Fischer-Tropsch wax catalytic cracking for the production of low olefin and high octane number gasoline: Process optimization and heat effect calculation

To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.

A History of Fischer-Tropsch Wax Upgrading at BP-from Catalyst Screening Studies to Full Scale Demonstration in Alaska

Conversion of Fischer-Tropsch wax into high quality synthetic crude or finished transportation fuels such as premium diesel has been studied over the past 15 years within BP. Catalyst screening and selection was carried out in dedicated micro-reactors and pilot plants, whose designs are critical to the performance selection. Variation in catalyst composition and defining the gas to oil feed ratios with the operating temperature are a few of the parameters studied. Product selection and maximizing diesel yield combined with stability （catalyst life） were the ultimate drivers. The selected catalyst was then tested under commercial conditions in a dedicated 300 barrel per day demonstration plant. The products were also tested in engines to assess their combustion characteristics.

Computer generation of detailed reaction networks in hydrocracking of Fischer-Tropsch wax

Fischer-Tropsch synthesis(FTS)wax is a mixture of linear hydrocarbons with carbon number from C7 to C70+.Converting FTS wax into high-quality diesel(no sulfur and nitrogen contents)by hydrocracking technology is attractive in economy and practicability.Kinetic study of the hydrocracking of FTS wax in elementary step level is very challenging because of the huge amounts of reactions and species involved.Generation of reaction networks for hydrocracking of FTS wax in which the chain length goes up to C70 is described on the basis of Boolean adjacency matrixes.Each of the species(including paraffins,olefins and carbenium ions)involved in the elementary steps is represented digitally by using a(N+3)N matrix,in which a group of standardized numbering rules are designed to guarantee the unique identity of the species.Subsequently,the elementary steps are expressed by computer-aided matrix transformations in terms of proposed reaction rules.Dynamic memory allocation is used in species storage and a characteristic vector with nine elements is designed to store the key information of a(N+3)N matrix,which obviously reduces computer memory consumption and improves computing efficiency.The detailed reaction networks of FTS wax hydrocracking can be generated smoothly and accurately by the current method.The work is the basis of advanced elementary-step-level kinetic modeling.

Boosting Fischer-Tropsch Synthesis via Tuning of N Dopants in TiO_(2)@CN-Supported Ru Catalysts

Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.

Probing the interaction between asphaltene-wax and its effects on the crystallization behavior of waxes in heavy oil via molecular dynamics simulation

High content of asphaltenes and waxes leads to the high pour point and the poor flowability of heavy oil,which is adverse to its efficient development and its transportation in pipe.Understanding the interaction mechanism between asphaltene-wax is crucial to solve these problems,but it is still unclear.In this paper,molecular dynamics simulation was used to investigate the interaction between asphaltenewax and its effects on the crystallization behavior of waxes in heavy oil.Results show that molecules in pure wax are arranged in a paralleled geometry.But wax molecules in heavy oil,which are close to the surface of asphaltene aggregates,are bent and arranged irregularly.When the mass fraction of asphaltenes in asphaltene-wax system(ω_(asp))is 0-25 wt%,the attraction among wax molecules decreases and the bend degree of wax molecules increases with the increase ofω_(asp).Theω_(asp)increases from 0 to 25 wt%,and the attraction between asphaltene-wax is stronger than that among waxes.This causes that the wax precipitation point changes from 353 to 333 K.While theω_(asp)increases to 50 wt%,wax molecules are more dispersed owing to the steric hindrance of asphaltene aggregates,and the interaction among wax molecules transforms from attraction to repulsion.It causes that the ordered crystal structure of waxes can't be formed at normal temperature.Simultaneously,the asphaltene,with the higher molecular weight or the more hetero atoms,has more obvious inhibition to the formation of wax crystals.Besides,resins also have an obvious inhibition on the wax crystal due to the formation of asphalteneresin aggregates with a larger radius.Our results reveal the interaction mechanism between asphaltene-wax,and provide useful guidelines for the development of heavy oil.

Differences in leaf cuticular wax induced by whole-genome duplication in autotetraploid sour jujube

Drought-resistant plants exhibit strong water retention capability.In this regard,the autotetraploid sour jujube leaves exhibit better water retention than diploid leaves.Morphological comparisons and physiological comparisons of diploid and autotetraploid leaves showed that the autotetraploid leaves had thicker leaf cuticles and more leaf wax accumulation than the diploid leaves,which could reduce cuticle permeability and improve the drought tolerance of leaves.In this study,the cuticular wax crystalloids on the adaxial and abaxial sides of young and mature jujube leaves were observed in the two ploidy types,and unique cuticular wax crystalloids covering a large area of the cuticle on autotetraploid sour jujube leaves may provide an advantage in reducing leaf non-stomata transpiration and improving plant drought tolerance.Based on the transcriptome,115 differentially expressed genes between diploids and autotetraploids were further analyzed and found to be involved in the accumulation of cuticular wax components,including terpenoids,fatty acids,and lipids,as well as ABC transporter and wax biosynthetic process.Finally,14 genes differentially expressed between glossy autotetraploid leaves and nonglossy diploid leaves,such as LOC107414787,LOC107411574 and LOC107413721,were screened as candidate genes by qRT-PCR analysis.This findings provided insights into how polyploidization improved drought tolerance.

Experimental study on wax deposition of highly paraffinic oil in intermittent gas-oil flow in pipelines

Oil-gas two phase wax deposition is a fairly common and open-ended question in flow assurance of multiphase transportation pipelines.This paper investigated the two main aspects of oil-gas two phase wax deposition layer:apparent thickness and crystal structure characteristics.A typical highly paraffinic oil in Bohai Sea,China,was used as the experimental material to investigate the wax deposition thickness in oil-gas two phase under the influence of different oil temperatures,superficial gas/liquid phase velocities and gas-oil ratios by using multiphase flow loop experimental device.Just as in the classical theory of wax molecular diffusion,it showed that wax deposition thickness of oil-gas two phase increased with increasing oil temperature.Analysis of the impact of different superficial phase velocities found that the actual liquid flow heat transfer and shear stripping was the gas phase dominant mechanisms determining wax deposit thickness.In addition,the crystal structure of the wax deposition layer was characterized with the help of small-angle X-ray scattering(SAXS)for different circumferential positions,flow rates and gas-oil ratios.The bottom deposition layer had a complex crystal structure and high hardness,which were subject to change over flow rate variations.Furthermore,the SAXS results provided evidence that the indirect effect of the actual liquid velocity modified by the gas phase was the main mechanism.Our study of the effect of gas phase on the wax deposition of oil-gas two phase will help shed light onto the mechanism by which this important process occurs.Our findings address a very urgent need in the field of wax deposition of highly paraffinic oil to understand the flow security of oilgas two phase that occurs easily in multiphase field pipelines.

ZmCER1,a putative ECERIFERUM 1 protein in maize,functions in cuticular wax biosynthesis and bulliform cell development

The cuticular wax,acting as the ultimate defense barrier,is essential for the normal morphogenesis of plant organs.Despite this importance,the connection between wax composition and leaf development has not been thoroughly explored.In this study,we characterized a new maize mutant,ragged leaf4(rgd4),which exhibits crinkled and ragged leaves starting from the sixth leaf stage.The phenotype of rgd4 is conferred by ZmCER1,which encoding an aldehyde decarbonylase involved in wax biosynthesis.ZmCER1 function deficient mutant displayed reduced cuticular wax density and disordered bulliform cells(BCs),while ZmCER1 overexpressing plants exhibited the opposite effects,indicating that ZmCER1 regulates cuticular wax biosynthesis and BCs development.Additionally,as the density of cuticular wax increased,the water loss rate of detached leaf decreases,suggesting that ZmCER1 is positively correlated with plant drought tolerance.

Modeling analysis of cobalt-based Fischer-Tropsch catalyst particles

The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.

涂装高浸透WAX应用说明

主要介绍了高浸透WAX材料的特性,以及基于现有设备基础进行相关的设备改造及注意事项。

Prediction Model of Wax Deposition Rate in Waxy Crude Oil Pipelines by Elman Neural Network Based on Improved Reptile Search Algorithm

A hard problem that hinders the movement of waxy crude oil is wax deposition in oil pipelines.To ensure the safe operation of crude oil pipelines,an accurate model must be developed to predict the rate of wax deposition in crude oil pipelines.Aiming at the shortcomings of the ENN prediction model,which easily falls into the local minimum value and weak generalization ability in the implementation process,an optimized ENN prediction model based on the IRSA is proposed.The validity of the new model was confirmed by the accurate prediction of two sets of experimental data on wax deposition in crude oil pipelines.The two groups of crude oil wax deposition rate case prediction results showed that the average absolute percentage errors of IRSA-ENN prediction models is 0.5476% and 0.7831%,respectively.Additionally,it shows a higher prediction accuracy compared to the ENN prediction model.In fact,the new model established by using the IRSA to optimize ENN can optimize the initial weights and thresholds in the prediction process,which can overcome the shortcomings of the ENN prediction model,such as weak generalization ability and tendency to fall into the local minimum value,so that it has the advantages of strong implementation and high prediction accuracy.

Pre-heating temperature induced flowability and wax deposition characteristics of crude oil adding wax inhibitors

This paper investigated the effects of pre-heating treatment temperatures(T_(pre))on the flowability and wax deposition characteristics of a typical waxy crude oil after adding wax inhibitors.It is found that there is little difference in wax precipitation exothermic characteristics of crude oils at different T_(pre),as well as the wax crystal solubility coefficient in the temperature range of 25-30℃.For the undoped crude oil,the flowability after wax precipitation gets much improved and the wax deposition is alleviated as T_(pre)increasing.At T_(pre)=50℃,the viscosity and wax deposition rate of crude oil adding wax inhibitors are higher than those of the undoped crude oil.When the T_(pre)increases to 60,70,and 80℃,the flowability of the doped crude oil are largely improved and the wax deposition is suppressed with the T_(pre)increase,but the wax content of wax deposit increases gradually.It is speculated that,on the one hand,the T_(pre)increase helps the dispersion of asphaltenes into smaller sizes,which facilitates the co-crystallization with paraffin waxes and generates more aggregated wax crystal flocs.This weakens the low-temperature gel structure and increases the solid concentration required for the crosslink to form the wax deposit.On the other hand,the decrease in viscosity increases the diffusion rate of wax molecules and accelerates the aging of wax deposits.The experimental results have important guiding significance for the pipeline transportation of doped crude oils.

Structures and Functions of Cuticular Wax in Postharvest Fruit and Its Regulation:A Comprehensive Review with Future Perspectives

Cuticular wax plays a major role in the growth and storage of plant fruits.The cuticular wax coating,which covers the outermost layer of a fruit’s epidermal cells,is insoluble in water.Cuticular wax is mainly composed of very long-chain fatty acids(VLCFAs);their derivatives,including esters,primary alcohols,secondary alcohols,aldehydes,and ketones;and triterpenoids.This complex mixture of lipids is probably biosynthesized in the epidermal cells of most plants and exuded onto the surface.Cuticular wax not only makes the fruit less susceptible to microbial infection but also reduces mechanical damage to the fruit,thereby maintaining the fruit’s commodity value.To date,research has mostly focused on the changes,function,and regulation of fruit wax before harvest,while ignoring the changes and functions of wax in fruit storage.This paper reviews on the composition,structure,and metabolic regulation of cuticular wax in fruits.It also focuses on postharvest factors affecting wax composition,such as storage temperature,relative humidity(RH),gas atmosphere,and as exogenous hormones;and the effects of wax on fruit postharvest quality,including water dispersion,fruit softening,physiological disorders,and disease resistance.These summaries may be of assistance in better understanding the changes in cuticular wax in postharvest fruit and the resulting effects on fruit quality.

Wax from Pyrolysis of Waste Plastics as a Potential Source of Phase Change Material for Thermal Energy Storage

Over the past half-century, plastic consumption has grown rapidly due to its versatility, low cost, and unrivaled functional properties. Among the diff erent implemented strategies for recycling waste plastics, pyrolysis is deemed the most economical option. Currently, the wax obtained from the pyrolysis of waste plastics is mainly used as a feedstock to manufacture chemicals and fuels or added to asphalt for pavement construction, with no other applications of wax being reported. Herein, the thermal pyrolysis of three common waste polyolefin plastics: high-density polyethylene(HDPE), low-density polyethylene(LDPE), and polypropylene(PP), was conducted at 450 ℃. The waste plastics-derived waxes were characterized and studied for a potential new application: phase change materials(PCMs) for thermal energy storage(TES). Gas chromatography–mass spectrometry analysis showed that paraffin makes up most of the composition of HDPE and LDPE waxes, whereas PP wax contains a mixture of naphthene, isoparaffin, olefin, and paraffin. Diff erential scanning calorimetry(DSC) analysis indicated that HDPE and LDPE waxes have a peak melting temperature of 33.8 ℃ and 40.3 ℃, with a relatively high latent heat of 103.2 J/g and 88.3 J/g, respectively, whereas the PP wax was found to have almost negligible latent heat. Fourier transform infrared spectroscopy and DSC results revealed good chemical and thermal stability of HDPE and LDPE waxes after 100 cycles of thermal cycling. Performance evaluation of the waxes was also conducted using a thermal storage pad to understand their thermoregulation characteristics for TES applications.

An optimized protocol using Steedman’s wax for high-sensitivity RNA in situ hybridization in shoot apical meristems and flower buds of cucumber

In situ mRNA hybridization(ISH)is a powerful tool for examining the spatiotemporal expression of genes in shoot apical meristems and flower buds of cucumber.The most common ISH protocol uses paraffin wax;however,embedding tissue in paraffin wax can take a long time and might result in RNA degradation and decreased signals.Here,we developed an optimized protocol to simplify the process and improve RNA sensitivity.We combined embedding tissue in low melting-point Steedman’s wax with processing tissue sections in solution,as in the whole-mount ISH method in the optimized protocol.Using the optimized protocol,we examined the expression patterns of the CLAVATA3(CLV3)and WUSCHEL(WUS)genes in shoot apical meristems and floral meristems of Cucumis sativus(cucumber)and Arabidopsis thaliana(Arabidopsis).The optimized protocol saved 4–5 days of experimental period compared with the standard ISH protocol using paraffin wax.Moreover,the optimized protocol achieved high signal sensitivity.The optimized protocol was successful for both cucumber and Arabidopsis,which indicates it might have general applicability to most plants.

Emerging low-density polyethylene/paraffin wax/aluminum composite as a form-stable phase change thermal interface material

Thermal interface materials(TIMs) play a vital role in the thermal management of electronic devices and can significantly reduce thermal contact resistance(TCR). The TCR between the solid–liquid contact surface is much smaller than that of the solid–solid contact surface, but conventional solid–liquid phase change materials are likely to cause serious leakage. Therefore, this work has prepared a new formstable phase change thermal interface material. Through the melt blending of paraffin wax(PW) and low-density polyethylene(LDPE), the stability is improved and it has an excellent coating effect on PW. The addition of aluminum(Al) powder improves the low thermal conductivity of PW/LDPE, and the addition of 15wt% Al powder improves the thermal conductivity of the internal structure of the matrix by 67%. In addition, the influence of the addition of Al powder on the internal structure, thermal properties, and phase change behavior of the PW/LDPE matrix was systematically studied. The results confirmed that the addition of Al powder improved the thermal conductivity of the material without a significant impact on other properties, and the thermal conductivity increased with the increase of Al addition. Therefore, morphologically stable PW/LDPE/Al is an important development direction for TIMs.

Overexpression of ZxABCG11 from Zygophyllum xanthoxylum enhances tolerance to drought and heat in alfalfa by increasing cuticular wax deposition

Drought and heat stresses cause yield losses in alfalfa,a forage crop cultivated worldwide.Improving its drought and heat tolerance is desirable for maintaining alfalfa productivity in hot,arid regions.Cuticular wax forms a protective barrier on aerial surfaces of land plants against environmental stresses.ABCG11encodes an ATP binding cassette(ABC) transporter that functions in the cuticular wax transport pathway.In this study,Zx ABCG11 from the xerophyte Zygophyllum xanthoxylum was introduced into alfalfa by Agrobacterium tumefaciens-mediated transformation.Compared to the wild type(WT),transgenic alfalfa displayed faster growth,higher wax crystal density,and thicker cuticle on leaves under normal condition.Under either drought or heat treatment in greenhouse conditions,the plant height and shoot biomass of transgenic lines were significantly higher than those of the WT.Transgenic alfalfa showed excellent growth and 50% greater hay yield than WT under field conditions in a hot,arid region.Overexpression of Zx ABCG11 up-regulated wax-related genes and resulted in more cuticular wax deposition,which contributed to reduction of cuticle permeability and thus increased water retention and photosynthesis capacity of transgenic alfalfa.Thus,overexpression of Zx ABCG11 can simultaneously improve biomass yield,drought and heat tolerance in alfalfa by increasing cuticular wax deposition.Our study provides a promising avenue for developing novel forage cultivars suitable for planting in hot,arid,marginal lands.

Cobalt supported on CNTs-covered γ-and nano-structured alumina catalysts utilized for wax selective Fischer-Tropsch synthesis

Cobalt supported on carbon nanotubes （CNTs）-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis （FTS）. Problems associated with shaping of Co/CNTs into extrudates or pellets as well as catalyst attrition rendered these materials unfavorable for industrial applications. In this investigation regular γ- and nano-structured （N-S） alumina as well as CNTs-covered regular γ- and N-S-alumina supports were impregnated by cobalt nitrate solution to make new cobalt-based catalysts which were also promoted by Ru. The catalysts were characterized and tested in a micro reactor to evaluate their applicability in FTS. γ-Al2O3 was prepared by calcination of bohemite and N-S-Al2O3 was prepared by sol-gel method using aluminum chloride as starting material. Catalyst evaluations indicated that N-S-Al2O3 was superior to regular γ-Al2O3 and that CNTs-covered alumina supports were favored over non-covered ones in terms of activity and heavy hydrocarbon selectivity. These were justified by porosimetric characteristics of the catalysts and existence of CNTs points of view. CNTs-covered catalysts also showed higher wax selectivity and better resistance to deactivation. Furthermore, TPR analysis indicated that the cobalt aluminate phase, which is responsible for the permanent deactivation of alumina supported Co-based catalysts, did not form on alumina supported Co-based catalysts covered with CNTs due to weaker interactions between cobalt and alumina.

Microchannel reactors for Fischer-Tropsch synthesis:Experimental investigation and mathematical modeling

The Fischer-Tropsch synthesis is a significant technology for converting coal,natural gas,and biomass into synthetic fuels.In recent years,the use of microchannel reactors for the Fischer-Tropsch synthesis has attracted significant attention.Fischer-Tropsch synthesis experiments were carried out in a microchannel reactor and the influences of reaction conditions on the experimental results were investigated in this study.Based on the experimental data,a dynamic multi-component pseudo-homogeneous variable-volume flow model of microchannel reactors for the Fischer-Tropsch synthesis was built to determine the pressure-,velocity-,conversion-and(component-wise)concentration-distributions in reaction channels.The model takes into account the combined effects of gas volume expansion caused by the frictional pressure drop and gas volume contraction caused by reaction consumption.A novel effective method for calculating the pressure and superficial gas velocity values in microchannel reactors was proposed in the model.Besides that,two sets of experimental data were selected from references to evaluate the validity and accuracy of the model.The reaction performances in the microchannels were analyzed carefully based on the calculated results.

Wax deposition modeling in oil-water stratified pipe flow

Wax deposition in oil-water stratified flow is commonly encountered onshore and offshore oil production pipe systems,and typically reduces transportation capacity of oil.The accurate predicted model of wax deposition has becomes an indispensable approach to design effective remediation strategies.However,a reliable mechanistic model for wax deposition prediction in oil-water two-phase stratified pipe flow is lacking to validate the deposition process.In this work,a three-dimensional(axial,radial,and angular)robust wax deposit model for oil-water stratified circular pipe flow was developed.The model of formation of a gel deposit based on the first principles of rheology was developed,associated with the results obtained from hydrodynamics and heat/mass transfer simulations.The predictions for wax deposition are found to compare satisfactorily with experimental data with two different oils for single phase and four different water cuts for oil-water stratified pipe flow.It can be seen from the wax gelation mechanism that an increase in water cut can help to reduce the wall/oil-deposit interface shear stress,thereby leading to an increase in the degree of gelation as well as the deposit rate.Furthermore,a local deposit analysis in the circumferential direction was conducted,for water cut 75%and total flow rate 5 m3/h,which provided insights to understand that the thickness on pipe wall was roughly uniformly distributed locates near the top of the pipe and the nearer the position gets close to two points,where the oil-water interface contacts the inner wall,the deposition thickness quickly dropped to 0.It was attributed to the fact that a roughly uniformly thickness far away from the oil-water interface contact the inner wall resulted in the slowly changes temperature along the circumferential pipe wall wetted by oil.