the recovery efficiency and multiphase gas flow in a reservoirs porous medium. The displacement tests were carried out at five different pore pressures ranging from 10.34 to 40.68 MPa, temperature of 433.15 K, and displacement rate of 10 cm/hr. Results determined that improved recovery by approximately 40% can be obtained by applying the highest pore pressure in comparison with the test conducted at low pore pressure.     

Risk Assessment of CO2 Geological Storage and the Calculation of Storage Capacity

Abstract

Greenhouse gas emission is becoming serious, and attention has been paid to CO₂ geological storage which will not only help to achieve CO₂ reduction in air but improve oil recovery. This article provides risk assessment of CO₂ geological storage and calculation of storage capacity, which was validated in an oilfield.     

The Effects of Miscible CO2 Injection on Oil Biomarker Parameters

The purpose of this research was to study the effect of CO₂ injection on the geochemistry of crude oil in order to determine the probability of using geochemical parameters for monitoring CO₂ injection. In this process, four oil samples from different offshore oil fields were collected, synthetic steady state oil reservoir (porous media) were made by slim tube apparatus, then CO₂ injection process was done in different pressures. Various geochemical analyses were also carried out on the injected oil before and after the injection. The results show that the bulky changes on oil sample by CO₂ injection. CO₂ injection is more likely to precipitate complex and large molecules such as asphaltenes-resins and also large normal alkanes. In this case, the percentage of aromatic molecules was increased during injection. In general view on chromatograms, the height and abundance of all saturated compound peaks after CO₂ injection were significantly decreased. However, biomarker analysis shows that CO₂ injection has a tendency to change source and maturity biomarker parameters.     

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%。     

Post-combustion of mazut with CO2 capture using aspen hysys

There is a wide range of resources for CO₂ emissions. The net amount of CO₂ emissions in the cement industry due to the consumption of fossil fuels and the chemical processes of cement production under heating raw materials is reported to be in the range of 15–25%; this industry, among all the industries and after the power plants and refineries, is the largest CO₂ gas producer throughout the world. Using CO₂ capture and storage (CCS), it can reduce greenhouse gas emissions in a short time. In this study, the technical feasibility study of recycling CO₂ in Abyek Cement Company, with a cement production capacity of about 12,500 tons per day in two production lines, has been studied as one of the largest cement industries throughout the world. Fuel oil (Mazut) is used as the primary fuel for furnaces in this industry. Affected by combustion, the emissions emitted from the five-stage preheater contain 5/24% vol% of CO₂, 7.6% H₂O, 4.8% vol% of O₂, and 63.1% N₂.     

Influence of injection pressure and injection volume of CO2 on asphaltene deposition

To further improve the oil displacement effect by CO₂ flooding, the trends and conditions of asphaltene deposition under different injection pressures and injection volumes of CO₂ were studied by SDS solid phase deposition testing system, high temperature and high pressure microscope, and P-X phase diagram. When the mole fraction of CO₂ in crude oil increases to a certain value, asphaltene deposition appears. The lower the pressure, the lower the mole fraction of CO₂ in crude oil causing the asphaltene deposition there is. After the onset of asphaltene deposition, the degree of deposition increases with an increase in pressure. The amount of the deposited asphaltene under miscible displacement is the highest, under near-miscible displacement is the second highest, and under immiscible displacement is the lowest. When the dissolution of CO₂ in crude oil reaches the saturation point, the asphaltene deposition becomes slow. Besides, it is feasible to prevent or reduce the asphaltene deposition by adjusting the thermodynamic parameters according to the phase behaviors of the CO₂-crude oil system. The experimental results can provide theoretical basis for optimization design of the parameters of CO₂ flooding.     

Mass Transfer of CO2 Into Water and Surfactant Solutions

Abstract

The mass transfer of CO₂ into water and aqueous solutions of sodium dodecyl sulphate (SDS) is experimentally studied using a pressure, volume, temperature (PVT) cell at different initial pressures and a constant temperature (T = 25°C). It is observed that the transfer rate is initially much larger than expected from a diffusion process alone. The model equations describing the experiments are based on Fick's Law and Henry's Law. The experiments are interpreted in terms of two effective diffusion coefficients—one for the early-stages of the experiments and the other one for the later stages. The results show that at the early stages, the effective diffusion coefficients are one order of magnitude larger than the molecular diffusivity of CO₂ in water. Nevertheless, in the later stages the extracted diffusion coefficients are close to literature values. It is asserted that at the early stages, density-driven natural convection enhances the mass transfer. A similar mass transfer enhancement was observed for the mass transfer between a gaseous CO₂ rich phase with an oil (n-decane) phase. It is also found that at the experimental conditions studied addition of pure SDS does not have a significant effect on the mass transfer rate of CO₂ in water.     

CH4/N2在活性炭上吸附性能的研究

变压吸附是分离油田伴生气中N_2和CH_4的可行性方法,采用质量法测定了N_2、CH_4在活性炭WHXR-LB20上的吸附等温线,分离系数为2.87,满足工业应用要求且再生效果好;同时测定了油田伴生气中C_2H_6、C_3H_8,n-C_4H_(10)等对WHXR-LB20的影响,结果表明,C_2H_6、C_3H_8在WHXR-LB20上再生效果很好,而n-C_4H_(10)在WHXR-LB20上有积累,该积累量使N_2和CH_4在WHXR-LB20上的饱和吸附量降低。