A molecular insight into coke formation process of vacuum residue in thermal cracking reaction

Understanding the coking behaviors has been considered to be really essential for developing better vacuum residue processing technologies.A battery of thermal cracking tests of typical vacuum residue at 410℃ with various reaction time were performed to evaluate the coke formation process.The total yields of ideal components including naphtha,atmospheric gas oil(AGO)and vacuum gas oil(VGO)of thermal cracking reactions increased from 10.89%to 40.81%,and the conversion ratios increased from8.05%to 43.33%with increasing the reaction time from 10 to 70 min.The asphaltene content increased from 12.14%to a maximum of 22.39%and then decreased,and this maximum of asphaltene content occurred at the end of the coking induction period.The asphaltenes during the coking induction period,at the end and after coking induction period of those tested thermal cracking reactions were characterized to disclose the structure changing rules for coke formation process,and the coke formation pathways were discussed to reveal the coke formation process at molecular level.

Continuous-discontinuous element method for three-dimensional thermal cracking of rocks

Thermal cracking of rocks can significantly affect the durability of underground structures in engineering practices such as geothermal energy extraction,storage of nuclear waste and tunnelling in freezeethaw cycle induced areas.It is a scenario of strong coupled thermomechanical process involving discontinuity behaviours of rocks.In this context,a numerical model was proposed to investigate the thermal cracking of rocks,in a framework of the continuous-discontinuous element method(CDEM)for efficiently capturing the initiation and propagation of multiple cracks.A simplex integration strategy was adopted to account for the influences of temperature-dependent material properties.Several benchmark tests were considered and the obtained results were compared with analytical solutions and numerical results from the literature.The results show that the fracture degree of the cases when considering temperature-dependent material parameters had 10%differences approximately compared with the cases with constant parameters.

Knowledge expression,numerical modeling and optimization application of ethylene thermal cracking:From the perspective of intelligent manufacturing

Applications of process systems engineering(PSE)in plants and enterprises are boosting industrial reform from automation to digitization and intelligence.For ethylene thermal cracking,knowledge expression,numerical modeling and intelligent optimization are key steps for intelligent manufacturing.This paper provides an overview of progress and contributions to the PSE-aided production of thermal cracking;introduces the frameworks,methods and algorithms that have been proposed over the past10 years and discusses the advantages,limitations and applications in industrial practice.An entire set of molecular-level modeling approaches from feedstocks to products,including feedstock molecular reconstruction,reaction-network auto-generation and cracking unit simulation are described.Multilevel control and optimization methods are exhibited,including at the operational,cycle,plant and enterprise level.Relevant software packages are introduced.Finally,an outlook in terms of future directions is presented.

Quantum Chemistry of PAHs Thermal Cracking with Different Hydrogenation Degree

In order to investigate the influence of hydrogenation degree and structural variety on reaction trend of polyaro- matic hydrocarbons (PAHs) in resins and asphaltenes portion of heavy oil, a series of PAHs with different hydrogenation degree were selected as model compounds to simulate their different hydrogenation stage, and the PAHs thermal cracking reaction was simulated based on free radical mechanism by the density functional theory (DFT) to search for reactions'transition state. By comparing the dynamic data obtained from reaction simulation, it is showed that processing difficulty could rise with increasing condensed aromatic ring number, and hydrogenation could promote ring cleavage reaction, but excessive hydrogenation would decrease the oil conversion rate to reduce light-end products. In conclusion, proper hydrogenation was quite critical in promoting light-end products conversion efficiency and saving the processing cost as well. Operational instructions were given based on both PAHs hydrogenation performance and conclusions were drawn up from reaction simulation results.

Kinetics and mechanisms of the catalytic thermal cracking of asphaltenes adsorbed on supported nanoparticles

The production of heavy and extra-heavy oil is challenging because of the rheological properties that crude oil presents due to its high asphaltene content.The upgrading and recovery processes of these unconventional oils are typically water and energy intensive,which makes such processes costly and environmentally unfriendly.Nanoparticle catalysts could be used to enhance the upgrading and recovery of heavy oil under both in situ and ex situ conditions.In this study,the effect of the Ni-Pd nanocatalysts supported on fumed silica nanoparticles on post-adsorption catalytic thermal cracking of n-C_7 asphaltenes was investigated using a thermogravimetric analyzer coupled with FTIR.The performance of catalytic thermal cracking of n-C_7asphaltenes in the presence of NiO and PdO supported on fumed silica nanoparticles was better than on the fumed silica support alone.For a fixed amount of adsorbed n-C_7asphaltenes（0.2 mg/m～2）,bimetallic nanoparticles showed better catalytic behavior than monometallic nanoparticles,confirming their synergistic effects.The corrected OzawaFlynn-Wall equation（OFW） was used to estimate the effective activation energies of the catalytic process.The mechanism function,kinetic parameters,and transition state thermodynamic functions for the thermal cracking process of n-C_7 asphaltenes in the presence and absence of nanoparticles are investigated.

A New Mathematical Simulation Approach for Thermal Cracking Furnace Studies

Thermal cracking of hydrocarbons for olefin production is normally carried out in long reactor tubes suspended in a large gas fired furnace. In this paper, a coupled furnace-reactor mathematical model based on a computational fluid dynamics (CFD) technique is developed to simulate the complex fluid dynamics phenomena in the thermal cracking furnace. The model includes mass transfer, momentum transfer, and heat transfer, as well as thermal cracking reactions, fuel combustion and radiative heat transfer. The rationality and reliability of the mathematical model is confirmed by the approximate agreement of predicted data and industrial data. The coupled furnace-reactor simulation revealed the details of both the transfer and reaction processes taking place in the thermal cracking furnace. The results indicate highly nonuniform distribution of the flue-gas velocity, concentration and temperature in the furnace, which cause nonuniform distribution of tube skin temperature and heat flux of the reactor tubes. Profiles of oil-gas velocity, pressure, temperature and product yields in the lengthwise direction of the reactor tube are obtained. Furthermore, in the radial direction steep velocity and temperature gradients and relatively slight gradients of species concentration are found. In conclusion, the model can provide more information on the fluid dynamics and reaction behavior in the thermal cracking furnace, and guidance for the design and improvement of thermal cracking furnaces.

A coupled CFD simulation approach for investigating the pyrolysis process in industrial naphtha thermal cracking furnaces

In the steam thermal cracking of naphtha,the hydrocarbon stream flows inside tubular reactors and is exposed to flames of a series of burners in the firebox.In this paper,a full three-dimensional computational fluid dynamics(CFD)model was developed to investigate the process variables in the firebox and reactor coil of an industrial naphtha furnace.This comprehensive CFD model consists of a standard k-εturbulence model accompanied by a molecular kinetic reaction for cracking,detailed combustion model,and radiative properties.In order to improve the steam cracking performance,the model is solved using a proposed iterative algorithm.With respect to temperature,product yield and specially propylene-toethylene ratio(P/E),the simulation results agreed well with industrial data obtained from a mega olefin plant of a petrochemical complex.The deviation of P/E results from industrial data was less than 2%.The obtained velocity,temperature,and concentration profiles were used to investigate the residence time,coking rate,coke concentration,and some other findings.The coke concentration at coil exit was1.9×10^(-3)%(mass)and the residence time is calculated to be 0.29 s.The results can be used as a scientific guide for process engineers.

THERMAL CRACK AND WEAR OF RAIL WHEEL AND DEVELOPMENT OF THERMAL CRACKING PROOF WHEELS

The thermal cracking and wear mechanism of rail wheel tread have been studied.The results showed that the thermal cracking of rail wheel tread is related to the chemical composition (mainly the carbon content)and the hardness of the wheels.When the composite braking shoes are used,the rate of wear of the wheel tread is related to the fracture toughness of the newly-formed“white layer”i.e.the martensite.The thermal cracking proof wheels(55SiMn) so far developed has achieved significant operating results in practical use.

Application of Thermal Cracking Mechanism of Chrysene Molecule Using Density Functional Theory

Density functional theory calculations were carried out to study the thermal cracking for chrysene molecule to estimate the bond energies for breaking C 10b-C 11, C 11-H 11 and C4a-C 12a bonds as well as the activation energies. It was found that for C 10b-C 11 C11-HI 1 and C4a-C12a reactions, it is often possible to identify one pathway for bond breakage through the singlet or triplet states. Thus, the C 11-H11 and C11-C10b bonds ruptured in triplet state whilst the C12a-C4a in singlet state. Also, it was fond that the activation energy value for C4a-C12a bond breakage is lower than required for C10b-C11 and C11-H11 bonds that enquired the C4a-C12a bond ＂bridge bond＂ is a weaker and ruptured firstly in thermal cracking process. It seems that the characteristic planarity for polyaromatic hydrocarbons is an important factor to acquire the molecule structure the required stability along the reaction paths as well as the full octet rule and Clar＇s n-sextet structure, especially when chrysene molecular lose the property of planarity. The atomic charges supported the observation that the breaking bonds C10b-C11, CI1-H11 and C4a-C12a in triplet or singlet states. The configurations in transition state and the conformation for the end products reaction were explained and discussed.

Thermally-induced cracking behaviors of coal reservoirs subjected to cryogenic liquid nitrogen shock

The benefits of using cryogenic liquid nitrogen shock to enhance coal permeability have been confirmed from experimental perspectives.In this paper,we develop a fully coupled thermo-elastic model in combination with the strain-based isotropic damage theory to uncover the cooling-dominated cracking behaviors through three typical cases,i.e.coal reservoirs containing a wellbore,a primary fracture,and a natural fracture network,respectively.The progressive cracking processes,from thermal fracture initiation,propagation or cessation,deflection,bifurcation to multi-fracture interactions,can be well captured by the numerical model.It is observed that two hierarchical levels of thermal fractures are formed,in which the number of shorter thermal fractures consistently exceeds that of the longer ones.The effects of coal properties related to thermal stress levels and thermal diffusivity on the fracture morphology are quantified by the fracture fractal dimension and the statistical fracture number.The induced fracture morphology is most sensitive to changes in the elastic modulus and thermal expansion coefficient,both of which dominate the complexity of the fracture networks.Coal reservoir candidates with preferred thermal-mechanical properties are also recommended for improving the stimulation effect.Further findings are that there exists a critical injection temperature and a critical in-situ stress difference,above which no thermal fractures would be formed.Preexisting natural fractures with higher density and preferred orientations are also essential for the formation of complex fracture networks.The obtained results can provide some theoretical support for cryogenic fracturing design in coal reservoirs.

Effect of rare earth elements on the thermal cracking resistance of high speed steel rolls

The effect of rare earth elements on the thermal cracking resistance of high speed steel （HSS） rolls was investigated. Laser rapid heating was used for thermal fatigue experiments. Thermal cracks and microstructure were observed using metalloscopy and scanning electron microscopy. The results showed that thermal cracks initiated from the interface between the matrix and eutectic carbides （including M6C and M7C3 type carbides）,and propagated along the interface between the two phases. MC type carbides enriched with vanadium could prevent the propagation of thermal cracks. The presence of rare earth elements decreased the quantity of big eutectic carbides,and proportionally increased spherical and rod-shaped MC type carbide content. HSS0 （0.00% RE） had approximately three times the thermal cracking density of HSS3 （0.12 wt.% RE）. Rare earth elements were shown to significantly improve the microstructure and thermal cracking resistance of HSS rolls.

Comparative study on thermal cracking characteristics and bio-oil production from different microalgae using Py-GC/MS

The yield and chemical composition of pyrolysis products of Chlorella pyrenoidosa and Schizochytrium limacinum were determined using thermogravimetric analyzer(TGA)and pyrolysis-gas chromatographic mass spectrometry(Py-GC/MS)by varying the temperature ranges.After further analysis of the total ion current(TIC)diagrams of Chlorella pyrenoidosa and Schizochytrium limacinum,it was concluded that both the pyrolysis products of each sample were mainly comprised of hydrocarbons,aromatics,fatty acids,nitrogen compounds,PAHs,phenols,etc,however,the relative content of each compound from Chlorella pyrenoidosa and Schizochytrium limacinum was different.The pyrolysis of Chlorella pyrenoidosa and Schizochytrium limacinum at 350℃ produced a maximum yield of bio-oil production(44.32%and 60.99%);moreover,Chlorella pyrenoidosa could lead to more pollutants(nitrogen compounds and PAHs)release(2.71%)compared to that of Schizochytrium limacinum(0.7%).Considering the reasonable bio-oil production and minimum release of pollutants,Schizochytrium limacinum was found to be superior for producing biofuel against Chlorella pyrenoidosa.

Thermal cracking products and bio-oil production from microalgae Desmodesmus sp.

Qualitative and quantitative analyses of thermal cracking products from Desmodesmus sp.were performed based on pyrolysis-gas chromatography-mass spectrometry(Py-GC/MS)at different temperature regimes(350℃-750℃).After further analysis of a series of total ions chromatogram(TIC)and summarized,thermal cracking products of Desmodesmus sp.at different temperature regimes can be obtained,which mainly comprised of aliphatic hydrocarbons,nitrogen compounds,aromatic hydrocarbons,fatty acids,ketones,alcohols,aldehydes and furan compounds.Compared to bio-oil production at 650℃(32.07%),Desmodesmus sp.pyrolyzed at 750℃could produce the highest bio-oil content of 42.25%.However,higher temperature could lead to the formation of contaminants(nitrogen compounds and PAHs)more easily.Therefore,considering the higher content of bio-oil conversion and less pollutants generation,the optimum temperature for Desmodesmus sp.thermal cracking conversion was about 650℃.

Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal crack-ing of home-made jet fuel RP-3 under supercritical con-ditions.The mechanism and precursor of coke forming were analyzed.The starting cracking temperature of RP-3 fuel was determined to be 471.8uC by differential scan-ning calorimetry(DSC).Temperature-programmed oxidation and scanning electron microscopy(SEM)characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon,amorphous carbon and filamentous coke in the solid deposits.More than 90%of coke deposits are carried away by the supercritical fluid,which has strong capabilities of extraction for coke deposits and their pre-cursors.There were 17.1 wt-%of iron and 11.1 wt-%of chromium found on the coke surface detected by energy dispersive spectroscopy(EDS)which suggests carbure-tion on alloy.RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids.

Acoustic emission assessment of interface cracking in thermal barrier coatings

In this paper,acoustic emission（AE） and digital image correlation methods were applied to monitor interface cracking in thermal barrier coatings under compression.The interface failure process can be identifie via its AE features,including buckling,delamination incubation and spallation.According to the Fourier transformation of AE signals,there arefourdifferentfailuremodes：surfaceverticalcracks,opening and sliding interface cracks,and substrate deformation.The characteristic frequency of AE signals from surface vertical cracks is 0.21 MHz,whilst that of the two types of interface cracks are 0.43 and 0.29 MHz,respectively.The energy released of the two types of interface cracks are 0.43 and 0.29 MHz,respectively.Based on the energy released from cracking and the AE signals,a relationship is established between the interface crack length and AE parameters,which is in good agreement with experimental results.

THERMAL FATIGUE CRACKING IN STEEL 5CrMnMo

The thermal fatigue behaviour of steel 5CrMnMo after various heat treatments has been examined by means of Coffin-model and self-strained thermal fatigue testing machines.The thermal fatigue crack initiation and propagation have been observed under SEM and TEM. The majority of thermal fatigue cracks of the quenched samples initiated firstly at the grain boundaries and that of the quenched-tempered samples at the breakage interface of the car- bide and matrix.The thermal fatigue cracks of either quenched or quenched-tempered steel propagated mainly along the breakage interface of carbide and grain boundaries.

Natural gas pyrolysis in double-walled reactor tubes using thermal plasma or concentrated solar radiation as external heating source

The thermal pyrolysis of natural gas as a clean hydrogen production route is examined. The concept of a double-walled reactor tube is proposed and implemented. Preliminary experiments using an external plasma heating source are carried out to validate this concept. The results point out the efficient CH4 dissociation above 1850 K （CH4 conversion over 90%） and the key influence of the gas residence time. Simulations are performed to predict the conversion rate of CH4 at the reactor outlet, and are consistent with experimental tendencies. A solar reactor prototype featuring four independent double-walled tubes is then developed. The heat in high temperature process required for the endothermic reaction of natural gas pyrolysis is supplied by concentrated solar energy. The tubes are heated uniformly by radiation using the blackbody effect of a cavity-receiver absorbing the concentrated solar irradiation through a quartz window. The gas composition at the reactor outlet, the chemical conversion of CH4, and the yield to H2 are determined with respect to reaction temperature, inlet gas flow-rates, and feed gas composition. The longer the gas residence time, the higher the CH4 conversion and H2 yield, whereas the lower the amount of acetylene. A CH4 conversion of 99% and H2 yield of about 85% are measured at 1880 K with 30% CH4 in the feed gas （6 L/min injected and residence time of 18 ms）, A temperature increase from 1870 K to 1970 K does not improve the H2 yield.

Effect of Hot Deformation on Formation and Growth of Thermal Fatigue Crackin Chromium Wear Resistant Cast Iron

The formation and growth of thermal fatigue crack in chromium wear resistant cast iron was investigated, and the effect of hot deformation on the crack was analyzed by means of optical microscope and scanning electron microscope and high frequency induction thermal fatigue tester. The results show that eutectic carbide is the main location and passage for initiation and extension of thermal fatigue cracks, hot deformation can improve the eutectic carbiders morphology and distribution, inhibit the generation and propagation of thermal fatigue cracks. In the experiment, the propagation rate of thermal fatigue crack reduces with the quantity of hot deformation increasing, which was analyzed in the point view of the activation energy of crack propagation.

Quantitative assessment of the surface crack density in thermal barrier coatings

In this paper, a modified shear-lag model is developed to calculate the surface crack density in thermal barrier coatings（TBCs）. The mechanical properties of TBCs are also measured to quantitatively assess their surface crack density. Acoustic emission（AE） and digital image correlation methods are applied to monitor the surface cracking in TBCs under tensile loading. The results show that the calculated surface crack density from the modified model is in agreement with that obtained from experiments. The surface cracking process of TBCs can be discriminated by their AE characteristics and strain evolution. Based on the correlation of energy released from cracking and its corresponding AE signals, a linear relationship is built up between the surface crack density and AE parameters, with the slope being dependent on the mechanical properties of TBCs.

Intrinsic Kinetic Modeling of Thermal Dimerization of C5 Fraction

This work aims to investigate the intrinsic kinetics of thermal dimerization of C_5 fraction in the reactive distillation process. Experiments are conducted in an 1000-m L stainless steel autoclave under some selected design conditions. By means of the weighted least squares method, the intrinsic kinetics of thermal dimerization of C_5 fraction is established, and the corresponding pre-exponential factor as well as the activation energy are determined. For example, the pre-exponential factor A is equal to 4.39×105 and the activation energy E4 a is equal to 6.58×10J/mol for the cyclopentadiene dimerization reaction. The comparison between the experimental and calculated results shows that the kinetics model derived in this work is accurate and reliable, which can be used in the design of reactive distillation columns.