2002—Emergence of the Gas-to-Liquids Industry:a Review of Global GTL Developments

This paper reviews the status of the gas-to-liquids (GTL) industry-including current commercial plants, announced projects and the technologies that are likely to be implemented in these future projects. Today, only 35,000 B/D of GTL products (0.1% of market) are manufactured from commercial gas-based plants. Advances in technology have lowered the cost of plants to the point where GTL plants can be profitable at crude oil prices of ＄16/B. The advanced stage of development of several proposed GTL projects and attractive integrated economics, for both the gas field and plant, show that GTL can be a significant alternative for monetizing natural gas in the 21st century. GTL technologies includes more than Fischer-Tropsch technology and extends to other liquid fuels, especially in the oxygenate family (methanol, dimethyl ether, etc.).

Fine quantitative characterization of high-H2S gas reservoirs under the influence of liquid sulfur deposition and adsorption

In order to clarify the influence of liquid sulfur deposition and adsorption to high-H2S gas reservoirs,three types of natural cores with typical carbonate pore structures were selected for high-temperature and high-pressure core displacement experiments.Fine quantitative characterization of the cores in three steady states(original,after sulfur injection,and after gas flooding)was carried out using the nuclear magnetic resonance(NMR)transverse relaxation time spectrum and imaging,X-ray computer tomography(CT)of full-diameter cores,basic physical property testing,and field emission scanning electron microscopy imaging.The loss of pore volume caused by sulfur deposition and adsorption mainly comes from the medium and large pores with sizes bigger than 1000μm.Liquid sulfur has a stronger adsorption and deposition ability in smaller pore spaces,and causes greater damage to reservoirs with poor original pore structures.The pore structure of the three types of carbonate reservoirs shows multiple fractal characteristics.The worse the pore structure,the greater the change of internal pore distribution caused by liquid sulfur deposition and adsorption,and the stronger the heterogeneity.Liquid sulfur deposition and adsorption change the pore size distribution,pore connectivity,and heterogeneity of the rock,which further changes the physical properties of the reservoir.After sulfur injection and gas flooding,the permeability of TypeⅠreservoirs with good physical properties decreased by 16%,and that of TypesⅡandⅢreservoirs with poor physical properties decreased by 90%or more,suggesting an extremely high damage.This indicates that the worse the initial physical properties,the greater the damage of liquid sulfur deposition and adsorption.Liquid sulfur is adsorbed and deposited in different types of pore space in the forms of flocculence,cobweb,or retinitis,causing different changes in the pore structure and physical property of the reservoir.

Analysis of Maximum Liquid Carrying Capacity Based on Conventional Tubing Plunger Gas Lift

China’s unconventional gas fields have a large number of low-productivity and low-efficiency wells, many of whichare located in remote and environmentally harsh mountainous areas. To address the long-term stable productionof these gas wells, plunger-lift technology plays an important role. In order to fully understand and accurately graspthe drainage and gas production mechanisms of plunger-lift, a mechanical model of plunger-liquid column uplift inthe plunger-lift process was established, focusing on conventional plunger-lift systems and representative wellboreconfigurations in the Linxing region. The operating casing pressure of the plunger-lift process and the calculationmethod for the maximum daily fluid production rate based on the work regime with the highest fluid recovery ratewere determined. For the first time, the critical flow rate method was proposed as a constraint for the maximumliquid-carrying capacity of the plunger-lift, and liquid-carrying capacity charts for conventional plunger-lift withdifferent casing sizes were developed. The results showed that for 23/8 casing plunger-lift, with a well depth ofshallower than 808 m, the maximum drainage rate was 33 m3/d;for 27/8 casing plunger-lift, with a well depth ofshallower than 742 m, the maximum drainage rate was 50.15 m3/d;for 31/2 casing plunger-lift, with a well depthof shallower than 560 m, the maximum drainage rate was 75.14 m3/d. This research provides a foundation for thescientific selection of plunger-lift technology and serves as a decision-making reference for developing reasonableplunger-lift work regimes.

The Future of Gas to Liquids as a Gas Monetisation Option

The paper introduces gas to liquids (GTL) as a monetising option from a technology, marketing and project perspective. GTL is complementary to LNG and pipelines. At the same time, using natural gas as a source for fuels in the form of GTL helps countries around the world to diversify their energy supplies. Furthermore, gas-based products are inherently cleaner than oil products. Shell's proprietary GTL technology or SMDS (Shell Middle Distillates Synthesis), is discussed in some detail. The paper also covers the challenges for successful implementation of GTL projects and why Shell is well positioned to take a lead in the industry on the basis of its long standing and broad experience in GTL research, plant operations, marketing and excellent track record in mega projects in the last thirty years. Shell's commitment to GTL is best demonstrated by the recent signing of a Heads of Agreement with Qatar Petroleum for the construction of the world's largest GTL plant. A key success factor is Shell's experience with marketing quantities of high quality GTL products from its 12,500 barrels per day plant at Bintulu, Malaysia since 1993. Further marketing opportunities will arise when new GTL capacity comes on-stream in the middle east when more quantities will become available to bulk users. Amongst the most interesting market will be automotive transportation, where clean GTL fuels can be positioned as an 'alternative fuel beyond oil' providing energy security to host countries. Shell is actively engaging with a number of regulators, automotive companies and governments worldwide including China, to demonstrate the performance of GTL and its cost effectiveness in reducing local emissions. An added benefit is that GTL can use existing infrastructure and requires no investment. Finally, the paper briefly discusses the coal to liquids (CTL) process as an alternative route to produce high quality GTL products and the key issues relating to the process.

GTL or LNG:Which is the best way to monetize "stranded" natural gas?

A large portion of world＇s natural gas reserves are ＂stranded＂ resources, the drive to monetize these resources leads to the development of gas-to-liquids （GTL） and liquefied natural gas （LNG） technologies. LNG has the advantage of having been developed for the past 40 years and having an excellent safety record. GTL on the other hand is another option with substantial benefits, but its development stage and commercial viability are far behind LNG. This paper presents a techno-economic comparison of GTL with LNG, including technical development, plant efficiency, market potential for the products, and capital cost for the infrastructure. The aim is to give an overall view on both LNG and GTL and provide a perspective on the profitability of these two technologies.

A Novel Process for Natural Gas Liquids Recovery from Oil Field Associated Gas with Liquefied Natural Gas Cryogenic Energy Utilization

A novel process to recovery natural gas liquids from oil field associated gas with liquefied natural gas (LNG)cryogenic energy utilization is proposed.Compared to the current electric refrigeration process,the proposed process uses the cryogenic energy of LNG and saves 62.6%of electricity.The proposed process recovers ethane, liquid petroleum gas(propane and butane)and heavier hydrocarbons,with total recovery rate of natural gas liquids up to 96.8%.In this paper,exergy analysis and the energy utilization diagram method(EUD)are used to assess the new process and identify the key operation units with large exergy loss.The results show that exergy efficiency of the new process is 44.3%.Compared to the electric refrigeration process,exergy efficiency of the new process is improved by 16%.The proposed process has been applied and implemented in a conceptual design scheme of the cryogenic energy utilization for a 300 million tons/yr LNG receiving terminal in a northern Chinese harbor.

Distribution performance of gas–liquid mixture in the shell side of spiral-wound heat exchangers

The non-uniformity of gas–liquid mixture is a critical issue which leads to the heat transfer deterioration of spiralwound heat exchangers(SWHEs).Two-phase mass flow rate and the content of gas are important parameters as well as structural parameters which have prominent influences on flow distribution uniformity of SWHE shell side.In order to investigate the influences of these parameters,an experimental test system was built using water and air as mediums and a novel distributor named"tubes distributor"was designed.The effects of mass flow rate and the content of gas on two-phase distribution performance were analyzed,where the mass flow rate ranged from 28.4 to 171.9 kg·h-1 and the content of gas changed from 0.2 to 0.8,respectively.The results showed that the mixture mass flow rate considerably influenced the liquid distribution than that of gas phase and the larger mass flow rate exhibited the better distribution uniformity of two-phase flow.It was also found that the tubes distributor had the better two-phase uniformity when the content of gas was around 0.4.Tube diameter played an important role in the distribution of gas phase and slit width was more significant for the uniformity of liquid phase.

Numerical investigation on flow process of liquid metals in melt delivery nozzle during gas atomization process for fine metal powder production

Based on volume of fluid(VoF)interface capturing method and shear-stress transport(SST)k-ω turbulence model,numerical simulation was performed to reveal the flow mechanism of metal melts in melt delivery nozzle(MDN)during gas atomization(GA)process.The experimental validation indicated that the numerical models could give a reasonable prediction on the melt flow process in the MDN.With the decrease of the MDN inner-diameter,the melt flow resistance increased for both molten aluminum and iron,especially achieving an order of 10^(2) kPa in the case of the MDN inner-diameter≤1 mm.Based on the conventional GA process,the positive pressure was imposed on the viscous aluminum alloy melt to overcome its flow resistance in the MDN,thus producing powders under different MDN inner-diameters.When the MDN inner-diameter was reduced from 4 to 2 mm,the yield of fine powder(<150μm)soared from 54.7%to 94.2%.The surface quality of powders has also been improved when using a smaller inner-diameter MDN.

Contribution of tuned liquid column gas dampers to the performance of offshore wind turbines under wind, wave, and seismic excitations

The main intention of the present study is to reduce wind, wave, and seismic induced vibrations of jacket- type offshore wind turbines （JOWTs） through a newly developed vibration absorber, called tuned liquid column gas damper （TLCGD）. Using a Simulink-based model, an analytical model is developed to simulate global behavior of JOWTs under different dynamic excitations. The study is followed by a parametric study to explore efficiency of the TLCGD in terms of nacelle acceleration reduction under wind, wave, and earthquake loads. Study results indicate that optimum frequency of the TLCGD is rather insensitive to excitation type. In addition, while the gain in vibration control from TLCGDs with higher mass ratios is generally more pronounced, heavy TLCGDs are more sensitive to their tuned frequency such that ill-regulated TLCGD with high mass ratio can lead to destructive results. It is revealed that a well regulated TLCGD has noticeable contribution to the dynamic response of the JOWT under any excitation.

Gas–liquid flow mass transfer in a T-shape microreactor stimulated with 1.7 MHz ultrasound waves

This paper describes the application of ultrasound waves on hydrodynamics and mass transfer characteristics in the gas–liquid flow in a T-shape microreactor with a diameter of 800 μm. A 1.7 MHz piezoelectric transducer(PZT) was employed to induce the vibration in this microreactor. Liquid side volumetric mass transfer coefficients were measured by physical and chemical methods of CO_2 absorption into water and Na OH solution. The approach of absorption of CO_2 into a 1 mol·L^(-1) Na OH solution was used for analysis of interfacial areas. With the help of a photography system, the fluid flow patterns inside the microreactor were analyzed. The effects of superficial liquid velocity, initial concentration of Na OH, superficial CO_2 gas velocity and length of microreactor on the mass transfer rate were investigated. The comparison between sonicated and plain microreactors(microreactor with and without ultrasound) shows that the ultrasound wave irradiation has a significant effect on kLa and interfacial area at various operational conditions. For the microreactor length of 12 cm, ultrasound waves improved kLa and interfacial area about 21% and 22%, respectively. From this study, it can be concluded that ultrasound wave irradiation in microreactor has a great effect on the mass transfer rate. This study suggests a new enhancement technique to establish high interfacial area and kLa in microreactors.

Numerical Simulation and Experimental Study on the Performance of Gas/liquid Spiral Separator

The gas/liquid spiral separator, a key component in the compressed air system, was used to remove liquid and oil from gas stream by centrifugal and gravitational forces. To optimize the design of the separator,the relationship between the performance and structural parameters of separators is studied. Computational fluid dynamics (CFD) method is employed to simulate the flow fields and calculate the pressure drop and separation efficiency of air-liquid spiral separators with different structural parameters. The RSM (Reynolds stress model)turbulence model is used to analyze the highly swirling flow fields while the stochastic trajectory model is used to simulate the traces of liquid droplets in the flow field. A simplified calculation formula of pressure drop in spiral structures is obtained by modifying Darcy's equation and verified by experiment.

Methane dehydroaromatization over Mo-modified H-MFI for gas to liquid catalysts

For direct gas to liquid（GTL）,a novel process producing energy sources for methane dehydroaromatization is needed.Supporting MoO3 on H-MFI zeolite shows the high catalytic capacity and a selective activity for dehydroaromatization of methane to benzene at 973 K in a fixed bed reactor.On the other hand,deactivation by coke on the active sites in all the catalysts is formed during the reaction.H2 co-feed suppressed the deactivation,which is probably due to the decrease in coking amount.Mo K-edge X-ray absorption fine structure（XAFS） results showed the formation of dispersed Mo2C species with low crystallinity after dehydroaromatization.Mo LIII-edge XANES（X-ray absorption near-edge structure） indicated the formation of active Mo species including Mo2C and Mo-oxycarbide（MoOxCy）,where the redox state should be independent in the absence/presence of H2.It is concluded that Mo-oxycarbide species act as highly active species,and their stability affected the durable activity in the presence of H2.

A liquid loading prediction method of gas pipeline based on machine learning

The liquid loading is one of the most frequently encountered phenomena in the transportation of gas pipeline,reducing the transmission efficiency and threatening the flow assurance.However,most of the traditional mechanism models are semi-empirical models,and have to be resolved under different working conditions with complex calculation process.The development of big data technology and artificial intelligence provides the possibility to establish data-driven models.This paper aims to establish a liquid loading prediction model for natural gas pipeline with high generalization ability based on machine learning.First,according to the characteristics of actual gas pipeline,a variety of reasonable combinations of working conditions such as different gas velocity,pipe diameters,water contents and outlet pressures were set,and multiple undulating pipeline topography with different elevation differences was established.Then a large number of simulations were performed by simulator OLGA to obtain the data required for machine learning.After data preprocessing,six supervised learning algorithms,including support vector machine(SVM),decision tree(DT),random forest(RF),artificial neural network(ANN),plain Bayesian classification(NBC),and K nearest neighbor algorithm(KNN),were compared to evaluate the performance of liquid loading prediction.Finally,the RF and KNN with better performance were selected for parameter tuning and then used to the actual pipeline for liquid loading location prediction.Compared with OLGA simulation,the established data-driven model not only improves calculation efficiency and reduces workload,but also can provide technical support for gas pipeline flow assurance.

Directional solidification casting technology of heavy-duty gas turbine blade with liquid metal cooling(LMC) process

In this work, some important factors such as ceramic shell strength, heat preservation temperature, standing time and withdrawal rate, which influence the formability of directionally solidified large-size blades of heavy-duty gas turbine with the liquid metal cooling(LMC) process, were studied through the method of microstructure analysis combining. The results show that the ceramic shell with medium strength(the high temperature flexural strength is 8 MPa, the flexural strength after thermal shock resistance is 12 MPa and the residual flexural strength is 20 MPa) can prevent the rupture and runout of the blade. The appropriate temperature(1,520 ℃ for upper region and 1,500 ℃ for lower region) of the heating furnace can eliminate the wide-angle grain boundary, the deviation of grain and the run-out caused by the shell crack. The holding time after pouring(3-5 min) can promote the growth of competitive grains and avoid a great deviation of columnar grains along the crystal orientation <001>, resulting in a straight and uniform grain structure. In addition, to avoid the formation of wrinkles and to ensure a smooth blade surface, the withdrawal rate should be no greater than the growth rate of grain. It is also found that the dendritic space of the blade decreases with the rise of solidification rate, and increases with the enlarging distance between the solidification position and the chill plate.

Ternary System of Fe-based Ionic Liquid,Ethanol and Water for Wet Flue Gas Desulfurization

Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 ： 1.5 ： 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.

Kinetic Rate Constant of Liquid Drainage from Colloidal Gas Aphrons

A kinetic model fitted by the empirical equation has been proposed to describe the liquid drainage behavior. Rate constants （kd） of liquid drainage equation could be obtained from the above empirical equation. In this paper, the stability of the colloidal gas aphrons （CGAs）, the effect of concentrations of sodium dodecyl benzene sulphate （SDBS）, dodecyl trimethylammonium bromide （HTAB） and polyoxyethylene sorbitol anhydride monolaurate（Tween-20）, temperature, stirring speed, stirring time, and various kinds of salts on the kd of liquid drainage are further investigated. The results show that the Arrhenius equation can be successfully used to describe the relation between kd arid absolute temperature （T）, and concentrations of surfactants, stirring speed, stirring time and salinities also have great effect on the kd. At last, the CGAs drainage mechanism is explained from analysis of the rate of liquid drainage as a function of time.

Parametric study of gas−liquid two-phase flow field in horizontal stirred tank

Based on Fluent software,the gas−liquid two-phase flow in the horizontal stirred tank was simulated with SST k−ωturbulence model,Eulerian−Eulerian two-fluid model,and multi-reference flame method.The mixing process in the tank was calculated by tracer method.The results show that increasing the rotating speed or gas flow is conducive to a more uniform distribution of the gas phase and accelerates the mixing of the liquid phase.When the rotating speed exceeds 93 r/min,the relative power demand remains basically constant.The change in the inclination angle of the upper impeller has minimal effect on the gas phase distribution.When the inclination angle is 50°,the relative power demand reaches the maximum.An appropriate increase in the impeller distance from the bottom improves the gas holdup and gas phase distribution but increases the liquid phase mixing time.

A power plant for integrated waste energy recovery from liquid air energy storage and liquefied natural gas

Liquefied natural gas(LNG)is regarded as one of the cleanest fossil fuel and has experienced significant developments in recent years.The liquefaction process of natural gas is energy-intensive,while the regasification of LNG gives out a huge amount of waste energy since plenty of high grade cold energy(-160℃)from LNG is released to sea water directly in most cases,and also sometimes LNG is burned for regasification.On the other hand,liquid air energy storage(LAES)is an emerging energy storage technology for applications such as peak load shifting of power grids,which generates 30%-40%of compression heat(-200℃).Such heat could lead to energy waste if not recovered and used.The recovery of the compression heat is technically feasible but requires additional capital investment,which may not always be economically attractive.Therefore,we propose a power plant for recovering the waste cryogenic energy from LNG regasification and compression heat from the LAES.The challenge for such a power plant is the wide working temperature range between the low-temperature exergy source(-160℃)and heat source(-200℃).Nitrogen and argon are proposed as the working fluids to address the challenge.Thermodynamic analyses are carried out and the results show that the power plant could achieve a thermal efficiency of 27%and 19%and an exergy efficiency of 40%and 28%for nitrogen and argon,respectively.Here,with the nitrogen as working fluid undergoes a complete Brayton Cycle,while the argon based power plant goes through a combined Brayton and Rankine Cycle.Besides,the economic analysis shows that the payback period of this proposed system is only 2.2 years,utilizing the excess heat from a 5 MW/40 MWh LAES system.The findings suggest that the waste energy based power plant could be co-located with the LNG terminal and LAES plant,providing additional power output and reducing energy waste.

Simple Model for Gas Holdup and Liquid Velocity of Annular Photocatalytic External-Loop Airlift Reactor Under both Bubble and Developing Slug Flow

Based on the momentum conservation approach, a theoretical model was developed to predict the superficial liquid velocity, and a correlation equation was established to calculate the gas holdup of an annular external-loop airlift reactor(AELAR)in the bubble flow and developing slug flow pattern. Experiments were performed by using tap-water and silicone oil with the viscosity of 2.0 mm^2/s(2cs-SiO)and 5.0 mm^2/s(5cs-SiO)as liquid phases. The effects of liquid viscosity and flow pattern on the AELAR performance were investigated. The predictions of the proposed model were in good agreement with the experimental results of the AELAR. In addition, the comparison of the experimental results shows that the proposed model has good accuracy and could be used to predict the gas holdup and liquid velocity of an AELAR operating in bubble and developing flow pattern.

Novel guanidinium-based ionic liquids as stationary phases for capillary gas chromatography

The present study describes guanidinium-based ionic liquids（GBILs） as stationary phases for capillary gas chromatography （CGC） and to the best of our knowledge,no related reports are available up to now.In this study,a hexaalkylguanidinium ionic liquid（DOTMG-NTf;） was synthesized and coated statically onto capillary columns.Selectivity of the stationary phase was evaluated by separating Grob test mixture,test mixture,alcohols mixture,and fatty acid methyl esters mixture,and thermal stability was investigated as well.The present study demonstrates that GBILs as CGC stationary phases exhibit satisfactory selectivity and thermal stability and have a great potential as new candidates for CGC stationary phases.