Tuning the selectivity of natural oils and fatty acids/esters deoxygenation to biofuels and fatty alcohols:A review

The chemical transformation of natural oils provides alternatives to limited fossil fuels and produces compounds with added value for the chemical industries.The selective deoxygenation of natural oils to diesel-ranged hydrocarbons,bio-jet fuels,or fatty alcohols with controllable selectivity is especially attractive in natural oil feedstock biorefineries.This review presents recent progress in catalytic deoxygenation of natural oils or related model compounds(e.g.,fatty acids)to renewable liquid fuels(green diesel and bio-jet fuels)and valuable fatty alcohols(unsaturated and saturated fatty alcohols).Besides,it discusses and compares the existing and potential strategies to control the product selectivity over heterogeneous catalysts.Most research conducted and reviewed has only addressed the production of one category;therefore,a new integrative vision exploring how to direct the process toward fuel and/or chemicals is urgently needed.Thus,work conducted to date addressing the development of new catalysts and studying the influence of the reaction parameters(e.g.,temperature,time and hydrogen pressure)is summarized and critically discussed from a green and sustainable perspective using efficiency indicators(e.g.,yields,selectivity,turnover frequencies and catalysts lifetime).Special attention has been given to the chemical transformations occurring to identify key descriptors to tune the selectivity toward target products by manipulating the reaction conditions and the structures of the catalysts.Finally,the challenges and future research goals to develop novel and holistic natural oil biorefineries are proposed.As a result,this critical review provides the readership with appropriate information to selectively control the transformation of natural oils into either biofuels and/or value-added chemicals.This new flexible vision can help pave the wave to suit the present and future market needs.

Purification of Produced Water from a Sour Oilfield in South Kuwait. 1. Oil-Water Separation and Industrial Salt Production

Produced water from an oil extraction site in South Kuwait was sampled after primary oil – water separation had been carried out. The produced water was filtered through a mixture of activated charcoal and esterified cellulosic material gained from spent coffee grounds as a tertiary adsorption treatment. The earth-alkaline metal ions and heavy metals were separated from the de-oiled produced water by addition of either sodium or potassium hydroxide in the presence of carbon dioxide or by direct addition of solid sodium carbonate. The resulting filtrate gave salt of industrial purity upon selective crystallization on evaporation.

Influence of pore structure heterogeneity on channeling channels during hot water flooding in heavy oil reservoir based on CT scanning

Hot water flooding is an effective way to develop heavy oil reservoirs.However,local channeling channels may form,possibly leading to a low thermal utilization efficiency and high water cut in the reservoir.The pore structure heterogeneity is an important factor in forming these channels.This study proposes a method that mixes quartz sand with different particle sizes to prepare weakly heterogeneous and strongly heterogeneous models through which hot water flooding experiments are conducted.During the experiments,computer tomography(CT)scanning identifies the pore structure and micro remaining oil saturation distribution to analyze the influence of the pore structure heterogeneity on the channeling channels.The oil saturation reduction and average pore size are divided into three levels to quantitatively describe the relationship between the channeling channel distribution and pore structure heterogeneity.The zone where oil saturation reduction exceeds 20%is defined as a channeling channel.The scanning area is divided into 180 equally sized zones based on the CT scanning images,and threedimensional(3D)distributions of the channeling channels are developed.Four micro remaining oil distribution patterns are proposed,and the morphology characteristics of micro remaining oil inside and outside the channeling channels are analyzed.The results show that hot water flooding is more balanced in the weakly heterogeneous model,and the oil saturation decreases by more than 20%in most zones without narrow channeling channels forming.In the strongly heterogeneous model,hot water flooding is unbalanced,and three narrow channeling channels of different lengths form.In the weakly heterogeneous model,the oil saturation reduction is greater in zones with larger pores.The distribution range of the average pore size is larger in the strongly heterogeneous model.The network remaining oil inside the channeling channels is less than outside the channeling channels,and the hot water converts the network remaining oil into cluster,film,and droplet remaining oil.

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil-water separation

This paper presents a superhydrophobic melamine(ME)sponge(ME-g-PLMA)prepared via high-energy radiation-induced in situ covalent grafting of long-alkyl-chain dodecyl methacrylate(LMA)onto an ME sponge for efficient oil–water separation.The obtained ME-g-PLMA sponge had an excellent pore structure with superhydrophobic(water contact angle of 154°)and superoleophilic properties.It can absorb various types of oils up to 66–168 times its mass.The ME-g-PLMA sponge can continuously separate oil slicks in water by connecting a pump or separating oil underwater with a gravity-driven device.In addition,it maintained its highly hydrophobic properties even after long-term immersion in different corrosive solutions and repeated oil adsorption.The modified ME-g-PLMA sponge exhibited excellent separation properties and potential for oil spill cleanup.

A CFD Model to Evaluate Near-Surface Oil Spill from a Broken Loading Pipe in Shallow Coastal Waters

Oil spills continue to generate various issues and concerns regarding their effect and behavior in the marine environment,owing to the related potential for detrimental environmental,economic and social implications.It is essential to have a solid understanding of the ways in which oil interacts with the water and the coastal ecosystems that are located nearby.This study proposes a simplified model for predicting the plume-like transport behavior of heavy Bunker C fuel oil discharging downward from an acutely-angled broken pipeline located on the water surface.The results show that the spill overall profile is articulated in three major flow areas.The first,is the source field,i.e.,a region near the origin of the initial jet,followed by the intermediate or transport field,namely,the region where the jet oil flow transitions into an underwater oil plume flow and starts to move horizontally,and finally,the far-field,where the oil re-surface and spreads onto the shore at a significant distance from the spill site.The behavior of the oil in the intermediate field is investigated using a simplified injection-type oil spill model capable of mimicking the undersea trapping and lateral migration of an oil plume originating from a negatively buoyant jet spill.A rectangular domain with proper boundary conditions is used to implement the model.The Projection approach is used to discretize a modified version of the Navier-Stokes equations in two dimensions.A benchmark fluid flow issue is used to verify the model and the results indicate a reasonable relationship between specific gravity and depth as well as agreement with the aerial data and a vertical temperature profile plot.

A Gasification Technology to Combine Oil Sludge with Coal-Water Slurry:CFD Analysis and Performance Determination

The development of more environment-friendly ways to dispose of oil sludge is currently regarded as a hot topic.In this context,gasification technologies are generally seen as a promising way to combine oil sludge with coal–water slurry(CWS)and generate resourceful fuel.In this study,a novel five-nozzle gasifier reactor was analyzed by means of a CFD(Computational fluid dynamic)method.Among several influential factors,special attention was paid to the height-to-diameter ratio of the gasifier and the mixing ratio of oil sludge,which are known to have a significant impact on the flow field,temperature distribution and gasifier performances.According to the numerical results,the optimal height-to-diameter ratio and oil mixing ratio are about 2.4:1 and 20%,respectively.Furthermore,the carbon conversion rate can become as high as 98.55%with the hydrolysis rate reaching a value of 53.88%.The consumption of raw coal and oxygen is generally reduced,while the effective gas production is increased to 50.93 mol/%.

Purification of Produced Water from a Sour Oilfield in South Kuwait. 2. Oil-Water Separation and Crystallization of Calcium Carbonate

Oil-water separation for produced water (PW) originating from an oil extraction site in South Kuwait was carried out using bleached, esterified cellulosic material from used coffee grounds. Thereafter, earth-alkaline metal ions, specifically calcium ions, of the de-oiled PW were removed by precipitation with sodium carbonate to give access to pure sodium chloride as industrial salt from the remaining PW. While the purity of the precipitated calcium carbonate (CaCO3) depends on the precipitation conditions, CaCO3 of up to 95.48% purity can be obtained, which makes it a salable product. The precipitation of CaCO3 decreases the amount of calcium ions in PW from 11,300 ppm to 84 ppm.

Selective adsorption of tetracycline by β-CD-immobilized sodium alginate aerogel coupled with ultrafiltration for reclaimed water

In this work,a novel composite material based on β-cyclodextrin-immobilized sodium alginate aerogel(β-CD/NaAlg) was developed utilizing cross-linker of epichlorohydrin and applied as an adsorbent to remove tetracycline antibiotics from reclaimed wastewater.A series of characterizations were utilized to confirm the successful synthesis of the adsorbent and this β-CD/NaAlg presented a three-dimensional network at the nanoscale or microscale.Under optimal conditions(pH=4,t=8 h,β-CD:NaAlg=9,adsorbent dosage = 1.5 g·L-1),the maximum removal rate of β-CD/NaAlg to tetracycline was 70%.The adsorption behavior of tetracycline on β-CD/NaAlg conformed to the Freundlich isotherm model(R2=0.9977) and the pseudo-second-order kinetic model(R^(2)=0.9993).Moreover,the adsorbent still removed 55.3% of tetracycline after five cycles.Specially,the adsorbent was integrated with ultrafiltration to adsorb tetracycline antibiotics from simulated reclaimed wastewater,and the removal rate of tetracycline reached 78.9% within 2 h.The existence of Cr(Ⅵ) had a negligible impact on tetracycline removal,while the presence of humic acid exhibited a promoting effect.The possible adsorption mechanisms were also elucidated through X-ray photoelectron spectroscopy and density functional theory analysis.In summary,β-CD/NaAlg represents an environmentally friendly,efficient,and sustainable adsorbent for removing tetracycline antibiotics from reclaimed water.

Effect of high-multiple water injection on rock pore structure and oil displacement efficiency

Experimental methods,including mercury pressure,nuclear magnetic resonance(NMR)and core(wateroil)displacement,are used to examine the effects of high-multiple water injection(i.e.water injection with high injected pore volume)on rock properties,pore structure and oil displacement efficiency of an oilfield in the western South China Sea.The results show an increase in the permeability of rocks along with particle migration,an increase in the pore volume and the average pore throat radius,and enhanced heterogeneity after high-multiple water injection.Compared with normal water injection methods,a high-multiple water injection is more effective in improving the oil displacement efficiency.The degree of recovery increases faster in the early stage due to the expansion of the swept area,and the transition from oil-wet to water-wet.The degree of recovery increases less in the late stage due to various factors,including the enhancement of heterogeneity in the rocks.Considering both the economic aspect and the production limit of water flooding,it is recommended to adopt other technologies to further enhance oil recovery after 300 PV water injection.

Remaining oil distribution characteristics in an oil reservoir with ultra-high water-cut

An accurate mapping and understanding of remaining oil distribution is very important for water control and stabilize oil production of mature oilfields in ultra-high water-cut stage.Currently,the Tuo-21 Fault Block of the Shengtuo Oilfield has entered the stage of ultra-high water cut(97.2%).Poor adaptability of the well pattern,ineffective water injection cycle and low efficiency of engineering measures(such as workover,re-perforation and utilization of high-capacity pumps)are the significant problems in the ultra-high water-cut reservoir.In order to accurately describe the oil and water flow characteristics,relative permeability curves at high water injection multiple(injected pore volume)and a semiquantitative method is applied to perform fine reservoir simulation of the Sand group 3e7 in the Block.An accurate reservoir model is built and history matching is performed.The distribution characteristics of remaining oil in lateral and vertical directions are quantitatively simulated and analyzed.The results show that the numerical simulation considering relative permeability at high injection multiple can reflect truly the remaining oil distribution characteristics after water flooding in an ultrahigh water-cut stage.The distribution of remaining oil saturation can be mapped more accurately and quantitatively by using the‘four-points and five-types’classification method,providing a basis for potential tapping of various remaining oil types of oil reservoirs in late-stage of development with high water-cut.

Sedimentary build-ups of pre-salt isolated carbonate platforms and formation of deep-water giant oil fields in Santos Basin,Brazil

In response to the problems of unclear distribution of deep-water pre-salt carbonate reservoirs and formation conditions of large oil fields in the Santos passive continental margin basin,based on comprehensive utilization of geological,seismic,and core data,and reconstruction of Early Cretaceous prototype basin and lithofacies paleogeography,it is proposed for the first time that the construction of pre-salt carbonate build-ups was controlled by two types of isolated platforms:inter-depression fault-uplift and intra-depression fault-high.The inter-depression fault-uplift isolated platforms are distributed on the present-day pre-salt uplifted zones between depressions,and are built on half-and fault-horst blocks that were inherited and developed in the early intra-continental and inter-continental rift stages.The late intra-continental rift coquinas of the ITP Formation and the early inter-continental rift microbial limestones of the BVE Formation are continuously constructed;intra-depression fault-high isolated platforms are distributed in the current pre-salt depression zones,built on the uplifted zones formed by volcanic rock build-ups in the early prototype stage of intra-continental rifts,and only the BVE microbial limestones are developed.Both types of limestones formed into mound-shoal bodies,that have the characteristics of large reservoir thickness and good physical properties.Based on the dissection of large pre-salt oil fields discovered in the Santos Basin,it has been found that both types of platforms could form large-scale combined structural-stratigraphic traps,surrounded by high-quality lacustrine and lagoon source rocks at the periphery,and efficiently sealed by thick high-quality evaporite rocks above,forming the optimal combination of source,reservoir and cap in the form of“lower generation,middle storage,and upper cap”,with a high degree of oil and gas enrichment.It has been found that the large oil fields are all bottom water massive oil fields with a unified pressure system,and they are all filled to the spill-point.The future exploration is recommended to focus on the inter-depression fault-uplift isolated platforms in the western uplift zone and the southern section of eastern uplift zones,as well as intra-depression fault-high isolated platforms in the central depression zone.The result not only provides an important basis for the advanced selection of potential play fairways,bidding of new blocks,and deployment of awarded exploration blocks in the Santos Basin,but also provides a reference for the global selection of deep-water exploration blocks in passive continental margin basins.

Experimental investigation on using CO_(2)/H_(2)O emulsion with high water cut in enhanced oil recovery

CO_(2) emulsions used for EOR have received a lot of interest because of its good performance on CO_(2)mobility reduction.However,most of them have been focusing on the high quality CO_(2) emulsion(high CO_(2) fraction),while CO_(2) emulsion with high water cut has been rarely researched.In this paper,we carried out a comprehensive experimental study of using high water cut CO_(2)/H_(2)O emulsion for enhancing oil recovery.Firstly,a nonionic surfactant,alkyl glycosides(APG),was selected to stabilize CO_(2)/H_(2)O emulsion,and the corresponding morphology and stability were evaluated with a transparent PVT cell.Subsequently,plugging capacity and apparent viscosity of CO_(2)/H_(2)O emulsion were measured systematically by a sand pack displacement apparatus connected with a 1.95-m long capillary tube.Furthermore,a high water cut(40 vol%) CO_(2)/H_(2)O emulsion was selected for flooding experiments in a long sand pack and a core sample,and the oil recovery,the rate of oil recovery,and the pressure gradients were analyzed.The results indicated that APG had a good performance on emulsifying and stabilizing CO_(2) emulsion.An inversion from H_(2)O/CO_(2) emulsion to CO_(2)/H_(2)O emulsion with the increase in water cut was confirmed.CO_(2)/H_(2)O emulsions with lower water cuts presented higher apparent viscosity,while the optimal plugging capacity of CO_(2)/H_(2)O emulsion occurred at a certain water cut.Eventually,the displacement using CO_(2)/H_(2)O emulsion provided 18.98% and 13.36% additional oil recovery than that using pure CO_(2) in long sand pack and core tests,respectively.This work may provide guidelines for EOR using CO_(2) emulsions with high water cut.

Effect of CO_(2)flooding in an oil reservoir with strong bottom-water drive in the Tahe Oilfield,Tarim Basin,Northwest China

The dissolution and diffusion of CO_(2)in oil and water and its displacement mechanism were investigated by laboratory experiment and numerical simulation for Block 9 in the Tahe oilfield,a sandstone oil reservoir with strong bottom-water drive in Tarim Basin,Northwest China.Such parameters were analyzed as solubility ratio of CO_(2)in oil,gas and water,interfacial tension,in-situ oil viscosity distribution,remaining oil saturation distribution,and oil compositions.The results show that CO_(2)flooding could control water coning and increase oil production.In the early stage of the injection process,CO_(2)expanded vertically due to gravity differentiation,and extended laterally under the action of strong bottom water in the intermediate and late stages.The CO_(2)got enriched and extended at the oil-water interface,forming a high interfacial tension zone,which inhibited the coning of bottom water to some extent.A miscible region with low interfacial tension formed at the gas injection front,which reduced the in-situ oil viscosity by about 50%.The numerical simulation results show that enhanced oil recovery(EOR)is estimated at 5.72%and the oil exchange ratio of CO_(2)is 0.17 t/t.

Comparison and Selection of Water Restoration Techniques for Artificial Landscape Lakes in Nantong City

As an important part of urban infrastructure,urban water system is of great and far-reaching significance for ensuring urban flood control and waterlogging safety,protecting ecological environment and building livable homes.Taking the urban water system of Nantong as an example,Nantong Water Resources Bureau issued R evision of Nantong Urban Water System Planning in 2017,and put forward the construction of the"two circles,eight lakes and nine veins"water system layout,giving new vitality to the urban water system.In view of problems existing in newly excavated artificial landscape lakes,such as fragile water ecosystem,strong eutrophication trend,poor environmental sensory effect and unsatisfactory water landscape effect,it is urgent to study the in-situ water ecological restoration technique of"algae-controlling zooplankton+submerged plant community"to build a"grass-type clear water"ecosystem for artificial landscape lakes,so as to improve the water sensory index and self-purification ability and finally realize the double improvement of"sensory effect and water quality"of artificial landscape lakes.

Variability in Quantity and Salinity of Produced Water from an Oil Production in South Kuwait

Produced water (PW) is the largest waste stream in the oil and gas industry. Water remains trapped for millions of years in the reservoir with oil and gas. When a hydrocarbon reservoir is infiltrated by a production well, the produced fluids commonly contain water. The understanding of this water’s constituents and volumes is vital for the sustainable continuity of production operations, as PW has a number of negative impacts on the infrastructure integrity of the operation. On the other hand, PW can be an alternative source of irrigation water as well as of industrial salt. Interestingly, both the quantity as well as the quality of PW do not remain constant but can vary, both progressively and erratically, even over short periods of time. This paper discusses such a situation of variable PW in an oil and gas operation in the State of Kuwait.

Diesel oil infiltration in soils with selected antecedent water content and bulk density

The effects of soil texture, initial water content and bulk density on diesel oil infiltration in fine sand and silty clay loam materials were evaluated. Three physical and two empirical equations express diesel oil infiltration through soils with time, with coefficients of determination greater than 0.99. Diesel oil infiltrates more quickly in the fine sand than in the silty clay loam material. Diesel oil infiltration rates are found to decrease with increasing initial water content and bulk density for the silty clay loam material. The infiltration rate of diesel oil in the fine sand material increases slightly with increasing initial water content. The diesel oil saturated conductivity(Kdiesel) decreases with increasing bulk density for the silty clay loam column. Diesel oil sorptivity(S) decreases linearly with increased initial water content and bulk density of the silty clay loam material. Changes in empirical parameters relative to initial water content and bulk density are similar to the parameter S.

Effects of Different Heavy Crude Oil Fractions on the Stability of Oil-in-water Emulsions —— Isolation of functional fractions from heavy crude oil and study of their properties

The functional fractions (acid, basic, amphoteric and neutral fractions) are isolated from the Liaohe Du-84 heavy crude oil and Shengli Gudao Kenxi heavy crude oil by ion-exchange chromatography, but the conventional fractions (saturates, aromatics, resins and asphaltenes) are also isolated from the heavy crude oil. These components have been characterized by spectroscopic methods (FT-IR), namely acid number, basic nitrogen number, ultimate analysis and molecular weight measurements using vapor pressure osmometry (VPO). The ion-exchange chromatography method based on separation by a functional group induces a little change on the nature of the crudes and reasonable mass balances can be easily obtained.

Experimental measurements of water content in crude oil emulsions by terahertz time-domain spectroscopy

We measured the water content （0.01% 0.25% w/w） in crude oil emulsions using terahertz time-domain spectroscopy （THz-TDS）. To improve the precision and range of the measurements, we used 1 and 10 mm thick quartz cells. The experiments were performed at 20 ℃ and the THz wave was transmitted vertically to the samples and detected on the other side. The experimental results suggest linear relation for the THz absorption coefficient and the water content of the crude oil emulsions in the observed range. The linear dependence facilitates high-precision measurements of the water content of crude oil. This suggests the potential of THz-TDS in determining the water concentration in crude oil and borehole fluid identification.

Performance of low-salinity water flooding for enhanced oil recovery improved by SiO_2 nanoparticles

Low-salinity water injection has been utilized as a promising method for oil recovery in recent years. Low-salinity water flooding changes the ion composition or brine salinity for improving oil recovery. Recently, the application of nanoparticles with low-salinity water flooding has shown remarkable results in enhanced oil recovery(EOR). Many studies have been performed on the effect of nanofluids on EOR mechanisms. Their results showed that nanofluids can improve oil recovery when used in low-salinity water flooding. In this work, the effects of injection of low-salinity water and low-salinity nanofluid(prepared by adding SiO_2 nanoparticles to low-salinity water) on oil recovery were investigated. At first, the effects of ions were investigated with equal concentrations in low-salinity water flooding. The experimental results showed that the monovalent ions had better performance than the divalent ions because of them having more negative zeta potential and less ionic strength. Also, low-salinity water flooding recovered 6.1% original oil in place(OOIP) more than the high-salinity flooding. Contact angle measurements demonstrated that low-salinity water could reduce the contact angle between oil and water. Then in the second stage, experiments were continued by adding SiO_2 nanoparticles to the K+ solution which had the highest oil recovery at the first stage. The experimental results illustrated that the addition of Si02 nanoparticles up to 0.05 wt% increased oil recovery by about 4% OOIP more than the low-salinity water flooding.

A Method for Crude Oil Selection and Blending Optimization Based on Improved Cuckoo Search Algorithm

Refineries often need to find similar crude oil to replace the scarce crude oil for stabilizing the feedstock property. We introduced the method for calculation of crude blended properties firstly, and then created a crude oil selection and blending optimization model based on the data of crude oil property. The model is a mixed-integer nonlinear programming(MINLP) with constraints, and the target is to maximize the similarity between the blended crude oil and the objective crude oil. Furthermore, the model takes into account the selection of crude oils and their blending ratios simultaneously, and transforms the problem of looking for similar crude oil into the crude oil selection and blending optimization problem. We applied the Improved Cuckoo Search(ICS) algorithm to solving the model. Through the simulations, ICS was compared with the genetic algorithm, the particle swarm optimization algorithm and the CPLEX solver. The results show that ICS has very good optimization efficiency. The blending solution can provide a reference for refineries to find the similar crude oil. And the method proposed can also give some references to selection and blending optimization of other materials.