Micro-aluminum powder with bi-or tri-component alloy coating as a promising catalyst:Boosting pyrolysis and combustion of ammonium perchlorate

A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.

A review on nitrogen transformation and conversion during coal pyrolysis and combustion based on quantum chemical calculation and experimental study

The emission of NOx during coal combustion contributes to the formation of acid rain and photochemical smog,which would seriously affect the quality of atmospheric environment.Therefore,the decrease of NOx is of great importance for improving the efficient utilization of coal.The present review comprehensively summarized the influence factors and mechanisms of migration and transformation of nitrogen during the coal pyrolysis and combustion based on experimental study and quantum chemical calculation.Firstly,in the process of pyrolysis:the occurrence state and transformation of nitrogen were concluded.The influence of temperature,atmosphere,heating rate and catalyst on formation of NOx precursor and nitrogen migration path at the molecular level were summarized;Secondly,during the process of combustion:the influence of temperature,ambient oxygen concentration,physical structure of coal char,catalyst on heterogeneous oxidation of char(N)were summarized;The effects of char surface properties,catalyst and ambient atmosphere on heterogeneous reduction of NOx were also concluded.Based on the quantum chemical calculation,the reaction path of heterogeneous oxidation of char-N and heterogeneous reduction of NOx were described in detail.Current studies focus more on the generation of HCN and NH3,but in order to reduce the pollution of NOx from the source,it is necessary to further improve the process conditions and the optimal formula of producing more N2 during pyrolysis,as well as clarify the path of the generation of N2.Experiments study and quantum chemistry calculation should be combined to complete the research of directional nitrogen reduction during pyrolysis and denitration during combustion.

A kinetic study on pyrolysis and combustion characteristics of oil cakes： Effect of cellulose and lignin content

Pyrolysis and combustion characteristics of three different oil cakes such as Pongamia(Pongamia Pinnata),Madhuca(Madhuca Indica),and Jatropha(Jatropha curcas) were investigated in this study.The cellulose and lignin contents of oil cakes play very important role in pyrolysis and combustion processes.A kinetic investigation of three oil cakes was carried out and major part of the samples decomposed between 210℃ and 500℃.Pyrolysis and combustion were carried out with the mixtures of cellulose and lignin chemicals in different ratios and compared with the oil cakes.The biomass with higher cellulose content showed faster rate of pyrolysis than the biomass with higher lignin content.However at higher temperatures(>600℃) all the oil cakes exhibited similar conversion at low heating rate in N2 atmosphere.Apparent activation energies increased for Madhuca and Pongamia oil cakes indicating the presence of more cellulose whereas,low activation energy of Jatropha confirms more lignin content.

Physicochemical,mineralogy,and thermo-kinetic characterisation of newly discovered Nigerian coals under pyrolysis and combustion conditions

In this study,the physicochemical,microstructural,mineralogical,thermal,and kinetic properties of three newly discovered coals from Akunza(AKZ),Ome(OME),and Shiga(SHG)in Nigeria were examined for potential energy recovery.Physicochemical analysis revealed high combustible but low levels of polluting elements.The higher heating values ranged from 18.65 MJ/kg(AKZ)to 26.59 MJ/kg(SHG).Microstructure and mineralogical analyses revealed particles with a rough texture,surface,and glassy lustre,which could be ascribed to metals,quartz,and kaolinite minerals.The major elements(C,O,Si,and Al),along with minor elements(Ca,Cu,Fe,K,Mg,S,and Ti)detected are associated with clays,salts,or the porphyrin constituents of coal.Thermal analysis showed mass loss(ML)ranges from 30.51%to 87.57%and residual mass(RM)from 12.44%to 69.49%under combustion(oxidative)and pyrolysis(non-oxidative)TGA conditions due to thermal degradation of organic matter and macerals(vitrinite,inertinite and liptinite).Kinetic analysis revealed the coals are highly reactive under the oxidative and non-oxidative conditions based on the Coats-Redfem Model.The activation energy(Ea)ranged from 23.81 to 89.56 kJ/mol,whereas the pre-exponential factor(kQ)was from 6.77×10^(-4)/min to 1.72×10^(3)/min under pyrolysis and combustion conditions.In conclusion,the coals are practical feedstocks for either energy recovery or industrial applications.

Synergetic NO reduction by biomass pyrolysis products simulating their reburning in circulating fluidized bed decoupling combustion

The present work investigated the synergetic effect of pyrolysis-derived char,tar and gas(py-gas)on NO reduction,which may occur in circulating fluidized-bed decoupling combustion(CFBDC)system treating N-rich fuel.Experiments were carried out in a lab-scale drop-tube reactor for NO reduction by some binary mixtures of reagents including char/py-gas,tar/py-gas and tar/char.At a specified total mass rate of0.15 g·min^-1 for NO-reduction reagent,the char/py-gas(binary reagent)enabled the best synergetic NO reduction in comparison with the others.There existed effective interactions between char and some species in py-gas(i.e.,H2,CxHy)during NO reduction by pyrolysis products,meanwhile the tar/py-gas or tar/char mixture only caused a positive effect when tar proportion was necessarily lowered to about 26%.On the other hand,the synergetic effects were not improved for all tested binary reagents by increasing the reaction temperature and residence time.

Pyrolysis behaviour and combustion kinetics of waste printed circuit boards

The effective recycling of waste printed circuit boards(WPCBs)can conserve resources and reduce environmental pollution.This study explores the pyrolysis and combustion characteristics of WPCBs in various atmospheres through thermogravimetric and Gaussian fitting analyses.Furthermore,this study analyses the pyrolysis products and combustion processes of WPCBs through thermogravimetric and Fourier transform infrared analyses(TG-FTIR)and thermogravimetry-mass spectrometry(TG-MS).Results show that the pyrolysis and combustion processes of WPCBs do not constitute a single reaction,but rather an overlap of multiple reactions.The pyrolysis and combustion process of WPCBs is divided into multiple reactions by Gaussian peak fitting.The kinetic parameters of each reaction are obtained by the Coats-Redfern method.In an argon atmosphere,pyrolysis consists of the overlap of the preliminary pyrolysis of epoxy resin,pyrolysis of small organic molecules,and pyrolysis of brominated flame retardants.The thermal decomposition process in the O_(2) atmosphere is mainly divided into two reactions:brominated flame retardant combustion and epoxy combustion.This study provided the theoretical basis for pollution control,process optimization,and reactor design of WPCBs pyrolysis.

Combustion characteristics of semicokes derived from pyrolysis of low rank bituminous coal

Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.

Pyrolysis and combustion kinetics of lycopodium particles in thermogravimetric analysis

Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion properties, of which microscopic images show that these particles have spherical shapes with identical diameters of 31 μm. The measured density of these particles is 1.0779 g/cm2. Lycopodium particles contain 64.06% carbon, 25.56% oxygen, 8.55% hydrogen and 1.83% nitrogen, and no sulfur. Thermogravimetric analysis in the nitrogen environment indicates that the maximum of particle mass reduction occurs in the temperature range of 250-550 ℃ where the maximum mass reduction in the DTG diagrams also occurs in. In the oxygen environment, an additional peak can also be observed in the temperature range of 500-600 ℃, which points to solid phase combustion and ignition temperature of lycopodium particles. The kinetics of reactions is determined by curve fitting and minimization of error.

Properties,combustion behavior,and kinetic triplets of coke produced by low-temperature oxidation and pyrolysis:Implications for heavy oil in-situ combustion

This work aimed at investigating the crucial factor in building and maintaining the combustion front during in-situ combustion(ISC),oxidized coke and pyrolyzed coke.The surface morphologies,elemental contents,and non-isothermal mass losses of the oxidized and pyrolyzed cokes were thoroughly examined.The results indicated that the oxidized coke could be combusted at a lower temperature compared to the pyrolyzed coke due primarily to their differences in the molecular polarity and microstructure.Kinetic triplets of coke combustion were determined using iso-conversional models and one advanced integral master plots method.The activation energy values of the oxidized and pyrolyzed cokes varied in the range of 130-153 k J/mol and 95-120 kJ/mol,respectively.The most appropriate reaction model of combustion of the oxidized and pyrolyzed cokes followed three-dimensional diffusion model(D_(3)) and random nucleation and subsequent growth model(F_(1)),respectively.These observations assisted in building the numerical model of these two types of cokes to simulate the ISC process.

Importance of oxygen-containing functionalities and pore structures of biochar in catalyzing pyrolysis of homologous poplar

Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar is an inherent catalyst for pyrolysis.In this study,in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil,three char catalysts(600C,800C,and 800AC)produced via pyrolysis of poplar wood at 600 or 800℃or activated at 800℃,were used for catalyzing pyrolysis of homologous poplar wood at 600℃,respectively.The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas(yield increase by 40.2%)and aromatization of volatiles to form more light or heavy phenolics,due to its abundant oxygen-containing functionalities acting as active sites.The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization.Nevertheless,the interaction with the volatiles consumed oxygen on 600C(decrease by 50%),enhancing the aromatic degree and increasing thermal stability.The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores.The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of -OH,while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.

Particle agglomeration and inhibition method in the fluidized pyrolysis reaction of waste resin

This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.

Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Unraveling the role of dual Ti/Mg metals on the ignition and combustion behavior of HTPB-boron-based fuel

Metal additives play an essential role in explosive and propellant formulations. Boron(B) is widely used in propellant applications owing to its high energetic content. The addition of B to explosives and propellants increases their energy density, making them more efficient and powerful. Nevertheless, B forms oxide layers on its surface during combustion, slowing down the combustion rate and reducing rocket motor efficiency. To overcome this issue, other metal additives such as aluminum(Al), magnesium(Mg),and titanium(Ti) are revealed to be effective in boosting the combustion rate of propellants. These additives may improve the combustion rate and therefore enhance the rocket motor’s performance. The present study focused on preparing and investigating the ignition and combustion behavior of pure hydroxyl-terminated polybutadiene(HTPB)-B fuel supplemented with nano-titanium and nanomagnesium. The burn rates of HTPB-B fuel samples were evaluated on the opposed flow burner(OFB)under a gaseous oxygen oxidizer, for which the mass flux ranges from 22 kg/(m^(2)·s) to 86 kg/(m^(2)·s). The addition of Ti and Mg exhibited higher regression rates, which were attributed to the improved oxidation reaction of B due to the synergetic metal combustion effect. The possible combustion/oxidation reaction mechanism of B-Mg and B-Ti by heating the fuel samples at 900℃ and 1100℃ was also examined in a Nabertherm burnout furnace under an oxygen atmosphere. The post-combustion products were collected and further subjected to X-ray diffraction(XRD) and field emission scanning electron microscopy(FE-SEM) analyses to inspect the combustion behavior of B-Ti and B-Mg. It has been observed that the B oxide layer at the interface between B-Ti(B-Mg) is removed at lower temperatures, hence facilitating oxygen transfer from the surroundings to the core B. Additionally, Ti and Mg decreased the ignition delay time of B, which improved its combustion performance.

Fabrication and characterization of multi-scale coated boron powders with improved combustion performance:A brief review

Boron has high mass and volume calorific values,but it is difficult to ignite and has low combustion efficiency.This literature review summarizes the strategies that are used to solve the above-mentioned problems,which include coatings of boron by using fluoride compounds,energetic composites,metal fuels,and metal oxides.Coating techniques include recrystallization,dual-solvent,phase transfer,electrospinning,etc.As one of the effective coating agents,the fluorine compounds can react with the oxide shell of boron powder.In comparison,the energetic composites can effectively improve the flame temperature of boron powder and enhance the evaporation efficiency of oxide film as a condensed product.Metals and metal oxides would react with boron powder to form metal borides with a lower ignition point,which could reduce its ignition temperature.

The regulation of ferrocene-based catalysts on heat transfer in highpressure combustion of ammonium perchlorate/hydroxyl-terminated polybutadiene/aluminum composite propellants

The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.

Relationship between hydrogenation degree and pyrolysis performance of jet fuel

Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is investigated.Fuels with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.

The nitrogen transformation behavior based on the pyrolysis products of wheat straw

In order to provide basic design parameters for the industrial pyrolysis process,the transformation behavior of nitrogen was investigated using wheat straw as raw material.The distributions of nitrogen in pyrolysis char,oil,and gas were obtained and the nitrogenous components in the products were analyzed systematically by X-ray photoelectron spectroscopy(XPS),pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)and thermogravimetric-Fourier transform infrared spectrometry(TG-FTIR).The nitrogen distribution ranges of the pyrolysis char,oil,and gas were 37.34%–54.82%,32.87%–40.94%and 10.20%–28.83%,respectively.More nitrogen was retained in char at lower pyrolysis temperature and the nitrogen distribution of oil was from rise to decline with increasing temperature.The most abundant N-containing compounds in three-phase products were pyrrole-N,amines,and HCN,respectively.In addition,the transformation mechanism of nitrogen from wheat straw to pyrolysis products was concluded.

Pyrolysis of Copper Phthalocyanine as Non-noble Metal Electrocatalysts for Oxygen Reduction Reaction

We investigated the relationship between oxygen reduction reaction(ORR)activity and the pyrolysis temperature(650-850℃)of CuPc in alkaline solution.The highly active sites were formed through the decomposition of CuPc or Cu-N_(4) structure after releasing 4-nitrophthalonitrile.Cu-Nx incorporated with carbon were the main active sites.The XPS measurement results show that,at lower temperature,the contents of pyridinic-N and pyrrolic-N account for the most of the total N.As the temperature is higher than 750℃,the content of graphitic N(26.11%)increases and pyridinic-N(58.81%)becomes the dominant specie.When the temperature is higher than 850℃,the content of graphitic N increases remarkably and becomes the dominant species.Moreover,the specific surface areas decrease with increased pyrolysis temperature.Benefiting from the synergistic effect,the pyrolysis temperature at 750℃of CuPc displays superior electrocatalytic properties.The obtained results reveal that the fabricated non-noble metal catalysts can be used as low-cost,efficient catalyst for water splitting ORR in metal-air batteries and fuel cells.

Spray pyrolysis feasibility of tungsten substitution for cobalt in nickel-rich cathode materials

Cobalt(Co)serves as a stabilizer in the lattice structure of high-capacity nickel(Ni)-rich cathode materials.However,its high cost and toxicity still limit its development.In general,it is possible to perform transition metal substitution to reduce the Co content.However,the traditional coprecipitation method cannot satisfy the requirements of multielement coprecipitation and uniform distribution of elements due to the differences between element concentration and deposition rate.In this work,spray pyrolysis was used to prepare LiNi_(0.9)Co_(0.1-x)W_(x)O_(2)(LNCW).In this regard,the pyrolysis behavior of ammonium metatungstate was analyzed,together with the substitu-tion of W for Co.With the possibility of spray pyrolysis,the Ni-Co-W-containing oxide precursor presents a homogeneous distribution of metal elements,which is beneficial for the uniform substitution of W in the final materials.It was observed that with W substitution,the size of primary particles decreased from 338.06 to 71.76 nm,and cation disordering was as low as 3.34%.As a consequence,the pre-pared LNCW exhibited significantly improved electrochemical performance.Under optimal conditions,the lithium-ion battery assembled with LiNi_(0.9)Co_(0.0925)W_(0.0075)O_(2)(LNCW-0.75mol%)had an improved capacity retention of 82.7%after 200 cycles,which provides insight in-to the development of Ni-rich low-Co materials.This work presents that W can compensate for the loss caused by Co deficiency to a cer-tain extent.