Comparative pyrolysis kinetics of heavy oil and its SARA fractions using distributed activation energy model

The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were determined by Friedman,one-parallel and four-parallel distributed activation energy model(DAEM),respectively.The results indicated that the pyrolysis behavior of QD-VR was similar to that of aromatics.For saturates,the release of H_(2),CH_(4),CO,and CO_(2) occurred in 80-400℃,while the temperature range for QD-VR and other fractions is 200-800℃.The average activation energy(Ea)via Friedman method was 179.72 kJ/mol and increased with the conversion ratio.One-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of the single SARA fractions,while four-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of heavy oil.Furthermore,comparing the weighted E_(a) from one-parallel(227.64 kJ/mol)and four-parallel Gaussian DAEM(204.63 kJ/mol),the results suggested that during pyrolysis process of heavy oil,there was an interaction between the SARA fractions,which could reduce the E_(a) of heavy oil pyrolysis.Specifically,during heavy oil pyrolysis,resins and asphaltenes could increase the E_(a) of saturates and aromatics,while saturates and aromatics could decrease the E_(a) of resins and asphaltenes.

Mechanism,Kinetics,and Thermodynamic Characteristics for the Demetallization of Used Lubricating Oil via Pyrolysis

This study analyzed the pyrolysis mechanism,developed a pyrolysis kinetic model,and determined the corresponding thermodynamic parameters for the removal of calcium from used lubricating oil using sulfurized calcium alkyl phenolate(T-115B)as a model compound.The pyrolysis process and products were evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy.Visual inspection indicated that the removal of calcium from T-115B depended primarily on the destruction of micelles caused by the pyrolysis of compounds at high temperatures.The pyrolysis characteristics of T-115B at different heating rates were investigated by thermogravimetry and differential thermal analysis,which revealed two distinct pyrolysis phases.Thus,the pyrolysis mechanism can be described by a twostep model.The activation energy and thermodynamic parameters(ΔH,ΔG,andΔS)were determined by applying the Kissinger-Akahira-Sunose,Flynn-Wall-Ozawa,Friedman,and Starink methods;the average activation energies for T-115B pyrolysis obtained using these methods were 115.80,119.84,124.96,and 116.14 kJ/mol,respectively.Further,both stages of the pyrolysis reaction followed Fn mechanisms with n=1.39 in the first stage and n=0.86 in the second stage.This study provides reliable and effective pyrolysis models along with kinetic and thermodynamic parameters to facilitate the largescale industrial application of used lubricating oil.

Pyrolysis Characteristics and Kinetics of Municipal Solid Waste

Based on a systemic survey, the pyrolysis characteristics and apparent kinetics of the municipal solid waste （ MSW） under different conditions were researched using a special pyrolysis reactor, which could overcome the disadvantage of thermo-gravimetric analyzer. The thermal decomposition behaviour of MSW was investigated using thermo-gravimetric （ TG ） analysis at rates of 4.8,6.6,8.4, 12.0 and 13. 2 K/min. The pyrolysis characteristics of MSW were also studied in different function districts. The pyrolysis of MSW is a complex reaction process and three main stages are found according to the results. The first stage represents the degradation of cellulose and hemicellulose, with the maximum degradation rate occuring at 150℃ -200 ℃： the second stage represents dehydrochlorination and depolymerization of intermediate products and the differential thermogravimetric （ DTG ） curves have shoulder peaks at about 300℃： the third stage is the decomposition of the residual big molecular organic substance and lignin at 400 ℃- 600 ℃. Within the range of given experimental conditions, the results of non-linear fitting algorithm and experiment are in agreement with each other and the correlation coefficients are over0. 99. The kinetic characteristics are concerned with the material component and heating rate. The activation energy of reaction decreases with the increase of heating rate.

Effect of demineralization on pyrolysis characteristics of LPS coal based on its chemical structure

The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.

Thermal decomposition characteristics and kinetics of methyl linoleate under nitrogen and oxygen atmospheres

The thermal decomposition characteristics of methyl linoleate （ML） under nitrogen and oxygen atmo- spheres were investigated, using a thermogravimetric analyzer at a heating rate of 10 ~C/min from room tem- perature to 600℃. Furthermore, the pyrolytic and kinetic characteristics of ML at different heating rates were stud- ied. The results showed that the thermal decomposition characteristics of ML under nitrogen and oxygen atmo- spheres were macroscopically similar, although ML exhibited relatively lower thermal stability under an oxy- gen atmosphere than under a nitrogen atmosphere. The initial decomposition temperature, the maximum weight loss temperature, the peak decomposition temperature, and the rate of maximum weight loss of ML under an oxygen atmosphere were much lower than those under a nitrogen atmosphere and increased with increasing heating rates under either oxygen or nitrogen atmosphere. In addition, the kinetic characteristics of thermal decomposition of ML were elucidated based on the experimental results and by the multiple linear regression method. The activation energy, pre-exponential factor, reaction order, and the kinetic equation for thermal decomposition of ML were obtained. The comparison of experimental and calculated data and the analysis of statistical errors of pyrolysis ratios demonstrated that the kinetic model was reliable for pyrolysis of ML with relative errors of about 1%. Finally, the kinetic compensation effect between the pre-exponential factors and the activation energy in the pyrolysis of ML was also confirmed.

Simple preparation of C(CS)/g-C_(3)N_(4)/Co carbon aerogel and its catalytic performance for ammonium perchlorate

Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a catalytic center point.The carbon aerogel(C(CS)/g-C_(3)N_(4)/Co)with a three-dimensional network-like structure was prepared by assembling the three materials through experimental operations such as freeze-drying and high-temperature carbonization.It was demonstrated by scanning and transmission characterization that the CS in the carbon aerogel could provide more active sites for the cobalt nanoparticles,and the doping of graphite-phase carbon nitride as a template dispersed the cobalt nanoparticles and changed the conductivity of the CS.To investigate the catalytic effect of carbon aerogel on ammonium perchlorate(AP),it was investigated by differential thermal analyzer and TG thermal analysis.This carbon aerogel was very effective in catalyzing AP,and the 10 wt% content of the catalyst reduced the AP pyrolysis peak from 703.9 to 595.5 K.And to further investigate the synergistic effect of the three materials,further carbon aerogels such as C(CS)/Co,g-C_(3)N_(4)/Co were prepared and applied to catalyze AP,and the same ratio reduced the AP pyrolysis peak by 98.1℃ and 97.7℃.This result indicates a synergistic effect of the assembly of the three materials.

The dynamic changes and mechanisms of Rehmanniae radix processing based on Maillard reaction

Background:Traditional Chinese medicines are usually processed before they are used for clinical treatment.This is done in a way associated with the Maillard reaction.Methods:Based on the Maillard reaction,this paper analyzed the degree of processing of rehmannia root(Rehmanniae radix)relative to the dynamic variation rules of Maillard reaction index parameters,including pH,A420,amino acids,and 5-hydroxymethylfurfural.Furthermore,this study introduced thermal analysis techniques and pyrolysis kinetics to assess the influence of the correlation between processing raw rehmannia root and the Maillard reaction during carbonization.It then went through the whole process of transforming the raw material to end-product in order to explain the scientific connotation of processing it.Results:The results showed that each time rehmannia root was processed,its pH value and amino acid content decreased,while the A420 value and 5-HMF increased.Processing with wine shows a significant difference in these experimental indexes.The position and intensity of the maximum thermal weight loss rate peak of processed rehmannia root at different degrees of processing are different.Comprehensive quantitative 221±0.2°C for processed rehmannia root carbonization was the processing temperature limit.Moreover,the kinetic solution verified that the activation energy corresponding to the carbonization temperature was close to the maximum value of the activation energy of the whole carbonization process,and the optimal mechanism function was g(α)=((1−α)−1/3−1)2.Conclusion:The Maillard reaction occurred during the processing of rehmannia root mixed with carbonization.With each increase of the number of steaming and drying cycles involved in the processing,the level of Maillard reaction increased significantly.The wine-steaming method had a significant effect on the quality of the processed product.

Analysis of safety characteristics of coal-based aviation kerosene

The risk and thermal safety characteristics of GX kerosene,HX kerosene and WX kerosene are studied.Firstly,the explosion lower limits of three kinds of kerosene steams are tested by using the self-made explosion limit measuring system.Then differential scanning calorimeter(DSC)is employed to perform linear heating experiment on kerosene to analyze its thermal decomposition characteristics.The pyrolysis kinetic parameters of three kinds of kerosene are calculated based on the thermal dynamic methods.The experimental results show that the flash point and lower explosion limit of GX kerosene are relatively low.The DSC test shows that the lowest initial decomposition temperature of HX kerosene is 116.5℃.According to pyrolysis kinetics calculation,the T_(D24) and apparent activation energy of HX kerosene are the minimum.ARC test shows that GX kerosene has the worst thermal stability under the adiabatic condition.The high temperature stabilities of the three kinds of kerosene all meet the requirements.On the whole,GX kerosene has the highest hazard,and HX kerosene has the lowest thermal safety.The accumulation of heat should be prevented during the storage and transportation of kerosene.This study provides the crucial safety characteristics data of coal-based aerospace kerosene-based,and provides technical support for engine reliability growth and performance improvement.

Transformation mechanism of nutrient elements in the process of biochar preparation for returning biochar to soil

Returning biochar to soil is a heavily researched topic because biochar functions well for soil improvement. There is a significant loss of nutrients, which occurs during biochar preparation before biochar is returned to soil,thereby seriously undermining biochar＇s efficacy. Therefore, the transformation mechanisms of biochar p H,mass, nutrients and metals during pyrolysis under different atmospheres and temperatures were studied such that the best method for biochar preparation could be developed. Several conclusions can be reached：（1） a CO2 atmosphere is better than a N2 atmosphere for biochar preparation, although preparation in a CO2 atmosphere is not a common practice for biochar producers;（2） 350 ℃is the best temperature for biochar preparation because the amount of nutrient loss is notably low based on the premise of straw transferred into biochar; and（3） transforming mechanisms of pH, N, P and K are also involved in the biochar preparation process.

Effects of iron compounds on pyrolysis behavior of coals and metallurgical properties of resultant cokes

The utilization of highly reactive and high-strength coke can enhance the efficiency of blast furnace by promoting indirect reduction of iron oxides.Iron compounds,as the main constituent in iron-bearing minerals,have aroused wide interest in preparation of highly reactive iron coke.However,the effects of iron compounds on pyrolysis behavior of coal and metallurgical properties of resultant cokes are still unclear.Thus,three iron compounds,i.e.,Fe;O;,Fe;O;and FeC;O;·2H;O,were adopted to investigate their effects on coal pyrolysis behavior and metallurgical properties of the resultant cokes.The results show that iron compounds have slight effects on the thermal behavior of coal blend originated from thermogravimetric and differential thermogravimetric curves.The apparent activation energy varies with different iron compounds ranging from 94.85 to 110.11 kJ/mol in the primary pyrolysis process,while lower apparent activation energy is required for the secondary pyrolysis process.Iron compounds have an adverse influence on the mechanical properties and carbon structure of cokes.Strong correlations exist among coke reactivity,coke strength after reaction,and the content of metallic iron in cokes or the values of crystallite stacking height,which reflect the dependency of thermal property on metallic iron content and carbon structure of cokes.

Synthesis and kinetics of non-isothermal degradation of acetylene terminated silazane

Novel acetylene terminated silazane compounds,with three types of substituent,were synthesized by the aminolysis of dichlorosilane with 3-aminophenylacetylene（3-APA）.Thermal property of the compounds is studied by thermogravimetry analysis （TGA）.It shows that the acetylene terminated silazane has high temperature resistance.The char yield at 1000℃is 77.6,81.9 and 68.7 wt%for methyl,vinyl,and phenyl substituted silazane,respectively.The pyrolysis kinetics of the silazane is investigated by non-isothermal thermogravimetric measurement.The pyrolysis undergoes three stages,which is resolved by PEAKFTT.The kinetic parameters are calculated by the Kissinger method.The role of functionalities on the thermal resistance is discussed.The vinyl-silazane exhibits higher thermal stability because of higher cross-linking density.

Effects of La-involvement on biomass pyrolysis behaviors and properties of produced biochar

In order to evaluate the effects of La-involvement on biomass pyrolysis behaviors and properties of produced biochar, oak sawdust（OS） and corn straw（CS） were employed for thermogravimetric-differential thermogravimetric（TG-DTG） analysis and producing biochar with/without La-involvement. Results indicated the initial and final temperatures were shifted toward lower temperature as LaCl3 was involved in pyrolysis. Mass loss and average mass loss rate during pyrolysis decreased with La-involvement. The kinetics indicated that the first-order reaction kinetic model well matched the pyrolysis process. As La-involved OS and CS were employed, their apparent activation energies（Ea） were reduced, and their pyrolysis characteristic index（I） were higher comparing with the OS and CS without La-involvement. Based on the produced biochar, the yield and ash content were increased by La-involvement, and the O/C ratio and iodine sorption value（ISV） were also enhanced. Obviously, the loaded LaCl3 could facilitate pyrolysis process, and the produced biochar exhibited a great adsorption potential in aqueous solution. According to the results from FT-IR（Fourier transform infrared spectroscopy） analysis, La in pyrolysis functioned as accelerating lignin decomposition via condensing –OH, breaking aliphatic C–H and aromatic rings on lignin, cutting the links of C-O-C among the monomers in lignocellulose. LaCl3 was finally converted to La2O3 in biochar after pyrolysis.

A Sustainable Strategy for Spent Cathode Carbon Blocks Hazardous Waste Recycling Using Binary Molten Salt Thermal Treatment

Waste-to-Energy treatment is a promising path to environment and energy management in the future.This work detailed a binary molten salt thermal treatment methodology for the detoxification of spent cathode carbon block(SCCB)waste and the recycling of carbonaceous materials.The thermal behavior of SCCB and SCCB blended with molten salts was investigated.It was found that the NaCl-Na_(2)CO_(3)binary molten salts significantly contributed to reducing pyrolysis onset temperature by 334.3 K compared to that of SCCB itself(i.e.,activation energy of pyrolysis reaction was reduced from 4.24×10^(5)to 2.30×10^(5)J/mol),thus helping to lower thermal treatment energy consumption.With the addition of binary molten salts,the residue after thermal treatment in a horizontal tube furnace experiment was separated into two layers.The bottom-layer residue was mainly composed of molten salts.The fluorine content in the form of NaF and CaF_(2)of top-layer residue was reduced significantly while the carbon content remained unchanged.Specifically,the leaching concentration of fluoride ion was decreased from 4620 mg/L to 856 mg/L.It is noted that the NaF and CaF_(2)can be removed through water-leaching and hydrothermal acid-leaching methods and thus the carbonaceous materials with a calorific value of 17.5 MJ/kg were obtained.