Recovery of oil and free fatty acids from spent bleaching earth using sub-critical water technology supported with kinetic and thermodynamic study

This work represents the extraction of oil with high free fatty acid content from spent bleaching earth using sub-critical water technology as a greener production pathway. The extraction efficiencies under different conditions were investigated. The studied parameters include temperatures in the range of 180 to 270°C, the feed to solventfeed-to-solvent (in this case water) ratio (1:1, 1:2, 1:3, 1:4 and 1:5) and extraction times in the range of 5-60 minutes. The results showed that the optimum temperature, feed to solventfeed-to-solvent ratio, and extraction time were 270°C, 1:3, and 20 minutes, respectively. In another experiment, the extracted free fatty acids were converted into mono-, di-, and triglycerides through esterification with glycerol to increase the value added of the extracted products. The kinetics of the extraction process was found to be corresponding to an irreversible consecutive unimolecular-type first order reaction, consisting of the extraction step followed by the decomposition reaction step. Both reaction rates of extraction and decomposition were estimated using the reaction rate equations utilizing the nonlinear regression method. The apparent activation energy was calculated to be 46.1 kJ·mol-1. This result indicates a diffusion controlled reaction. For more exploration and deep understanding of the extraction mechanism, other thermodynamic parameters were also calculated and analyzed including,ΔH#, ΔS#, and ΔG# of the extraction step.

Application of Sub-Critical Water Extraction in Pharmaceutical Industry

Sub-critical water extraction is a brand-new separation technology. This paper mainly discussed the principle, advantages of sub-critical water extraction, and its applications ranging from the medicinal plants traditionally used in Europe and Asia to produce pharmaceutical extracts (such as volatile oil, tannins, flavonoids, anthraquinone, lactone, etc.). Meanwhile, the prospect of sub-critical water extraction in plant extractives is also explored. It will be widely used in the field of medical plants, bringing huge economic benefits, environmental benefits and social benefits.

Effects of water content on the shear behavior and critical state of glacial till in Tianmo Gully of Tibet, China

Glacial tills are widely distributed in Tibet, China, and are highly susceptible to landslides under intense rainfalls. Failures of the slope during rainfall are closely related to the shear behavior of glacial tills at different moisture conditions. This study investigates the shear behavior and critical state of saturated and unsaturated glacial tills through a series of drained direct shear tests. The tests were conducted on two types of compacted glacial tills with different water contents and total normal stresses. A strain softening mode of failure is observed for all water content conditions accompanied by noticeable dilation. Dilatancy is found to decrease with increasing water content. Unsaturated samples showed increased rates of dilation as water content is decreased for all applied normal stresses a behavior which cannot be predicted well by classical stressdilatancy models. Furthermore, it was found that the Critical State Line(CSL), plotted on the(e-ln) plane, can be used to define the shear behavior of unsaturated glacial tills at different water contents.The CSL of saturated glacial tills run parallel to this line. The experimental results in this study are aimed to provide a basic understanding to the underlying failure mechanisms of glacial tills.

Critical discharge at Datong for controlling operation of South-to-North Water Transfer Project in dry seasons

Previous research shows that there is a strong correlation between saltwater intrusion in the Yangtze Estuary and discharge at Datong. In the near future, the discharge of the Yangtze River during dry seasons will decrease due to the construction and operation of large water diversion projects, including the South-to-North Water Transfer Project, which will further exacerbate saltwater intrusion in the estuary. In this paper, a nested 1D river network model and a 2D saltwater numerical model are used to associate saltwater intrusion in the Yangtze Estuary with different values of discharge at Datong. It is concluded that 13 000 m3/s is the critical discharge at Datong for preventing saltwater intrusion and controlling the volume of water transferred by the South-to-North Water Transfer Project. Furthermore, based on the analysis of river discharge from Datong to Xuliujing and in consideration of the influence of all of the water diversion projects, operation schemes are proposed for the Eastern Route of the South-to-North Water Transfer Project for different hydrological years.

Critical chain construction with multi-resource constraints based on portfolio technology in South-to-North Water Diversion Project

Recently, the critical chain study has become a hot issue in the project management research field. The construction of the critical chain with multi-resource constraints is a new research subject. According to the system analysis theory and project portfolio theory, this paper discusses the creation of project portfolios based on the similarity principle and gives the definition of priority in multi-resource allocation based on quantitative analysis. A model with multi-resource constraints, which can be applied to the critical chain construction of the A-bid section in the South-to-North Water Diversion Project, was proposed. Contrast analysis with the comprehensive treatment construction method and aggressive treatment construction method was carried out. This paper also makes suggestions for further research directions and subjects, which will be useful in improving the theories in relevant research fields.

Critical parameters of horizontal well influenced by semi-permeable barrier in bottom water reservoir

It is well-known that barriers have a significant impact on the production performance of horizontal wells developed in a bottom water drive reservoir. In most cases, reservoir barriers are semi-permeable. Based on previous research on impermeable reservoir barrier, a mathematical flow model was derived for a horizontal well of a bottom water drive reservoir with a semi-permeable barrier. Besides, analytical equations were also presented to calculate critical parameters, such as production rate,pressure and potential difference. The effects of barrier, well and reservoir parameters on our model results were further investigated.The results show that the larger the barrier size is or the higher the barrier location is, the higher the critical production rate and potential difference of a horizontal well are. When the barrier permeability equals the formation permeability or the barrier width equals zero, the critical production rates converge to the values same to that of the case with no barrier. When the barrier permeability equals zero, the problem is regarded as a case of impermeable barrier. This model can be applied to predicting horizontal wells' critical production parameters in reservoirs with semi-permeable barriers.

Role of hydro-geochemical functions on karst critical zone hydrology for sustainability of water resources and ecology in Southwest China

Focusing on sustainability of water resources and ecology in the complex karst critical zone, we illustrated functions of the hydro-geochemical analysis on hydrology from the aspects of connection and interaction among hydrology–vegetation–soils/rock fractures along the karst subsurface profile. We reviewed isotopic and geochemical interpretations on tracing water sources for plant uptake, quantifying watershed outlet flow composition and residence times, and evaluating long-term evolution among climate–landscape–hydrology in the karst critical zone. In this paper, the application of the hydro-geochemical analysis on the above aspects in the karst areas of southwest China was summarized.

The critical rate of horizontal wells in bottom-water reservoirs with an impermeable barrier

Barrier impacts on water cut and critical rate of horizontal wells in bottom water-drive reservoirs have been recognized but not investigated quantitatively. Considering the existence of impermeable barriers in oil formations, this paper developed a horizontal well flow model and obtained mathematical equations for the critical rate when water cresting forms in bottom-water reservoirs. The result shows that the barrier increases the critical rate and delays water breakthrough. Further study of the barrier size and location shows that increases in the barrier size and the distance between the barrier and oil-water contact lead to higher critical rates. The critical rate gradually approaches a constant as the barrier size increases. The case study shows the method presented here can be used to predict the critical rate in a bottom-water reservoir and applied to investigate the water cresting behavior of horizontal wells.

Decomposition Behavior and Decomposition Products of Epoxy Resin Cured with MeHHPA in Near-critical Water

A kind of chemical method that used water as the liquid reaction medium to decompose epoxy resin was studied. The thermosetting epoxy resin was decomposed successfully under the condition of near-critical water. The decomposition rate of epoxy resin raised rapidly as the reaction time and reaction temperature increased. The decomposition reaction products were characterized by infra-red spectra and gas chromatography-mass spectrometry. The phenol, isopropylphenol, 4, 4＇-（1-methylethylidene） bis-phenol were found as the main compounds in liquid products, which were common monomers from epoxy resin. When reaction was carried out at the temperature of 260℃ -300 ℃, the decomposition mechanism of epoxy resin was envisaged as the ether and ester bonds cracking.

Critical Heat Flux with Subcooled Flowing Water in Tubes for Pressures from Atmosphere to Near-Critical Point

During last 45 years, two groups of the experimental data on critical heat flux were obtained in bare tubes, covering the pressures from atmosphere to near-critical point. One group of the data were obtained in the inner diameter of 2.32, 5.16, 8.05, 10.0 and 16.0 mm, respectively, with the ranges of pressure of 0.1-1.92 MPa, velocity of 1.47-23.3 m/s, local subcooling of 3.7-108.7 ℃ and heat flux of up to 38.3 MW/m2. Another group of the data were obtained in the inner diameter of 4.62, 7.98 and 10.89 mm, respectively, with the ranges of pressure of 1.7-20.6 MPa, mass flux of 454-4,055 kg/（m2.s） and inlet subcooling of 53-361 ℃. The results showed complicated effects of the pressure, mass flux, subcooling and diameter on the critical heat flux. They were formulated by two empirical correlations. A mechanistic model on the limit of heat transfer capability from the bubbly layer to the subcooled core was also proposed for all the results.

Correlation of Critical Loci for Water-Hydrocarbon Binary Systems by EOS Based on the Multi-Fluid Nonrandom Lattice Theory

Quantitative representation of complicated behavior of fluid mixtures in the critical region by any of equation-of-state theories re-mains as a difficult thermodynamic topics to date. In the present work, a computational efforts were made for representing various types of critical loci of binary water with hydrocarbon systems showing Type II and Type III phase behavior by an elementary equation of state [called multi-fluid nonrandom lattice fluid EOS (MF-NLF EOS)] based on the lattice statistical mechanical theory. The model EOS requires two mo-lecular parameters which representing molecular size and interaction energy for a pure component and single adjustable interaction energy pa-rameter for binary mixtures. Critical temperature and pressure data were used to obtain molecular size parameter and vapor pressure data were used to obtain interaction energy parameter. The MF-NLF EOS model adapted in the present study correlated quantitatively well the critical loci of various binary water with hydrocarbon systems.

Gibbs Density Surface of Water and Steam: 2nd Debate on the Absence of Van Der Waals’ “Critical Point”

A revised phase diagram for water shows three distinct fluid phases. There is no continuity of liquid and gas, and no “critical point” on Gibbs’ density surface as hypothesized by van der Waals. A supercritical colloidal mesophase bounded by percolation transition loci separates supercritical liquid water and gas-phase steam. The water phase is bounded by a percolation transition (PA) of available volume, whereas steam is bounded by the loci of a percolation transition (PB) at a density whereupon a bonded molecular cluster suddenly percolates large distances. At the respective percolation densities, there is no barrier to nucleation of water to steam (PA) or steam to water (PB). Below the critical temperature, the percolation loci become the metastable spinodals in the two-phase coexistence region. A critical divide is defined by the interception of PA and PB the p-T plane. Critical parameters are obtainable from slopes and intercepts of pressure-density supercritical isotherms within the mesophase. The supercritical mesophase is a fourth equilibrium state besides ice, water and steam. A thermodynamic state function rigidity (dp/dρ)T defines a distinction between liquid and gas, and shows a remarkable symmetry due to an equivalence in number density fluctuations, arising from available volume and molecular clusters, in liquid and gas respectively. Following an earlier debate in these pages [“Fluid phases of argon: A debate on the absence of van der Waals’ critical point” Natural Science 5 (2) 194-206 (2013)], we here report further debate on a science of criticality applied to water and steam (APPENDIX 1).

Study on the Critical Production Calculation Method of the Water-Flooding Reservoir with Gas Cap

The aim of this paper is to solve the problems that the existing method of critical production of gas cap reservoir is only suitable for single-phase flow, and the method of critical production of gas cap reservoir under water-flooding is still blank. In this paper, the relationships between dynamic and static equilibrium, plane radial flow theory, oil-water infiltration method and three-dimensional seepage field decomposition theory, were applied to study a calculation method for critical production of directional wells and horizontal wells. Furthermore, the effects of different factors on critical output were studied, such as horizontal permeability, ratio of horizontal permeability to vertical permeability, length of horizontal section, effective thickness, viscosity of crude oil and water content etc. Results show that the critical production increases with the increment of the horizontal permeability, the ratio of the vertical permeability to the horizontal permeability, the reservoir thickness and the horizontal well length;when the viscosity of crude oil is small, the critical production decreases first and then increases with the increase of water content;when the viscosity of crude oil is high, the critical production increases continuously with the increase of water content. This study could provide theoretical and technical guidance for changing of the working system of oil wells. It can avoid gas channeling and improve the development effect.

Investigation on two－phase critical flow for loss－of－coolant accident of pressurized water reactor

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The Corrected Simulation Method of Critical Heat Flux Prediction for Water-Cooled Divertor Based on Euler Homogeneous Model

An accurate critical heat flux（CHF） prediction method is the key factor for realizing the steady-state operation of a water-cooled divertor that works under one-sided high heating flux conditions.An improved CHF prediction method based on Euler＇s homogeneous model for flow boiling combined with realizable k-ε model for single-phase flow is adopted in this paper in which time relaxation coefficients are corrected by the Hertz-Knudsen formula in order to improve the calculation accuracy of vapor-liquid conversion efficiency under high heating flux conditions.Moreover,local large differences of liquid physical properties due to the extreme nonuniform heating flux on cooling wall along the circumference direction are revised by formula IAPWSIF97.Therefore,this method can improve the calculation accuracy of heat and mass transfer between liquid phase and vapor phase in a CHF prediction simulation of water-cooled divertors under the one-sided high heating condition.An experimental example is simulated based on the improved and the uncorrected methods.The simulation results,such as temperature,void fraction and heat transfer coefficient,are analyzed to achieve the CHF prediction.The results show that the maximum error of CHF based on the improved method is 23.7%,while that of CHF based on uncorrected method is up to 188%,as compared with the experiment results of Ref.[12].Finally,this method is verified by comparison with the experimental data obtained by International Thermonuclear Experimental Reactor（ITER）,with a maximum error of 6% only.This method provides an efficient tool for the CHF prediction of water-cooled divertors.

Long-term phosphorus accumulation and agronomic and environmtal critical phosphorus levels in Haplic Luvisol soil, northern China

Sufficient soil phosphorus （P） content is essential for achieving optimal crop yields, but accumulation of P in the soil due to excessive P applications can cause a risk of P loss and contribute to eutrophication of surface waters. Determination of a critical soil P value is fundamental for making appropriate P fertilization recommendations to ensure safety of both environment and crop production. In this study, agronomic and environmental critical P levels were determined by using linear-linear and linear-plateau models, and two segment linear model, for a maize （Zea mays L.）-winter wheat （Triticum aestivum L.） rotation system based on a 22-yr field experiment on a Haplic Luvisol soil in northern China. This study included six treatments： control （unfertilized）, no P （NoP）, application of mineral P fertilizer （MinP）, MinP plus return of maize straw （MinP＋StrP）, MinP plus low rate of farmyard swine manure （MinP＋L.Man） and MinP plus high rate of manure （MinP＋ H.Man）. Based on the two models, the mean agronomic critical levels of soil Olsen-P for optimal maize and wheat yields were 12.3 and 12.8 mg kg-1, respectively. The environmental critical P value as an indicator for P leaching was 30.6 mg Olsen-P kg-1, which was 2.4 times higher than the agronomic critical P value （on average 12.5 mg P kg-1）. It was calculated that soil OIsen-P content would reach the environmental critical P value in 41 years in the MinP treatment, but in only 5-6 years in the two manure treatments. Application of manure could significantly raise soil Olsen-P content and cause an obvious risk of P leaching. In conclusion, the threshold range of soil Olsen-P is from 12.5 to 30.6 mg P kg-1 to optimize crop yields and meanwhile maintain relatively low risk of P leaching in Haplic Luvisol soil, northern China.

Critical State Sedimentation Line of Soft Marine Clays

The compression behavior responsible for unity sensitivity is very valuable in quantitative assessment of the effects of soil structure on the compression behavior of soft marine sediments. However, the quantitative assessment of such effects is not possible because of unavailability of the formula for the compression curve of marine sediments responsible for unit sensitivity. In this study, the relationship between the remolded state and the conventional critical state line is presented in the deviator stress versus mean effective stress plot. The analysis indicates that the remolded state is on the conventional critical state line obtained at a relatively small strain. Thus, a unique critical state sedimentation line for marine sediments of unit sensitivity is proposed. The comparison between the critical state sedimentation line proposed in this study and the existing normalized consolidation curves obtained from conventional oedometer tests on remolded soils or reconstituted soils explains well the

Thermodynamic Fit Functions of the Two-Phase Fluid and Critical Exponents

Two-phase fluid properties such as entropy, internal energy, and heat capacity are given by thermodynamically defined fit functions. Each fit function is expressed as a temperature function in terms of a power series expansion about the critical point. The leading term with the critical exponent dominates the temperature variation between the critical and triple points. With β being introduced as the critical exponent for the difference between liquid and vapor densities, it is shown that the critical exponent of each fit function depends (if at all) on β. In particular, the critical exponent of the reciprocal heat capacity c﹣1 is α=1-2β and those of the entropy s and internal energy u are?2β, while that of the reciprocal isothermal compressibility?κ﹣1T is γ=1. It is thus found that in the case of the two-phase fluid the Rushbrooke equation conjectured α +?2β + γ=2 combines the scaling laws resulting from the two relations c=du/dT and?κT=dlnρ/dp. In the context with c, the second temperature derivatives of the chemical potential μ and vapor pressure p are investigated. As the critical point is approached, ﹣d2μ/dT2 diverges as c, while?d2p/dT2 converges to a finite limit. This is explicitly pointed out for the two-phase fluid, water (with β=0.3155). The positive and almost vanishing internal energy of the one-phase fluid at temperatures above and close to the critical point causes conditions for large long-wavelength density fluctuations, which are observed as critical opalescence. For negative values of the internal energy, i.e. the two-phase fluid below the critical point, there are only microscopic density fluctuations. Similar critical phenomena occur when cooling a dilute gas to its Bose-Einstein condensate.

Strategic Coordination for Sustainable Investment in Critical Infrastructure

In demonstrating the prime place of infrastructure investment in its national long-term development framework encapsulated in Vision 2030, as well as in the related New Growth Path, South Africa recently put together a comprehensive National Infrastructure Plan. Aside from mapping out short and medium-term priorities for scaling up investment in strategic sectors and enhancing infrastructure links across the country, the initiative underscores development objectives such as community empowerment and skills development. This paper zeroes into one of the 18 strategic programs in the plan—specifically devoted to water and sanitation infrastructure—and presents the principal elements for pursuing effective inter-project coordination and integration, as well as, ultimately, for ensuring the sustainable implementation of critical infrastructure. The approaches that have influenced the success of strategic coordination include participatory planning, project prioritization, regular tracking and unblocking of implementation hurdles, localization, active stakeholder engagement and ongoing program integration.