Modification of CaO-based sorbents prepared from calcium acetate for CO_2 capture at high temperature

CaO-based sorbent is considered to be a promising candidate for capturing CO_2 at high temperature. However,the adsorption capacity of CaO decreases sharply with the increase of the carbonation/calcination cycles. In this study, CaO was derived from calcium acetate(CaAc_2), which was doped with different elements(Mg, Al,Ce, Zr and La) to improve the cyclic stability. The carbonation conversion and cyclic stability of sorbents were tested by thermogravimetric analyzer(TGA). The sorbents were characterized by N_2 isothermal adsorption measurements, scanning electron microscopy(SEM) and X-ray diffraction(XRD). The results showed that the cyclic stabilities of all modified sorbents were improved by doping elements, while the carbonation conversions of sorbents in the 1st cycle were not increased by doping different elements. After 22 cycles, the cyclic stabilities of CaO–Al, CaO–Ce and CaO–La were above 96.2%. After 110 cycles, the cyclic stability of CaO–Al was still as high as 87.1%. Furthermore, the carbonation conversion was closely related to the critical time and specific surface area.

Co-pyrolysis of bituminous coal and biomass in a pressured fluidized bed

An experimental study on co-pyrolysis of bituminous coal and biomass was performed in a pressured fluidized bed reactor.The blend ratio of biomass in the mixture was varied between 0 and 100 wt%,and the temperature was over a range of 550–650℃ under 1.0 MPa pressure with different atmospheres.On the basis of the individual pyrolysis behavior of bituminous coal and biomass,the influences of the biomass blending ratio,temperature,pressure and atmosphere on the product distribution were investigated.The results indicated that there existed a synergetic effect in the co-pyrolysis of bituminous coal and biomass in this pressured fluidized bed reactor,especially when the condition of bituminous coal and biomass blend ratio of 70:30(w/w),600℃,and 0.3 MPa was applied.The addition of biomass influenced the tar and char yields and gas and tar composition during co-pyrolysis.The tar yields were higher than the calculated values from individual pyrolysis of each fuel,and consequently the char yields were lower.The experimental results showed that the composition of the gaseous products was not in accordance with those of their individual fuel.The improvement of composition in tar also indicated synergistic effect in the co-pyrolysis.

Effect of pre-calcination for modified CaO-based sorbents on multiple carbonation/calcination cycles

In the present work,the effect of pre-calcination on carbonation conversion and cyclic stability of modi fied CaObased sorbent was investigated by thermogravimetric analyzer(TGA).The modi fied CaO-based sorbents with CaAc_2 as precursor were respectively doped with different elements(Mg,Al,Ce,Zr and La).The speci fic surface area,pore volume and pore size distribution were tested by N_2 isothermal adsorption measurements.The phase compositions of sorbents were characterized by X-ray diffraction(XRD).The results showed that the cyclic stabilities of the sorbents were improved by pre-calcination.The pre-calcination was conducted at 900°C for 5 h in air by the muf fle furnace.With pre-calcination,the cyclic stabilities of sorbents could be as high as 96% after 22 cycles,such as CaO-Al,CaO-Ce and CaO-La.After contact with air,the carbonation conversions of spent sorbents with pre-calcination suddenly increased by about one-sixth due to the change of channel structure by hydration.Both the cyclic stability of sorbent and the durability of reactivation were related to the structural stability of sample,especially the stability of mesopores between 2 nm and 5.5 nm.The present work also provided an easy and low-cost method for reactivating the spent CaO-based sorbents.

Selective preparation of light aromatic hydrocarbons from catalytic fast pyrolysis vapors of coal tar asphaltene over transition metal ion modified zeolites

The catalytic cracking of coal tar asphaltene(CTA)pyrolysis vapors was carried out over transition metalion modified zeolites to promote the generation of light aromatic hydrocarbons(L-ArHs)in a pyrolysisgas chromatography/mass spectrometry(Py-GC/MS)micro-reactor system.The effects of ultra stable Y(USY),Co/USY and Mo/USY on the selectivity and yield of L-ArHs products and the extent of deoxygenation(Edeoxygenation),lightweight(Elightweight)from CTA pyrolysis volatiles were investigated.Results showed that the yields of L-ArHs are mainly controlled by the acid sites and specific surface area of the catalysts,while the deoxygenation effect is determined by theirs pore size.The Eligltweight of CTA pyrolysis volatiles over USY is 9.65%,while the Edeoxygenation of CTA pyrolysis volatiles over Mo/USY reaches 20.85%.Additionally,the modified zeolites(Mo/USY and Co/USY)exhibit better performance than USY on L-ArHs production,owing to the synergistic effect of metal ions(Mo,Co)and acid sites of USY.Compared with the non-catalytic fast pyrolysis of CTA,the total yield of L-ArHs obtained over USY(4032 mg·kg^(-1)),Co/USY(4363 mg·kg^(-1))and Mo/USY(4953 mg·kg^(-1))were increased by 27.03%,38.19%and 54.78%,respectively.Furthermore,the possible catalytic conversion mechanism of transition metal ion(Co and Mo)modified zeolites was proposed based on the distribution of products and the characterizations of catalysts.

Catalytic conversion of asphaltenes to BTXN using metal-loaded modified HZSM-5

HZSM-5 zeolites with Si/Al ratios of 20,35,50 and 65 were prepared by the directing crystallization process of silicalite-1 seeds.The influence of Si/Al ratios on the production of benzene,toluene,xylene and naphthalene(BTXN)originated from asphaltenes catalytic pyrolysis was explored by adopting Py-GC/MS.Modified Z5-50 zeolites were prepared by various metal ions(Ni^(2+),Mo^(6+),Fe^(3+),and Co^(2+))with different loading rates(3%(mass),5%(mass),7%(mass),and 9%(mass))and the physical and chemical properties of these zeolites were characterized by XRD,SEM,ICP-OES,XPS,NH_(3)-TPD,FTIR,Py-IR and N_(2)adsorption-desorption isotherm.In addition,they were employed to catalyze the conversion of asphaltenes pyrolysis production to BTXN using Py-GC/MS.Results show that the highest relative content of aromatics has been obtained over HZSM-5 with Si/Al ratio of 50(Z5-50),reaching 61.87%.Besides,the loading of Ni,Mo,Fe,and Co on Z5-50 leads to an increase of acid strength and provides new active sites.The relative content of BTXN increases by 3.17%over 3Ni-Z5,which may be ascribed to that Ni promoted the conversion of polycyclic aromatic hydrocarbons(PAHs)to monocyclic aromatics due to the cracking of aliphatic side chains of PAHs and the decrease of phenolic activation energy.While under the catalysis of 5Mo-Z5,the relative content of aromatics and BTXN augmented by 5.75%and 4.02%,respectively.In addition,the highest relative content of aromatics reaches 70.09%when the loading rate of Fe was 7%(mass),and the relative content of BTXN increases from 25.87%to 29.42%.The results demonstrate that the active sites provided by different metal species expressed diverse effects on BTXN.Although the Bronsted/Lewis acid ratios of HZSM-5 modified by metal decreased,the acid strength and the relative content of BTXN both increased,which illustrated that there is a synergistic catalysis with the Bronsted acid sites and Lewis acid sites provided by metal species.In general,the performance of the catalyst is affected by the pore structure,acidity and metal active sites.Moreover,the possible formation mechanism of BTXN derived from asphaltenes catalytic pyrolysis was proposed on the basis of structural features and catalytic performances of a series of zeolites.

Study on attrition of spherical-shaped Mo/HZSM-5 catalyst for methane dehydro-aromatization in a gas–solid fluidized bed

As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,longtime rapid movement and chemical reaction.Existing evaluation methods for attrition resistance,such as ASTM D5757 and Jet Cup test,are targeted for fresh catalysts at ambient temperature,which cannot well reflect the real process.In this study,spherical-shaped Mo/HZSM-5 catalyst prepared by dipping and spray drying was placed in a self-made apparatus for attrition testing,in which the catalyst attrition under different system temperatures,running time and process factors was investigated with percent mass loss(PML),particle size-mass distribution(PSMD)and scanning electron microscope(SEM).Carbon deposition on the catalyst before and after activation,aromatization and regeneration was analyzed by thermogravimetry(TG),and the attrited catalysts were evaluated for methane dehydro-aromatization(MDA).The results show that the surface abrasion and body breakage of catalyst particles occur continuously,with the increase of system temperature and running time,and make the PML rise gradually.The process factors of activation,aromatization and regeneration can cause the catalyst attrition and carbon deposits,which broaden the PSMD in varying degrees,and the carbon-substances on catalysts greatly improve their attrition resistance at high temperature.Catalyst attrition has a certain influence on its catalytic performance,and the main reasons point to particle breakage and fine powder escape.

Development of a new continuous process for the production of 3,5-dimethylpiperidine

This paper developed a new clean continuous process for the hydrogenation of 3,5-dimethylpyridine(DPY)to 3,5-dimethylpiperidine(DPI)without solvent.A series of Ru/C catalysts were prepared by impregnation method,which were characterized by the BET,ICP,CO chemisorptions,XRD,SEM,EDS,TEM and TG.The effect of active species,loading,catalyst support,reaction temperature and pressure on the catalytic performance was investigated.The influence of internal and external diffusion in the trickle-bed reactor(TBR)was basically eliminated by adjusting the particle size and dosage of the Ru/C catalyst.The reaction performance of the hydrogenation of DPY to DPI in the TBR and kettle reactor(KR)was compared,and the superiority of the TBR process was analyzed.The results show that this new continuous process developed in this study is an efficient way to realize the hydrogenation of DPY to DPI,and has a good industrial application prospect.

Mass Loss Behavior and Volatile Composition during Pyrolysis of a Bituminous Coal

The thermogravimetry analyzer coupled with the pyrolysis gas chromatography/time-of-flight mass spectrometry technology was used in this study to investigate the mass loss behavior and volatile release characteristics of a bituminous coal. The results showed that with an increasing heating rate, the characteristic parameters and TG/DTG curves shifted obviously to the higher temperature region. The pyrolysis of a bituminous coal at different heating rates can be divided into two stages according to the Coats-Redfern(C-R) plots. The activation energy obtained from the C-R method is 50.21—85.14 kJ/mol and 5.14—7.24 kJ/mol at a heating rate range of 8—300 °C/min for the first and second pyrolysis stages, respectively. Aromatic hydrocarbons were dominant in the volatile products during fast pyrolysis of the coal, followed by the olefins, whereas the phenols were the third major components. With the increase of pyrolysis temperature, the heavy components in the volatile species increased; meanwhile the phenol cracking reactions were intensified. The carbon number of olefins was mainly concentrated in 3—9, and the aromatics were mainly composed of the compounds of C_6—C_(13).This study can provide a basic reference for fast pyrolysis of coal and other thermal chemical conversion processes.

Effect of gas composition on nitric oxide removal from simulated flue gas with DBD-NPC method

A new method for nitric oxide(NO)removal was developed by combining dielectric barrier discharge(DBD)and negative pulse corona(NPC).The effects of gas composition(O2,CO2,and H2 O)on NO removal were investigated with this method,and the effect of alcohols(methanol and ethanol)addition on NO removal was also investigated as well as the reaction mechanisms to enhance the NO removal efficiency.The experimental results showed that O2,CO2,and H2 O had obvious inhibition effects on NO removal,and the negative effects were in the following order:O2>CO2>H2 O.The addition of methanol or ethanol in the reaction system could mitigate the negative effects of O2,CO2 and H2 O on NO removal,and also eliminated the production of N02.The positive effect of alcohols addition with DBD-NPC denitration method was also validated in the simulated flue gas,in which the NOx(NO,NO2)was mainly converted into N2.

A study on simultaneous removal of NO and SO2 by using sodium persulfate aqueous scrubbing

Nitric oxide(NO) removal and sulfur dioxide(SO_2) removal by sodium persulfate(Na_2S_2O_8) were studied in a Bubble Column Reactor. The proposed reaction pathways of NO and SO_2 removal are discussed. The effects of temperatures(35–90 °C), Na_2S_2O_8(0.05–0.5 mol·L^(-1)), Fe SO4(0.5–5.0 m mol·L^(-1)) and H_2O_2(0.25 mol·L^(-1))on NO and SO_2 removal were investigated. The results indicated that increased persulfate concentration led to increase in NO removal at various temperatures. SO_2 was almost completely removed in the temperature range of 55–85 °C. Fe^(2+)accelerated persulfate activation and enhanced NO removal efficiency. At 0.2 mol·L^(-1) Na_2S_2O_8 and 0.5–1.0 mmol·L^(-1) Fe^(2+), NO removal of 93.5%–99% was obtained at 75–90 °C, SO_2 removal was higher than 99% at all temperatures. The addition of 0.25 mol·L^(-1) H_2O_2 into 0.2 mol·L^(-1) Na_2S_2O_8 solution promoted NO removal efficiency apparently until utterly decomposition of H2 O2, the SO_2 removal was as high as98.4% separately at 35 °C and 80 °C.

Development of a CH4 dehydroaromatization–catalyst regeneration fluidized bed system

A pilot-scale methane dehydroaromatization–H_2regeneration fluidized bed system(MDARS)was developed.In the MDARS,the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help of a catalyst feeder allowed methane dehydroaromatization(MDA)and H_2regeneration to be carried out simultaneously,which is good for maintaining a stable MDA catalytic activity.A fixed bed reactor(FB)and a single fluidized bed reactor(SFB)were also used for a comparative study.The experimental results showed that the catalytic activity in the MDARS was more stable than that in the FB and SFB reactors.The effects of some parameters of MDARS on the CH_4conversion and product selectivity were investigated.To verify the feasibility and reliability of the MDARS,an eight-hour long-term test was carried out,which demonstrated that the operation of the MDARS was stable and that the catalytic activity remained stable throughout the entire experimental period.

Selective catalytic hydrogenation of naphthalene to tetralin over a NiMo/Al2O3 catalyst

The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated.A series of Al2O3 catalysts containing different active metals(Co,Mo,Ni,W)were prepared by incipient wetness impregnation.The effects of different active metals forms(oxidation,reduction,sulfuration)and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD,XPS,BET,NH3-TPD and SEM.Especially,Ni-Mo/Al2O3 was first used in this reactive system.The results show that the oxidative4%Ni O-20%MoO3/Al2O3 is the best catalyst for the preparation of tetralin.The conversion of naphthalene and the selectivity of tetralin can reach 95.62%and 99.75%respectively at 200℃,8 h and 6 MPa.Compared with reduced and sulfureted 4%Ni O-20%MoO3/Al2O3 catalysts,oxidative 4%Ni O-20%MoO3/Al2O3 has a well dispersed and uniform monolayer of the active metals,larger pore volume and size,and larger total acidity.NiO-MoO3/Al2O3 has a synergistic effect between NiO activity and MoO3 selectivity.

Co-pyrolysis characteristics and interaction route between low-rank coals and Shenhua coal direct liquefaction residue

To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.

Life cycle assessment of HFC-134a production by calcium carbide acetylene route in China

HFC-134a is a widely used environment-friendly refrigerant.At present,China is the largest producer of HFC-134a in the world.The production of HFC-134a in China mainly adopts the calcium carbide acetylene route.However,the production route has high resource and energy consumption and large waste emission,and few of the studies addressed on the environmental performance of its production process.This study quantified the environmental performance of HFC-134a production by calcium carbide route via carrying out a life cycle assessment(LCA)using the CML 2001 method.And uncertainty analysis by Monte-Carlo simulation was also carried out.The results showed that electricity had the most impact on the environment,followed by steam,hydrogen fluoride and chlorine,and the impact of direct CO_(2) emissions in calcium carbide production stage on the global warming effect also could not be ignored.Therefore,the clean energy(e.g.,wind,solar,biomass,and natural gas)was used to replace coal-based electricity and coal-fired steam in this study,showing considerable environmental benefits.At the same time,the use of advanced production technologies could also improve environmental benefits,and the environmental impact of the global warming category could be reduced by 4.1%via using CO_(2) capture and purification technology.The Chinese database of HFC-134a production established in this study provides convenience for the relevant study of scholars.For the production of HFC-134a,this study helps to better identify the specific environmental hotspots and proposes useful ways to improve the environmental benefits.

The effect of hydrothermal pretreatment on the structure and fast pyrolysis behaviors of Sheng Li lignite

The structure and composition of coal determine its fast pyrolysis characteristics,and the study of the relationship between them can play an important role in the efficient and clean utilization of coal.So,in this work,hydrothermal pretreatment was used to artificially change the structure and composition of Sheng Li(SL)lignite,which was used to investigate the influence of structural changes on pyrolysis.The physicochemical structure and composition of samples were characterized by X-ray diffraction,specific surface area and porosity analyzer,solid-state 13C nuclear magnetic resonance,Fourier transform infrared spectroscopy,and elemental analyzer.Pyrolysis experiments were carried out in a powderparticle fluidized bed reactor,and the distribution and composition of the pyrolysis products were analyzed.The gasification activity of char was investigated by thermogravimetric analysis with a CO_(2) atmosphere.The results show that hydrothermal pretreatment(HTP)can destroy the cross-linking structure of SL lignite,and affect its aromaticity,pore structure,functional group,and carbon structure to change the distribution and composition of pyrolysis products of SL lignite,especially the composition of tar.Finally,the structure–activity relationship between the structure,composition,and pyrolysis characteristics of coal was comprehensively studied.

Life cycle assessment and economic analysis of HFC-134a production from natural gas compared with oil-based and coal-based production

China is the largest producer and consumer of HFC-134a(1,1,1,2-tetrafluoroethane)in the world.Coal-based route is mainly adopted to produce HFC-134a,which suffers from large waste and CO_(2) emissions.Natural gas is a low-carbon and clean energy resource,and no research has been found on the environment and economy of producing HFC-134a from natural gas.In this study,CML 2001 method was used to carry out the life cycle assessment of natural gas(partial oxidation)-based and natural gas(plasma cracking)-based routes(abbreviated as gas(O)-based and gas(P)-based routes,respectively),and their environmental performances were compared with coal-based and oil-based routes.Meanwhile,considering that China is vigorously promoting the transformation of energy structure,and the application of electric heating equipment to replace fossil-based heating equipment in industrial field,which has a great impact on the environmental performance of the production processes,the authors conducted a scenario analysis.The results showed that the gas(O)-based route had the most favourable environmental benefits.However,the gas(P)-based route had the highest potential for reducing environmental burdens,and its environmental benefit was the most favourable in scenario 2050.Additionally,the economic performance of the gas(P)-based route was significantly better than that of gas(O)-based and coal-based routes.

Development of an in-situ H_(2)reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor

The Ru/C catalyst prepared by impregnation method was used for hydrogenation of 3,5-dimethylpyridine in a trickle bed reactor.Under the same reduction conditions(300°C in H_(2)),the catalytic activity of the non-in-situ reduced Ru/C-n catalyst was higher than that of the in-situ reduced Ru/C-y catalyst.Therefore,an in-situ H_(2)reduction and moderate oxidation method was developed to increase the catalyst activity.Moreover,the influence of oxidation temperature on the developed method was investigated.The catalysts were characterized by Brunauer–Emmett–Teller method,hydrogen temperature programmed reduction H_(2)-TPR,hydrogen temperature-programmed dispersion(H_(2)-TPD),X-ray diffraction,energy dispersive spectroscopy,X-ray photoelectron spectroscopy,Raman spectroscopy,O2 chemisorption and oxygen temperature-programmed dispersion(O2-TPD)analyses.The results showed that there existed an optimal Ru/RuO_(x)ratio for the catalyst,and the highest 3,5-dimethylpyridine conversion was obtained for the Ru/C-i1 catalyst prepared by in-situ H_(2)reduction and moderate oxidation(oxidized at 100°C).Excessive oxidation(200°C)resulted in a significant decrease in the Ru/RuO_(x)ratio of the in-situ H_(2)reduction and moderate oxidized Ru/C-i2 catalyst,the interaction between RuO_(x)species and the support changed,and the hard-to-reduce RuO_(x)species was formed,leading to a significant decrease in catalyst activity.The developed in-situ H_(2)reduction and moderate oxidation method eliminated the step of the non-in-situ reduction of catalyst outside the trickle bed reactor.

Multi-fluid Eulerian simulation of mixing of binary particles in a gas-solid fluidized bed with a cohesive particle-particle drag model

A particle-particle(p-p)drag model is extended to cohesive particle flow by introducing solid surface energy to characterize cohesive collision energy loss.The effects of the proportion of cohesive particles on the mixing of binary particles were numerically investigated with the use of a Eulerian multiphase flow model incorporating the p-p drag model.The bed expansion,mixing,and segregation of Geldart-A and C particles were simulated with varying superficial velocities and Geldart-C particle proportions,from which we found that the p-p drag model can reasonably predict bed expansion of binary particles.Two segregation types of jetsam-mixture-flotsam and mixture-flotsam processes were observed during the fluidization processes for the Geldart-A and C binary particle system.The mixing processes of the binary particle system can be divided into three scales:macro-scale mixing,meso-scale mixing,and micro-scale mixing.At a constant superficial velocity the optimal mixing was observed for a certain cohesive particle proportion.