Microscopic mechanism study and process optimization of dimethyl carbonate production coupled biomass chemical looping gasification system

Biomass chemical looping gasification technology is one of the essential ways to utilize abundant biomass resources.At the same time,dimethyl carbonate can replace phosgene as an environmentfriendly organic material for the synthesis of polycarbonate.In this paper,a novel system coupling biomass chemical looping gasification with dimethyl carbonate synthesis with methanol as an intermediate is designed through microscopic mechanism analysis and process optimization.Firstly,reactive force field molecular dynamics simulation is performed to explore the reaction mechanism of biomass chemical looping gasification to determine the optimal gasification temperature range.Secondly,steady-state simulations of the process based on molecular dynamics simulation results are carried out to investigate the effects of temperature,steam to biomass ratio,and oxygen carrier to biomass ratio on the syngas yield and compositions.In addition,the main energy indicators of biomass chemical looping gasification process including lower heating value and cold gas efficiency are analyzed based on the above optimum parameters.Then,two synthesis stages are simulated and optimized with the following results obtained:the optimal temperature and pressure of methanol synthesis stage are 150℃ and 4 MPa;the optimal temperature and pressure of dimethyl carbonate synthesis stage are 140℃ and 0.3 MPa.Finally,the pre-separation-extraction-decantation process separates the mixture of dimethyl carbonate and methanol generated in the synthesis stage with 99.11%purity of dimethyl carbonate.Above results verify the feasibility of producing dimethyl carbonate from the perspective of multi-scale simulation and realize the multi-level utilization of biomass resources.

Performance Assessment of an Allothermal Auger Gasification System for On-Farm Grain Drying

Biomass gasification is a well-developed technology with the potential to convert agricultural residues to value-added products. The availability of on-farm gasifiers that can handle low-density agricultural wastes such as soybean residue, an underutilized feedstock, is limited. Therefore, the goal of this research was to install and assess an allothermal, externally heated, auger gasifier capable of converting agricultural wastes to combustible gas for on-farm grain drying. The system was used to convert soybean residues under different reactor temperature, i.e., 700°C, 750°C, 800°C, and 850°C. The results showed that increasing the reactor temperature from 700°C to 850°C increased the producer gas molar fractions of H2, CO, and CH4, from 1.1% to 1.5%, from 15.0% to 23.8%, and from 5.1% to 7.7%, respectively. The higher heating value of the producer gas reached 6.3 MJ/m3 at reactor temperature of 850°C. Specific gas yield increased from 0.32 to 0.58 m3/kgbiomass while char and particulate yield decreased from 41.7% to 33.6% by increasing the reactor temperature from 700°C to 850°C. Maximum carbon sequestration achieved, in the form of biochar-carbon, was 32% of the raw feedstock carbon. Gasification of collectable soybean residues from 1 acre would be sufficient to dry 1132 kg of soybean seeds (the average yield from one acre)

A biomass gasification system for synthesis gas from the new method

This paper describes a single fluidized bed by the two-step gasification of the working method, process and biomass and coal co-gasification by a certain proportion of the results of a typical run. The results show that the biomass gasifi-cation technology for raw materials has a wide adaptability, the tar content in the gas is less than 10mg/m3,component in it ,the H2+CO>70%, H2/C ≈1~2,especially suitable for biomass from hydrogen, synthetic alcohol fuel, is a promising approach.

Role of iron ore in enhancing gasification of iron coke:Structural evolution,influence mechanism and kinetic analysis

The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.

Gasification kinetics of bulk coke in the CO2/CO/H2/H2O/N2 system simulating the atmosphere in the industrial blast furnace

The gasification characteristics and gasification kinetics of coke in complex CO2/CO/H2/H2O/N2 systems similar to the gas system of industrial blast furnace (BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model (RPM), Volumetric Model (VM), and Grain Model (GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples (Coke Reaction Index (CRI)>50) is due to the high Fe2O3 in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.

The Role of Diatomite Particles in the Activated Sludge System for Treating Coal Gasification Wastewater

Diatomite is a kind of natural low-cost mineral material. It has a number of unique physical properties and has been widely used as an adsorbent in wastewater treatment. This study was conducted to investigate the aerobic biodegradation of coal gasification wastewater with and without diatomite addition. Experimental results indicated that diatomite added in the activated sludge system could promote the biomass and also enhance the performance of the sludge settling. The average mixed-liquor volatile suspended solids （MLVSS） is increased from 4055 mg.L^-1 to 4518 mg.L^-1 and the average settling volume （SV） are changed only from 45.9% to 47.1%. Diatomite additive could enhance the efficiency of chemical oxygen demand （COD） and total phenols removal from the wastewater. The COD removal increased from 73.3% to near 80% and the total phenols removal increased from 81.4% to 85.8%. The mechanisms of the increase of biomass and pollutants removal may correlates to the improvement of bioavailability and sludge settlement characteristics by diatomite added. Micrograph of the sludge in the diatomite-activated sludge system indicated that the diatomite added could be the carrier of the microbe and also affect the biomass and pollutant removal.

Coal Gasification Wastewater Pretreatment with Coagulation and N_2 Flotation Combined System

A N 2 flotation tank combined with coagulation was developed as a pretreatment equipment of biological process to remove oil and other pollutants in coal gasification wastewater( CGW). With optimal PAC dosage of 20 mg / L,the sole coagulation process achieves removal efficiencies of 29. 34% and 26. 83% for oil and COD,respectively. For the sole N 2 floatation process,the optimal N 2 flux and HRT are 20 m3/ h and 20 min. Meanwhile,the oil and COD removal efficiencies are 35. 41% and 14. 26%,respectively. For the combined system of coagulation and N 2 floatation,the optimal parameter values are the same as the ones of separate processes. Correspondingly,the removal efficiencies are 46. 28% and 31. 89% for oil and COD, respectively. Besides,BOD 5 / COD of the effluent is improved. In contrast with conventional dissolved air floatation,the inert gas- N 2 prevents the formation of cyclopentenone, pyridine derivatives, and other heterocyclic aromatic hydrocarbons,thus improving the biodegradability of influent for the subsequent biological processes.

Numerical Calculation of a 3000MWt MHD-steam Combined Cycel System with Tail Gasification

A numerical calculation of a 3000MWt MHD steam combined cycle system with tail gasification is described . The research scheme has been set up and the parameters of this system have been designed. Then the efficiency of the combined cycle system has been calculated which is up to 53.9%.

Structural properties of residual carbon in coal gasification fine slag and their influence on flotation separation and resource utilization:A review

Coal gasification fine slag(FS)is a typical solid waste generated in coal gasification.Its current disposal methods of stockpil-ing and landfilling have caused serious soil and ecological hazards.Separation recovery and the high-value utilization of residual carbon(RC)in FS are the keys to realizing the win-win situation of the coal chemical industry in terms of economic and environmental benefits.The structural properties,such as pore,surface functional group,and microcrystalline structures,of RC in FS(FS-RC)not only affect the flotation recovery efficiency of FS-RC but also form the basis for the high-value utilization of FS-RC.In this paper,the characteristics of FS-RC in terms of pore structure,surface functional groups,and microcrystalline structure are sorted out in accordance with gasification type and FS particle size.The reasons for the formation of the special structural properties of FS-RC are analyzed,and their influence on the flotation separation and high-value utilization of FS-RC is summarized.Separation methods based on the pore structural characterist-ics of FS-RC,such as ultrasonic pretreatment-pore-blocking flotation and pore breaking-flocculation flotation,are proposed to be the key development technologies for improving FS-RC recovery in the future.The design of low-cost,low-dose collectors containing polar bonds based on the surface and microcrystalline structures of FS-RC is proposed to be an important breakthrough point for strengthening the flotation efficiency of FS-RC in the future.The high-value utilization of FS should be based on the physicochemical structural proper-ties of FS-RC and should focus on the environmental impact of hazardous elements and the recyclability of chemical waste liquid to es-tablish an environmentally friendly utilization method.This review is of great theoretical importance for the comprehensive understand-ing of the unique structural properties of FS-RC,the breakthrough of the technological bottleneck in the efficient flotation separation of FS,and the expansion of the field of the high value-added utilization of FS-RC.

Status of an MWth integrated gasification fuel cell powergeneration system in China

Abstract Here,we provide a status update of an integrated gasification fuel cell(IGFC)power-generation system being developed at the National Institute of Clean-and-Low-Carbon in China at the megawatt thermal(MWth)scale.This system is designed to use coal as fuel to produce syngas as a first step,similar to that employed for the integrated gasification combined cycle.Subsequently,the solid-oxide fuel-cell(SOFC)system is used to convert chemical energy to electricity directly through an electrochemical reaction without combustion.This system leads to higher efficiency as compared with that from a traditional coal-fired power plant.The unreacted fuel in the SOFC system is transported to an oxygencombustor to be converted to steam and carbon dioxide(CO_(2)).Through a heat-recovery system,the steam is condensed and removed,and CO_(2) is enriched and captured for sequestration or utilization.Comprehensive economic analyses for a typical IGFC system was performed and the results were compared with those for a supercritical pulverized coal-fired power plant.The SOFC stacks selected for IGFC development were tested and qualified under hydrogen and simulated coal syngas fuel.Experimental results using SOFC stacks and thermodynamic analyses indicated that the control of hydrogen/CO ratio of syngas and steam/CO ratio is important to avoid carbon deposition with the fuel pipe.A 20-kW SOFC unit is under development with design power output of 20 kW and DC efficiency of 50.41%.A 100 kW-level subsystem will consist of 6920-kW power-generation units,and the MWth IGFC system will consist of 59100 kWlevel subsystems.

Investigation on a Supercritical Water Gasification System with CO_(2)as Transporting Medium

As a benign energy vector,hydrogen has been discussed for a long time.Supercritical water gasification was one of good ways to produce hydrogen.However,supercritical water gasification system with H_(2)O transporting was energy consuming in the process of heating due to the high specific heat of H_(2)O.A new supercritical water gasification system was established in this paper with supercritical CO_(2)as medium instead.Phenolic plastics were used as the sample transported by CO_(2).Production yields,energy flow and exergy flow of the system were collected and the influence of temperature,pressure,gasification concentration and transporting concentration was investigated.Mass flow of H_(2)O input into the reactor was 1000 kg/h.The typical condition was as follow:temperature 923.15 K,pressure 23 MPa,and the mass ratio of water,sample and transporting medium was 100:9:9.Yield of H_(2),CH4,CO and CO_(2)at this condition was 8.1 kg/h,39.6 kg/h,6.6 kg/h and 137.5 kg/h,respectively.Similar system with H_(2)O transporting was used to compare with the supercritical CO_(2)transporting system and proved that system with CO_(2)transporting could reduce the loss of both energy and exergy while the reduce of each gas production yield was less than 0.1 mol/mol.

Investigation on gasification of glycerol and palm shell mixed wastes by fluidization system

In this paper, gasification was utilized in order to produce syngas from crude glycerol and palm shell waste which are by-product of biodiesel production. Experiments were carried out in a fluidized bed quartz reactor using alumina ball with 1 mm diameter as fluidizing medium with equivalent ration of 0.05 with raw materials （mixed crude glycerol and palm shell wastes） at 10 g/min feed rate under 700℃ and 900℃. Glycerol and palm shell powder were fed separately to gasifier at different weight ratio varied from 100：0, 70：30, 50：50, 30：70, 0：100. Decomposition of crude glycerol resulted in much less char when compared with other biomass. From the results, it could be found that combustible gas productions increased with the increasing of crude glycerol fraction and temperature; syngas production was highest at 900℃with only glycerol in feed; gas production rate yields under optimum condition were 4.29% CO2, 8.70% CO, 10.48% H2, and 8.24% CH4 L/min; LHV and H2/CO at optimum condition were 4.87 MJ/m^3 and 1.20, respectively, which were sufficient for power utilization. Obtained H2/CO ratio also indicated that syngas from gasification of crude glycerol and palm shell waste should be suitable for further conversion to methanol and other chemical reagents, and thus closing the chemical recovery cycle of biodiesel production process to ensure the sustainahility status for the use of biodiesel as a prominent renewable energy source.

Agglomeration of coal and polyethylene mixtures during fixed‑bed co‑gasification

The article presents the results of experimental studies on the gasification of mixtures of brown coal and polyethylene(up to 20 wt%fraction)in a laboratory reactor.The work aims to study the agglomeration process during the heating and oxidation of the mixtures.The measurement results(gas composition,pressure drop)provide indirect information on the dynamics of thermal decomposition and structural changes in the fuel bed.We have shown that the interaction between polyethylene and a coal surface leads to the formation of dense agglomerates,in which the molten polymer acts as a binder.Clinkers form as a result of interfacial interactions between components and filtration flow rearranging.The hydrogen/carbon ratio in the solid residue of coal-polyethylene co-gasification increases from 0.07–0.2 to 1.11,indicating the formation of stable hydrocarbon compounds on the carbon surface.The conducted research makes it possible to identify possible interactions between chemical reactions and transfer processes that lead to agglomeration in mixtures of coal with polyethylene.

Upcycling municipal solid waste to sustainable hydrogen via two-stage gasification-reforming

As global municipal solid waste(MSW)quantities continue to escalate,serious socio-environmental challenges arise,necessitating innovative solutions.Waste-to-hydrogen(WTH)via two-stage gasification-reforming(TSGR)presents an emergent technology for MSW upcycling,offering to ease waste management burdens and bolster the burgeoning hydrogen economy.Despite early initiatives to advance TSGR technology,a cohesive and critical analysis of cutting-edge knowledge and strategies to enhance hydrogen production remains lacking.This review aggregates literature on MSW upcycling to hydrogen via TSGR,with a focus on optimizing process control and catalytic efficiency.It underscores technological avenues to augment hydrogen output,curtail catalyst costs,and refine system performance.Particularly,the review illuminates the potential for integrating chemical and calcium looping into TSGR processes,identifying opportunities,and pinpointing challenges.The review concludes with a summary of the current state of techno-economic analysis for this technology,presenting outstanding challenges and future research directions,with the ultimate goal of transitioning WTH from theoretical to practical application.

Multiscale analysis of fine slag from pulverized coal gasification in entrained-flow bed

Fine slag(FS)is an unavoidable by-product of coal gasification.FS,which is a simple heap of solid waste left in the open air,easily causes environmental pollution and has a low resource utilization rate,thereby restricting the development of energy-saving coal gasification technologies.The multiscale analysis of FS performed in this study indicates typical grain size distribution,composition,crystalline structure,and chemical bonding characteristics.The FS primarily contained inorganic and carbon components(dry bases)and exhibited a"three-peak distribution"of the grain size and regular spheroidal as well as irregular shapes.The irregular particles were mainly adsorbed onto the structure and had a dense distribution and multiple pores and folds.The carbon constituents were primarily amorphous in structure,with a certain degree of order and active sites.C 1s XPS spectrum indicated the presence of C–C and C–H bonds and numerous aromatic structures.The inorganic components,constituting 90%of the total sample,were primarily silicon,aluminum,iron,and calcium.The inorganic components contained Si–O-Si,Si–O–Al,Si–O,SO_(4)^(2−),and Fe–O bonds.Fe 2p XPS spectrum could be deconvoluted into Fe 2p_(1/2) and Fe 2p_(3/2) peaks and satellite peaks,while Fe existed mainly in the form of Fe(III).The findings of this study will be beneficial in resource utilization and formation mechanism of fine slag in future.

Effective separation of coal gasification fine slag: Role of classification and ultrasonication in enhancing flotation

Effective separation of residual carbon and ash is the basis for the resource utilization of coal gasification fine slag(CGFS).The conventional flotation process of CGFS has the bottlenecks of low carbon recovery and high collector dosage.In order to address these issues,CGFS sample taken from Shaanxi,China was used as the study object in this paper.A new process of size classification-fine grain ultrasonic pretreatment flotation(SC-FGUF)was proposed and its separation effect was compared with that of wholegrain flotation(WGF)as well as size classification-fine grain flotation(SC-FGF).The mechanism of its enhanced separation effect was revealed through flotation kinetic fitting,flotation flow foam layer stability,particle size composition,surface morphology,pore structure,and surface chemical property analysis.The results showed that compared with WGF,pre-classification could reduce the collector dosage by 84.09%and the combination of pre-classification and ultrasonic pretreatment could increase the combustible recovery by 17.29%and up to 93.46%.The SC-FGUF process allows the ineffective adsorption of coarse residual carbon to collector during flotation stage to be reduced by pre-classification,and the tightly embedded state of fine CGFS particles is disrupted and surface oxidizing functional group occupancy was reduced by ultrasonic pretreatment,thus carbon and ash is easier to be separated in the flotation process.In addition,some of the residual carbon particles were broken down to smaller sizes in the ultrasonic pretreatment,which led to an increase in the stability of flotation flow foam layer and a decrease in the probability of detachment of residual carbon particles from the bubbles.Therefore,SCFGUF could increase the residual carbon recovery and reduce the flotation collector dosage,which is an innovative method for carbon-ash separation of CGFS with good application prospect.

A critical review on direct catalytic hydrogasification of coal into CH_(4):catalysis process configurations,evaluations,and prospects

Coal catalytic hydrogasification(CCHG)is a straightforward approach for producing CH_(4),which shows advantages over the mature coal-to-CH_(4) technologies from the perspectives of CH_(4) yield,thermal efficiency,and CO_(2) emission.The core of CCHG is to make carbon in coal convert into CH_(4) efficiently with a catalyst.In the past decades,intensive research has been devoted to catalytic hydrogasification of model carbon(pitch coke,activated carbon,coal char).However,the chemical process of CCHG is still not well understood because the coal structure is more complicated,and CCHG is a combination of coal catalytic hydropyrolysis and coal char catalytic hydrogasification.This review seeks to shed light on the catalytic process of raw coal during CCHG.The configuration of suitable catalysts,operating conditions,and feedstocks for tailoring CH_(4) formation were identified,and the underlying mechanisms were elucidated.Based on these results,the CCHG process was evaluated,emphasizing pollutant emissions,energy efficiency,and reactor design.Furthermore,the opportunities and strategic approaches for CCHG under the restraint of carbon neutrality were highlighted by considering the penetration of“green”H2,biomass,and CO_(2) into CCHG.Preliminary investigations from our laboratories demonstrated that the integrated CCHG and biomass/CO_(2) hydrogenation process could perform as an emerging pathway for boosting CH_(4) production by consuming fewer fossil fuels,fulfilling the context of green manufacturing.This work not only provides systematic knowledge of CCHG but also helps to guide the efficient hydrogenation of other carbonaceous resources such as biomass,CO_(2),and coal-derived wastes.

Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers

Coal gasification fly ash(CGFA)is an industrial solid waste from the coal circulating fluidized bed(CFB)gasification process,and it needs to be effectively disposed to achieve sustainable development of the environment.To realize the application of CGFA as a precursor of porous carbon materials,the physicochemical properties of three kinds of CGFA from industrial CFB gasifiers are analyzed.Then,the activation potential of CGFA is acquired via steam activation experiments in a tube furnace reactor.Finally,the fluidization activation technology of CGFA is practiced in a bench-scale CFB test rig,and its advantages are highlighted.The results show that CGFA is characterized by a high carbon content in the range of 54.06%–74.09%,an ultrafine particle size(d50:16.3–26.1 μm),and a relatively developed pore structure(specific surface area SSA:139.29–551.97 m^(2)·g^(-1)).The proportion of micropores in CGFA increases gradually with the coal rank.Steam activation experiments show that the pore development of CGFA mainly includes three stages:initial pore development,dynamic equilibrium between micropores and mesopores and pore collapse.The SSA of lignite fly ash(LFA),subbituminous fly ash(SBFA)and anthracite fly ash(AFA)is maximally increased by 105%,13%and 72%after steam activation;the order of the largest carbon reaction rate and decomposition ratio of steam among the three kinds of CGFA is SBFA>LFA>AFA.As the ratio of oxygen to carbon during the fluidization activation of LFA is from 0.09 to 0.19,the carbon conversion ratio increases from 14.4%to 26.8%and the cold gas efficiency increases from 6.8%to 10.2%.The SSA of LFA increases by up to 53.9%during the fluidization activation process,which is mainly due to the mesoporous development.Relative to steam activation in a tube furnace reactor,fluidization activation takes an extremely short time(seconds)to achieve the same activation effect.It is expected to further improve the activation effect of LFA by regulating the carbon conversion ratio range of 27%–35%to create pores in the initial development stage.

A Gasification Technology to Combine Oil Sludge with Coal-Water Slurry:CFD Analysis and Performance Determination

The development of more environment-friendly ways to dispose of oil sludge is currently regarded as a hot topic.In this context,gasification technologies are generally seen as a promising way to combine oil sludge with coal–water slurry(CWS)and generate resourceful fuel.In this study,a novel five-nozzle gasifier reactor was analyzed by means of a CFD(Computational fluid dynamic)method.Among several influential factors,special attention was paid to the height-to-diameter ratio of the gasifier and the mixing ratio of oil sludge,which are known to have a significant impact on the flow field,temperature distribution and gasifier performances.According to the numerical results,the optimal height-to-diameter ratio and oil mixing ratio are about 2.4:1 and 20%,respectively.Furthermore,the carbon conversion rate can become as high as 98.55%with the hydrolysis rate reaching a value of 53.88%.The consumption of raw coal and oxygen is generally reduced,while the effective gas production is increased to 50.93 mol/%.

Mechanism of K/Ni Etching for Biochar-H_(2)O Gasification

Biomass-H_(2)O gasification is a complex thermochemical reaction,including three processes of volatile removal:homogeneous/heterogeneous reforming,biochar gasification and etching.The rate-determining step is biochar-H_(2)O gasification and etching so the DFT is carried out to see the catalytic role of different metal elements(K/Ni)in the zigzag biochar model.The calculation results show that the gasification of biochar-H_(2)O needs to go through four processes:dissociative adsorption of water,hydrogen transfer(hydrogen desorption,hydrogen atom transfer),carbon dissolution and CO desorption.The energy barrier indicated that the most significant step in reducing the activation energy of K is reflected in the hydrogen transfer step,which is reduced from 374.14 kJ/mol to 152.41 kJ/mol;the catalytic effect of Ni is mainly reflected in the carbon dissolution step,which is reduced from 122.34 kJ/mol to 84.8 kJ/mol.The existence of K causes the edge to have a stronger attraction to H and does not destroy theπbonds of biochar molecules.The destruction ofπbonds is mainly due to the role of H free radicals,while the destruction ofπbonds will lead to easier C-C bond rupture.Ni shows a strong attraction to O in OH,which forms strong Ni-O chemical bonds.Ni can also destroy the aromatic structure directly,making the gasification easier to happen.This study explored the catalytic mechanism of K/Ni on the biochar-H_(2)O gasification at the molecular level and looked forward to the potential synergy of K/Ni,laying a foundation for experimental research and catalyst design.