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.

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.

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.

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.

On the treatment of thermal cracks in lining concrete of water conveyance system of Three Gorges Project permanent ship locks

A comprehensive investigation was performed for repairing the different types of cracks appearing on the surface or inside the concrete lining at various depths.The mate- rial properties used in grouting and two methods for crack repair were discussed in details, and consequently reliable repair measures were proposed and implemented.It is a better choice to adopt the hole-drilling method for the relatively regular crack.The grouting pres- sure should not be too high and it is generally between 0.4～0.6 MPa.For the second time grouting,the pressure maybe increased to 0.8 MPa.Other method is the pasting nozzles method which is more suitable for irregular cracks such as cracks with intensive density and crossing cracks.Its grouting pressure is generally between 0.6～1.0 MPa.The in-situ tests in Three Gorges Project demonstrate favorably the feasibility and applicability of the proposed methods for crack repair within the lining concrete.

Alternative Diesel Grade Fuel Transformed from Polypropylene (PP) Municipal Waste Plastic Using Thermal Cracking with Fractional Column Distillation

Day by day worldwide use of plastics is increasing because of their light weight and durable characteristics. Waste plastics are major environmental problems all over the world. Waste plastics are not bio-degradable, it remains in the landfill for a long period of time causing vegetation and aquatic ecosystem dilemmas. Abandoned waste plastic thrown into the ocean causes friction of ocean waves and then broken down by sunlight into small pieces and takes the shape of plastic like soup. Aquatic organism mistakes the plastic soup as their food and can’t digest, either they die or through food chain it affects human health. To avoid severe environmental degradation problems of waste plastics some countries and big cities banned or restricted the use of plastic products. The worldwide generation of waste plastics is approximately 280 million tons/year. All most all of these waste plastics are dumped either in land or ocean. City municipalities spend huge amount of money each year just to dispose of these waste plastics into landfill because most waste plastics are not recycled. When the waste plastics are subjected to incineration, they release harmful toxic gas into the environment causing severe pollution. These waste plastics gradually enhance the hazardous environmental problems. Generally plastics are made from crude oil, however crude oil is a very limited natural resource and non-renewable. Every year millions of barrels of crude oil are to produce the waste plastics and when plastics are discarded after use the energy source is lost. A new developed technology plan minimizes the environment pollution problems simultaneously boost up energy sector by renovating the waste plastics into high energy content fuel. The produced fuel is obtained using a unique thermal degradation of waste plastics and converting them into hydrocarbon fuel like materials. Preliminary tests proved that this fuel burns cleaner and the production cost is very low. Unique production setup demonstrated to produce 93% fuel from waste plastic in the pilot scale. The Fuel produced has been tested and proven to work on majority types of internal combustion engines. This technology utilized can avoid waste plastic pollution problem worldwide by the implementation of newly developed technology. Through the utilization of the technology the use of reliable plastics won’t need to be banned and serve as a very reliable alternate source of energy. The technology will also help reduce a significant amount of import oil from foreign countries and help provide a steady economy.

Study on the Role of Thermal Cracking in FCC Cycle

A bench-scale fixed fluidized bed reactor was used to study the distribution and quality of productsderived from thermal cracking of VGO. Test results had shown that the space velocity has minor effect onthermal cracking reaction. The depth of thermal cracking reaction was mainly affected by the reaction temperature.At different reaction temperatures the form of free radicals thus initiated varied, resulting in different productdistribution. At low temperature C10= and C11= olefins dominated in thermally cracked gasoline products,whereas at higher temperature C6=C9= olefins dominated in thermally cracked gasoline products, amongwhich C6 and C7 olefins were mainly composed of 2M1C5= and 2E1C5=. Difference in olefin structure can leadto different reaction pathways of catalytic cycle.

Spatial Thermal Crack Control in Mass Concrete

The finite element software,MIDAS is used to predict the distribution of temperatures and,analyzes the cracking control methods within a hydrating mass concrete.The temperature control of mass concrete has great significance in assuring the project quality.Adiabatic or semi adiabatic temperature measurement is mostly used for measuring and controlling the temperature fluctuation during construction.The temperature distribution produced by the finite element thermal analysis of the model is used to quantify the maximum allowable internal temperature difference before crack initiation on concrete.This study analyzes the data from one high-rise structure project in Shanghai are used to verify the finite element model developed.Results suggest that reliance on a limiting maximum temperature differential to control cracking in massive concrete applications should be supplemented with a requirement for analysis showing the calculated spatial temperature and stress response to the predicted temperature distribution within the concrete,to ensure that the induced tensile stresses will not exceed the tensile strength of the concrete and so minimize the risk of having thermal cracks at early age.

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.

Thermal Stresses and Cracks During the Growth of Large-sized Sapphire with SAPMAC Method

The finite-element method has been used to study the thermal stress distribution in large-sized sapphire crystals grown with the sapphire growth technique with micro-pulling and shoulder-expanding at cooled center （SAPMAC） method. A critical defect model has been established to explain the growth and propagation of cracks during the sapphire growing process. It is demonstrated that the stress field depends on the growth rate, the ambient temperature and the crystallizing direction. High stresses always exist near the growth interfaces, at the shoulder-expanding locations, the tailing locations and the sites where the diameters undergo sharp changes. The maximum stresses always occur at the interface of seeds and crystals. Cracks often form in the critical defect region and spread in the m-planes and a-planes under applied tensile stresses during crystal growth. The experimental results have verified that with the improved system of crystal growth and well-controlled techniques, the large-sized sapphire crystals of high quality can be grown due to absence of cracks.

Power generation and heat sink improvement characteristics of recooling cycle for thermal cracked hydrocarbon fueled scramjet

In order to further investigate how much fuel heat sink could be increased and how much power generation could be obtained by using recooling cycle for a regeneratively cooled scramjet,the energy conversion from heat to electricity and the fuel heat sink increase in recooling cycle are experimentally investigated for fuel conversion rate and components of gas cracked fuel products at different fuel temperatures.The results indicate that the total fuel heat sink(i.e.,physical+chemical+recooling) of a recooling cycle is obviously higher than the heat sink of fuel itself,and the maximum heat sink increment is as high as 0.4 MJ/kg throughout the recooling cycle.Furthermore,the cracked fuel mixture has a significant capacity of doing work.The thermodynamic power generation scheme,which adopts the cracked fuel gas mixture as the working fluid,is a potential power generation cycle,and the maximum specific power generation is about 500 kW/kg.Turbine-pump scheme using cracked fuel gas mixture is also a potential fuel feeding cycle.

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℃.