Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Effect of the surface properties of an activated coke on its desulphurization performance

Commercial coke was modified by H2O2 and/or NH3.H2O to obtain an activated coke containing additional oxygen functional groups and/or nitrogen functional groups. The aim of the modification was to enhance the SO2 adsorption capacity of the activated coke. Several techniques, including total nitrogen content measurements, SO2 adsorption, XPS and FTIR analysis, were used to characterize the coke samples. The XPS and FTIR spectra suggest the existence of -CONH2 groups in the H2O2 plus ammonia modified coke. The SO2 adsorption capacity of an activated coke increases slightly with an increase in H2O2 concentration during the modification process. The desulphurization performance of a modified coke is considerably enhanced by increasing the treatment temperature during ammonia modification. The amount of nitrogen in a coke modified by H2O2 plus NH3.H2O is the highest, and the SO2 adsorption capacity of the coke is also the highest (89.9 mg/gC). The NH3.H2O (only) modified sample has lower nitrogen content and lower desulphurization capacity (79.9 mg/gC). H2O modification gives the lowest SO2 adsorption capacity (28.9 mg/gC). The H2O2 pre-treatment is beneficial for the introduction of nitrogen onto the surface of a sample during the following ammonia treatment process.

Effects of surface chemical properties of activated coke on selective catalytic reduction of NO with NH_3 over commercial coal-based activated coke

Surface chemical properties of typical commercial coal-based activated cokes were characterized by Xray photoelectron spectroscopy(XPS) and acid-base titration, and then the influence of surface chemical properties on catalytic performance of activated cokes of NO reduction with NH3 was investigated in a fixed-bed quartz micro reactor at 150 ℃. The results indicate that the selective catalytic reduction(SCR) activity of activated cokes with the increase of its surface acidic sites and oxygen content,obviously, a correlation between catalytic activity and surface acidic sites content by titration has higher linearity than catalytic activity and surface oxygen content by XPS. While basic sites content by acid-base titration have not correlation with SCR activity. It has been proposed that surface basic sites content measured by titration may not be on adjacent of acidic surface oxides and then cannot form of NO2-like species, thus the reaction of reduction of NO with NH3 have been retarded.

Systematic investigation of SO_(2) adsorption and desorption by porous powdered activated coke:Interaction between adsorption temperature and desorption energy consumption

Porous carbon materials have been widely used for the removal of SO_(2) from flue gas.The main objective of this work is to clarify the effects of adsorption temperature on SO_(2) adsorption and desorption energy consumption.Coal-based porous powdered activated coke(PPAC)prepared in the drop-tube reactor was used in this study.The N_(2) adsorption measurements and Fourier transform infrared spectrometer analysis show that PPAC exhibits a developed pore structure and rich functional groups.The experimental results show that with a decrease in adsorption temperature in the range of 50–150℃,the adsorption capacity of SO_(2) increases linearly;meanwhile,the adsorption capacity of H_(2)O increases,resulting in the increase in desorption energy consumption per unit mass of adsorbent.The processes of SO_(2) and H_(2)O desorption were determined by the temperature-programmed desorption test,and the desorption energies for each species were calculated.Considering the energy consumption per unit of desorption and the total amount of adsorbent,the optimal adsorption temperature yielding the minimum total energy consumption of regeneration is calculated.This study systematically demonstrates the effect of adsorption temperature on the adsorption–desorption process,providing a basis for energy saving and emission reduction in desulfurization system design.

Fluidized bed combustion of high water content alcohol extracted herb residue and the impacts of blending wasted activated coke

Combustion of herb residues(HRs)for heat recovery is a good way for their utilization,but there exists such a problem as high concentration NOx emission in flue gas.The alcohol extracted herb residue(AEHR),one special type of HRs,was chosen as the object and was subjected to immediate combustion in a fluidized bed reactor to investigate the characteristics of its resulting NOx emission.The results showed that,most of the NOx in the flue gas was produced from the char nitrogen(C-N);as the fuel water content increased,the NOx emission concentration exhibited a trend of first decreasing and then increasing;and a properly low combustion temperature inhibited the NOx emission upon the premise of ensuring full combustion.Air staging combustion was adopted to effectively control NOx:the NOx emission concentration in the flue gas was reduced to 296 mg⋅m􀀀3 and the NOx emission reduction rate reached 46.51%compared to conventional combustion.Co-combustion by blending wasted activated coke(WAC)into the AEHR helped both stabilize the combustion state and reduce further the NOx emission.When the blending ratio of WAC fell within a proper range of 20-30%,the NOx emission concentration in the flue gas was as low as 231.4 mg⋅m􀀀3.In addition to the dilution effect of the combustion flue gas of the blended WAC,the local reducing atmosphere caused by its incomplete combustion as well as its strong absorbability and catalytical effect was accountable for the further decrease of the NOx emission concentration.

Organic pollutants removal from 2,4,6-trinitrotoluene (TNT) red water using low cost activated coke

We treated 2,4,6-trinitrotoluene （TNT） red water from the Chinese explosive industry with activated coke （AC） from lignite. Since the composition of TNT red water was very complicated, chemical oxygen demand （COD） was used as the index for evaluating treatment efficiency. This study focused on sorption kinetics and equilibrium sorption isotherms of AC for the removal of COD from TNT red water, and the changes of water quality before and after adsorption were evaluated using high performance liquid chromatography, UV-Vis spectra and gas chromatography/mass spectroscopy. The results showed that the sorption kinetics of COD removal from TNT red water onto AC fitted well with the pseudo second-order model. The adsorption process was an exothermic and physical process. The sorption isotherm was in good agreement with Redlich-Peterson isotherm. At the conditions of initial pH = 6.28, 20°C and 3 hr of agitation, under 160 g/L AC, 64.8% of COD was removed. The removal efficiencies of 2,4-dinitrotoluene-3-sulfonate （2,4-DNT-3- SO3-） and 2,4-dinitrotoluene-5-sulfonate （2,4-DNT-5-SO3-） were 80.5% and 84.3%, respectively. After adsorption, the acute toxicity of TNT red water reduced greatly, compared with that of unprocessed TNT red water.

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature

Cu-Co multiple-oxides modified on HNO_3-pretreated activated coke(AC_(N))were optimized for the simultaneous removal of gaseous CO and elemental mercury(Hg^(0))at low temperature(<200℃).It was found that 2%CuOx-10%CoOx/AC_(N)catalyst calcined at 400℃resulted in the coexistence of complex oxides including CuO,Cu_2 O,Co_(3)O_(4,Co_(2)O_(3)and CoO phases,which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg^(0)by Cu-species,benefiting from the synergistic catalysis during the electrointeraction between Go and Cu cations(CoO■Co_(3)O_(4)and Cu_(2)O■CuO).The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining94.7%at 200℃,while no obvious promoting effect on the Hg^(0)removal(68.3%-78.7%).These materials were very substitute for the removal of CO and Hg^(0)from the flue gas with the conditions of 8-20 vol.%O_(2)and flue-gas temperature below 200℃.The removal of Hg^(0)followed the combination processes of adsorption and catalytic oxidation reaction via LangmuirHinshelwood mechanism,while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.

Properties change of activated coke for sintering flue gas purification in cyclic removal of SO_(2) and NO_(x)

The properties of activated coke(AC)for sintering flue gas purification greatly affect the efficiency of desulfurization and denitration,but they gradually change during cycles.The change in properties of coal-based AC during cycles was studied to clarify the change law and AC optimization index.The AC oxygen content rapidly increases 13.49 to 17.87 wt.%in the early cycles to form phenol,which promotes the denitration rate 55.63%to 78.20%.The denitration performance slowly increases in subsequent cycles becaof the generation of quinone AC slow oxidation.However,the oxygen-containing groups are not conducive to adsorption capacity of AC for NO.The adsorbed NO species which can be replaced SO2 is the main NO species on AC,and its amount decreases with the decrease in CC content of AC.The AC chemical loss leads to the opening of closed pores,expansion of original pores and formation of new pores,causing micropore volume to increase 0.085%to 0.152%,compressive strength to decrease 472 to 336 N,and abrasive resistance to decrease 97.87%to 94.16%during cycles.The low oxygen content and high micropore volume are favorable to the initial desulfurization performance,and the former is more decisive.After a while,the desulfurization rate is linearly positively correlated with the micropore volume regardless of the chemistry.4-h desulfurization rate increased 69.03%to 85.91%during 25 cycles due to the increasing micropore volume.The AC properties change in cycles will greatly affect the desulfurization and denitration rate in the height direction of the flue gas purification system.Selecting the coal-based AC with moderate micropore volume,easy oxidation surface and less original oxygen-containing groups facilitates the better purification efficiency at lower cost for sintering plants.

Optimization of process parameters for preparation of powdered activated coke to achieve maximum SO_(2)adsorption using response surface methodology

Powdered activated coke(PAC)is a good adsorbent of SO_(2),but its adsorption capacity is affected by many factors in the preparation process.To prepare the PAC with a high SO_(2)adsorption capacity using JJ-coal under flue gas atmosphere,six parameters(oxygen-coal equivalent ratio,reaction temperature,reaction time,O_(2)concentration,CO_(2)concentration,and H_(2)O concentration)were screened and optimized using the response surface methodology(RSM).The results of factor screening experiment show that reaction temperature,O_(2)concentration,and H_(2)O(g)concentration are the significant factors.Then,a quadratic polynomial regression model between the significant factors and SO_(2)adsorption capacity was established using the central composite design(CCD).The model optimization results indicate that when reaction temperature is 904.74℃,O_(2)concentration is 4.67%,H_(2)O concentration is 27.98%,the PAC(PAC-OP)prepared had a higher SO_(2)adsorption capacity of 68.15 mg/g while its SO_(2)adsorption capacity from a validation experiment is 68.82 mg/g,and the error with the optimal value is 0.98%.Compared to two typical commercial activated cokes(ACs),PAC-OP has relatively more developed pore structures,and its SBET and Vtot are 349 m^(2)/g and 0.1475 cm3/g,significantly higher than the 186 m^(2)/g and 0.1041 cm3/g of AC1,and the 132 m^(2)/g and 0.0768 cm3/g of AC2.Besides,it also has abundant oxygen-containing functional groups,its surface O content being 12.09%,higher than the 10.42%of AC1 and 10.49%of AC2.Inevitably,the SO_(2)adsorption capacity of PAC-OP is also significantly higher than that of both AC1 and AC2,which is 68.82 mg/g versus 32.53 mg/g and 24.79 mg/g,respectively.

Analysis of operational parameters affecting denitrification rate of sintering flue gas in cross-flow activated coke purification facility

The denitrification rate of the cross-flow activated coke flue gas purification facility varies with operational parameters. According to the simulated experiments, the denitrification rate with the height drop of the denitrification unit experiences 100%, rapid decreasing, and gradual rising to the equilibrium. According to the correlation analysis results based on production data, several operational parameters affecting the denitrification rate have been obtained. The denitrification rate has negative relationships with the activated coke bed temperature, the flue gas flow, the H2O content, the SO2 content and the NH3 slip, and has positive relationships with the O2 content, the NOx content, the NH3–NOx molar ratio, the flue gas pressure and the regeneration temperature. Properly increasing the sintering air leakage or the cooling air added into flue gas is beneficial to increase the denitrification rate. Priority should be given to O2, NH3–NOx molar ratio and flue gas flow to improve the denitrification rate. Additionally, a linear model, which had been validated, was developed and can be used to predict and control the denitrification rate.

Co-Ce-Ni Ternary Metal Oxide Modified N-activated Carbon:The Superior Low Temperature NH3-SCR Performance

Introducing reduced metal and nitrogen species is a powerful strategy to improve the reactivity of carbon-based materials for selective catalytic reduction of NO_(x) with NH_(3).To further improve the NH_(3)-SCR performance of non-pitch coal activated coke(NPAC),a series of metal oxides(e.g.,Co,Ce,and Ni)were loaded on nitrogen modified NPAC.The outstanding performance of NPAC-N-CoCeNi as well as the superior SO_(2)-and H_(2)O-tolerate performance are attributed to the extra electrons caused by the modification of N species,and these extra electrons are more conducive to the electron transfer.More importantly,the interaction of the major active component Co^(3+)and the promoter catalysts CeO_(2),NiOx,or CoNiO_(2) can also increase the charge transfer and produce more oxygen vacancy and unsaturated chemical bonds,leading to improving the redox performance of NPAC-N-CoCeNi.In addition,the NH3-SCR reaction is promoted after the metal oxides co-doping mainly via the Mars-van-Krevelen mechanism.

Preparation of active coke combining coal with biomass and its denitrification performance

To improve the selective catalytic reduction of NO with NH3 over active coke(AC),coal–biomass ACs were prepared from the mixture of poplar and 1/3 coking coal for increasing the active sites.The resultant ACs were characterized by N2 adsorption and X-ray photoelectron spectroscopy.Furthermore,the denitrification performance was tested at laboratory scale.In addition,density functional theory was used to analyze active sites on the surface of AC.The result revealed that,with an increase in poplar content,the decrease in micropores volume appeared in the reduction of denitrification space.However,C−O group including hydroxyl and ether increased with the increase in poplar content,which was found to be most likely responsible for the promoted catalytic activity of AC toward NO reduction mainly because of enhancing NH3 adsorption.The comprehensive effect of two factors made the denitrification ability of AC increased first and then decreased.