Chemical looping reforming of the micromolecular component from biomass pyrolysis via Fe_(2)O_(3)@SBA-16

To solve the problems of low gasification efficiency and high tar content caused by solid–solid contact between biomass and oxygen carrier in traditional biomass chemical looping gasification process.The decoupling strategy was adopted to decouple the biomass gasification process,and the composite oxygen carrier was prepared by embedding Fe_(2)O_(3) in molecular sieve SBA-16 for the chemical looping reforming process of pyrolysis micromolecular model compound methane,which was expected to realize the directional reforming of pyrolysis volatiles to prepare hydrogen-rich syngas.Thermodynamic analysis of the reaction system was carried out based on the Gibbs free energy minimization method,and the reforming performance was evaluated by a fixed bed reactor,and the kinetic parameters were solved based on the gas–solid reaction model.Thermodynamic analysis verified the feasibility of the reaction and provided theoretical guidance for experimental design.The experimental results showed that the reaction performance of Fe_(2)O_(3)@SBA-16 was compared with that of pure Fe_(2)O_(3) and Fe_(2)O_(3)@SBA-15,and the syngas yield was increased by 55.3%and 20.7%respectively,and it had good cycle stability.Kinetic analysis showed that the kinetic model changed from three-dimensional diffusion to first-order reaction with the increase of temperature.The activation energy was 192.79 kJ/mol by fitting.This paper provides basic data for the directional preparation of hydrogen-rich syngas from biomass and the design of oxygen carriers for pyrolysis of all-component chemical looping reforming.

Chaos Transfer in Fluidized Beds Accompanied with Biomass Pyrolysis

Experiments of biomass pyrolysis were carried out in a fluidized bed, and dynamic signals of pressure and temperature were recorded. Correlation dimension was employed to characterize the chaotic behavior of pressure and temperature signals. Both pressure and temperature signals exhibit chaotic behavior, and the chaotic behavior of temperature signals is always weaker than that of pressure signals. Chaos transfer theory was advanced to explain the above phenomena. The discussion on the algorithm of the correlation dimension shows that the distance definition based on rhombic neighborhood is a better choice than the traditional one based on spherical neighborhood. The former provides a satisfactory result in a much shorter time.

Insight into the selective separation of CO_(2)from biomass pyrolysis gas over metal-incorporated nitrogen-doped carbon materials:a first-principles study

The composition of biomass pyrolysis gas is complex,and the selective separation of its components is crucial for its further utilization.Metal-incorporated nitrogen-doped materials exhibit enormous potential,whereas the relevant adsorption mechanism is still unclear.Herein,16 metal-incorporated nitrogen-doped carbon materials were designed based on the density functional theory calculation,and the adsorption mechanism of pyrolysis gas components H2,CO,CO_(2),CH_(4),and C2H6 was explored.The results indicate that metal-incorporated nitrogen-doped carbon materials generally have better adsorption effects on CO and CO_(2)than on H_(2),CH_(4),and C_(2)H_(6).Transition metal Mo-and alkaline earth metal Mg-and Ca-incorporated nitrogen-doped carbon materials show the potential to separate CO and CO_(2).The mixed adsorption results of CO_(2)and CO further indicate that when the CO_(2)ratio is significantly higher than that of CO,the saturated adsorption of CO_(2)will precede that of CO.Overall,the three metal-incorporated nitrogen-doped carbon materials can selectively separate CO_(2),and the alkaline earth metal Mg-incorporated nitrogen-doped carbon material has the best performance.This study provides theoretical guidance for the design of carbon capture materials and lays the foundation for the efficient utilization of biomass pyrolysis gas.

Effect of flue gas recirculation technology on soot and NO formation in the biomass pyrolysis-combustion system

Pyrolysis of biomass followed by combustion of pyrolytic vapors to replace fossil fuels is an economic low-carbon solution.However,the polycyclic aromatic hydrocarbons and N-containing species in biomass pyrolysis vapors result in the soot and NO emissions.The flue gas recirculation(FGR)technology,having the potential to reduce the soot and NO emissions,was introduced to the biomass pyrolysis-combustion system.In addition,it was numerically studied by simulating the biomass pyrolysis vapors based co-flow diffusion flames with CO_(2)addition.Both the experimental and simulated results showed that the FGR had significant suppression effects on the soot formation.When the FGR ratio(i.e.,CO_(2)addition ratio)increased from 0%to 15%,the experimental and simulated soot volume fraction respectively decreased by 32%and 21%,which verified the models used in this study.The decrease in OH concentration caused by the CO_(2)addition was responsible for the decrease in the decomposition rate of A2(A2+OH=A2–+H_(2)O).Hence,more benzo(ghi)fluoranthene(BGHIF)was generated through A1C_(2)H–+A2→BGHIF+H_(2)+H,leading to the increase in inception rate.The decrease in benzo(a)pyrene(BAPYR)concentration was the major factor in the decrease in soot condensation rate.Moreover,the decrease in the C_(2)H_(2) and OH concentrations was responsible for the decrease in the HACA surface growth rate.Furthermore,the simulated results showed that the NO concentration decreased by 0.4%when the content of CO_(2)was increased by 1 vol.%.The decrease in OH concentration suppressed the NO formation via decreasing reaction rates of N+OH=NO+H and HNO+OH=NO+H_(2)O and enhanced the NO consumption via increasing reaction rate of HO_(2)+NO=NO_(2)+OH.

Towards carbon neutrality of calcium carbide-based acetylene production with sustainable biomass resources

Acetylene is produced from the reaction between calcium carbide(CaC_(2))and water,while the production of CaC_(2) generates significant amount of carbon dioxide not only because it is an energy-intensive process but also the raw material for CaC_(2) synthesis is from coal.Here,a comprehensive biomass-to-acetylene process was constructed that integrated several units including biomass pyrolysis,oxygen-thermal CaC_(2) fabrication and calcium looping.For comparison,a coal-to-acetylene process was also established by using coal as feedstock.The carbon efficiency,energy efficiency and environmental impacts of the bio-based calcium carbide acetylene(BCCA)and coal-based calcium carbide acetylene(CCCA)processes were systematically analyzed.Moreover,the environmental impacts were further evaluated by applying thermal integration at system level and energy substitution in CaC_(2) furnace.Even though the BCCA process showed lower carbon efficiency and energy efficiency than that of the CCCA process,life cycle assessment demonstrated the BCCA(1.873 kgCO_(2eq) kg-prod^(-1))a lower carbon footprint process which is 0.366 kgCO_(2eq) kg-prod^(-1) lower compared to the CCCA process.With sustainable energy(biomass power)substitution in CaC_(2) furnace,an even lower GWP value of 1.377 kgCO_(2eq) kg-prod^(-1) can be achieved in BCCA process.This work performed a systematic analysis on integrating biomass into industrial acetylene production,and revealed the positive role of biomass as raw material(carbon)and energy supplier.

Effect of temperature on suspension magnetization roasting of hematite using biomass waste as reductant:A perspective of gas evolution

The magnetization reduction of hematite using biomass waste can effectively utilize waste and reduce CO_(2) emission to achieve the goals of carbon peaking and carbon neutrality.The effects of temperatures on suspension magnetization roasting of hematite using biomass waste for evolved gases have been investigated using TG-FTIR,Py-GC/MS and gas composition analyzer.The mixture reduction process is divided into four stages.In the temperature range of 200-450℃ for mixture,the release of CO_(2),acids,and ketones is dominated in gases products.The yield and concentration of small molecules reducing gases increase when the temperature increases from 450 to 900℃.At 700℃,the volume concentrations of CO,H_(2) and CH_(4) peak at 8.91%,8.90% and 4.91%,respectively.During the suspension magnetization roasting process,an optimal iron concentrate with an iron grade of 70.86%,a recovery of 98.66% and a magnetic conversion of 45.70% is obtained at 700℃.Therefore,the magnetization reduction could react greatly in the temperature range of 600 to 700℃ owing to the suitable reducing gases.This study shows a detail gaseous evolution of roasting temperature and provides a new insight for studying the reduction process of hematite using biomass waste.

Direct Reduction of High-phosphorus Oolitic Hematite Ore Based on Biomass Pyrolysis

Direct reduction of high-phosphorus oolitic hematite ore based on biomass pyrolysis gases （CO, H2, and CH4 ）, tar, and char was conducted to investigate the effects of reduction temperature, iron ore-biomass mass ratio, and reduction time on the metallization rate. In addition, the effect of particle size on the dephosphorization and iron recovery rate was studied by magnetic separation. It was determined that the metallization rate of the hematite ore could reach 99.35 % at iron ore-biomass mass ratio of 1 ： 0.6, reduction temperature of 1100℃, and reduction time of 55 min. The metallization rate and the aggregation degree of iron particles increase with the increase of reduction temperature. The particle size of direct reduced iron （DRI） has a great influence on the quality of the iron concentrate during magnetic separation. The separation degree of slag and iron was improved by the addition of 15 mass% sodium carbonate. DRI with iron grade of 89.11%, iron recovery rate of 83.47%, and phosphorus content of 0.28% can be obtained when ore fines with particle size of -10μm account for 78.15%.

An analytical model for pyrolysis of a single biomass particle

Decreasing in emissions of greenhouse gases to confront the global warming needs to replace fossil fuels as the main doer of the world climate changes by renewable and clean fuels produced from biomass like wood waste which is neutral on the amount of CO2. An analytical and engineering model for pyrolysis process of a single biomass particle has been presented. Using a two-stage semi global kinetic model which includes both primary and secondary reactions, the effects of parameters like shape and size of particle as well as porosity on the particle temperature profile and product yields have been investigated. Comparison of the obtained results with experimental data shows that our results are in a reasonable agreement with previous researchers' works. Finally, a sensitivity analysis is done to determine the importance of each parameter on pyrolysis of a single biomass particle which is affected by many constant parameters.

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.

Production of Benzoic Acid through Catalytic Transformation of Renewable Lignocellulosic Biomass

In the present work, we reported a novel route for the conversion of lignocellulosic biomass （sawdust） to a high-value chemical of benzoic acid under atmospheric pressure. The trans- formation involved the catalytic pyrolysis of sawdust into aromatics, the decomposition of heavier alkylaromatics to toluene, and the liquid-phase oxidation of toluene-rich aromatics to benzoic acid. The production of the desired benzoic acid from the sawdust-derived aro- matics, with the benzoic acid selectivity of 85.1 C-mol% and nearly complete conversion of toluene, was achieved using the MnO2/NHPI catalyst at 100 ℃ for 5 h. The in uence of adding methanol on the catalytic conversion of sawdust to the core intermediate of toluene was also investigated in detail.

The swirl and pyrolysis reaction synergistically enhance solid-solid heat transfer and product separation in cyclone pyrolyzer Author links open overlay panel

Cyclone pyrolyzer is a novel type of downer that combines centrifugal force field and double-layer cyclone vortex.Research on transfer behavior is helpful to optimize the pyrolyzer to meet the needs of pyrolysis.In this study,the Computational Particle Fluid Dynamics(CPFD)model is used to analyze the transfer behavior of binary particles,and finds that the swirl and reaction have a synergistic effect.This effect can increase the heating rate of the particles to the range of flash pyrolysis,and its mechanism lies in the flow field structure of the pyrolyzer.Due to the centrifugal force field,the particles gather to the near wall.The rapid swirl,which facilitates intense gas-solid heat transfer,leads to the rapid heating and pyrolysis of biomass particles.As the pyrolysis proceeds,the mass of the biomass particles becomes smaller and they are more easily affected by the gas flow in pyrolyzer.Under the action of gas flow,char particles serve as new heat carrier to form the inner cycle of particles,which strengthens the heating process.The pyrolysis products are discharged from the exhaust port in time with the flow field of the pyrolyzer to achieve separation from the heat carrier and inhibit the occurrence of secondary reactions.

Catalytic hydrodeoxygenation of pyrolysis bio-oil to jet fuel: A review

Bio-oil from biomass pyrolysis cannot directly substitute traditional fuel due to compositional deficiencies.Catalytic hydrodeoxygenation(HDO)is the critical and efficient step to upgrade crude bio-oil to high-quality bio-jet fuel by lowering the oxygen content and increasing the heating value.However,the hydrocracking reaction tends to reduce the liquid yield and increase the gas yield,causing carbon loss and producing hydrocarbons with a short carbon-chain.To obtain high-yield bio-jet fuel,the elucidation of the conversion process of biomass catalytic HDO is important in providing guidance for metal catalyst design and optimization of reaction conditions.Considering the complexity of crude bio-oil,this review aimed to investigate the catalytic HDO pathways with model compounds that present typical bio-oil components.First,it provided a comprehensive summary of the impact of physical and electronic structures of both noble and non-noble metals that include monometallic and bimetallic supported catalysts on regulating the conversion pathways and resulting product selectivity.The subsequent first principle calculations further corroborated reaction pathways of model compounds in atom-level on different catalyst surfaces with the experiments above and illustrated the favored C-O/C-O scission orders thermodynamically and kinetically.Then,it discussed hydrogenation effects of different H-donors(such as hydrogen and methane)and catalysts deactivation for economical and industrial consideration.Based on the descriptions above and recent researches,it also elaborated on catalytic HDO of biomass and bio-oil with multi-functional catalysts.Finally,it presented the challenges and future prospective of biomass catalytic HDO.

A granular-biomass high temperature pyrolysis model based on the Darcy flow

We established a model for the chemical reaction kinetics of biomass pyrolysis via the hightemperature thermal cracking of liquid products. We divided the condensable volatiles into two groups, based on the characteristics of the liquid prdoducts., tar and biomass oil. The effects of temperature, residence time, particle size, velocity, pressure, and other parameters on biomass pyrolysis and high-temperature tar cracking were investigated numerically, and the results were compared with experimental data. The simulation results showed a large endothermic pyrolysis reaction effect on temperature and the reaction process. The pyrolysis reaction zone had a constant temperature period in several layers near the center of large biomass particles. A purely physical heating process was observed before and after this period, according to the temperature index curve.

Effects of temperature and composite alumina on pyrolysis of sewage sludge

An interactive dual-circulating fluidized bed system has been proposed in which the pyrolysis of sewage sludge（SS） and incineration of biomass proceed simultaneously, and alumina is used as the bed material and heat carrier. The alumina coated with biomass ash would mix with sewage sludge in the pyrolysis reactor of this device. It is important to know the influence of composite alumina（CA） on the pyrolysis progress. Sewage sludge was pyrolyzed in a fixed bed reactor from 400 to 600°C using CA as catalyst. The effects of temperature and CA additive ratio on the products were investigated. The product yields and component distribution of non-condensable gas were more sensitive to the change of temperature, and the maximum liquid yield of 48.44 wt.% and maximum Useable Energy of Liquid of 3871 k J/kg sludge were observed at 500°C with 1/5 CA/SS（mass ratio）. The gas chromatography–mass spectrometry results showed that the increase of temperature enhanced devolatilization of organic matter and promoted cyclization and aromatization of aliphatics. The presence of CA could strengthen secondary cracking and interaction among primary products from different organic compounds, such as acid–amine condensation,and reduce the content of oxygenated compounds. When the CA additive amount exceeded a certain proportion, the aromatization was clearly strengthened. The effects of CA on decomposition of fatty acids and formation of aromatics were similar to that of temperature. This means that the reaction temperature could be lowered by introducing CA, which has a positive effect on reducing energy consumption.