Articles in press have been peer-reviewed and accepted, which are not yet assigned to volumes /issues, but are citable by Digital Object Identifier (DOI).
Enhancement of the production of light aromatics from poplar wood by combined approach of wet torrefaction pretreatment and catalytic fast pyrolysis using metal modified hierarchical zeolite
CAI Wei, HUANG Ming, ZHU Liang, ZHENG Yu-bo, CAI Bo, MA Zhong-qing
 doi: 10.19906/j.cnki.JFCT.2023004
Abstract(25) HTML(7) PDF 1285KB(11)
Light aromatics are extremely important building blocks in the chemical industry which can be produced from the catalytic fast pyrolysis (CFP) of biomass. In this work, wet torrefaction pretreatment (WTP) was employed to improve the quality of poplar wood (PW) in terms of the synergetic deoxygenation and demineralization. Then, metal-modified hierarchical HZSM-5 was prepared by the combined approach of NaOH desilication pretreatment and metal (Zn、Ga, and Fe) modification. At last, the CFP of torrefied PW was carried out by using the metal-modified hierarchical HZSM-5 as catalyst to produce light aromatics. Results showed that the deoxygenation and demineralization rates gradually increased with the increase of WTP temperature from 180 to 260 ℃, the maximum removal rates of oxygen, K, Mg, Ca, and Na were 47.96%, 90.99%, 86.65%, 66.09%, and 36.29%, respectively. NaOH desilication pretreatment and metal modification on HZSM-5 promoted the formation of light aromatics. The Zn-modified hierarchical HZSM-5 presented the highest yield of light aromatics. The yield of aromatics increased first with the raise of catalyst-to-torrefied PW ratio from 1:1 to 1∶3, then decreased slightly at the highest catalyst-to-torrefied PW ratio of 1∶5. At last, the operation parameter of WTP and CFP was optimized which the maximum yield of light aromatics was 7.83 × 107 p.a./mg at WTP temperature of 220 ℃, catalyst-to-biomass ratio of 1∶3, and CFP temperature of 850 ℃.
Preparation of rice husk-based carbon material-supported Ruthenium as a catalyst for the hydrolytic dehydrogenation of ammonia borane
WU Hui, ZHENG Jun-ning, ZUO You-hua, XU Li-xin, YE Ming-fu, WAN Chao
 doi: 10.1016/S1872-5813(23)60349-4
Abstract(5) HTML(4) PDF 10032KB(0)
The development of efficient dehydrogenation catalysts is the key to promoting the application of solid chemical hydrogen storage materials ammonia borane (NH3BH3, AB) in the field of hydrogen energy. In this paper, a nitrogen-doped rice husk activated carbon carrier (N-RHC) was prepared by roasting melamine and rice husk at high temperature under N2 atmosphere, and then RuCl3 metal solution was added to it by impregnation method, and the active component Ru was loaded onto the N-RHC support to synthesize Ru/N-RHC catalyst, and its effect on the catalytic hydrogen production performance of ammonia borane was explored. The results show that the load of Ru is 5 wt%, the reaction conversion frequency (TOF) value of the catalyst is the largest, the TOF of the catalyst is 83.71 min−1 in Ru/N-RHC catalyst, and the activation energy (Ea) of ammonia borane hydrolysis on the catalyst decreases from 88.9 kJ/mol to 64.9 kJ/mol under photocatalysis, and the hydrogen production rate of ammonia borane is positively correlated with the concentration of ammonia borane and the concentration of the catalyst.
Utilization of domestic waste biomass char in the context of carbon neutrality—low NOx decoupled combustion
WANG Xin-kun, ZHANG Jie-han, CHEN Zhao-hui, FAN Hui-ling, YU Jian, GAO Shi-qiu
 doi: 10.19906/j.cnki.JFCT.2023013
Abstract(12) HTML(3) PDF 1719KB(3)
The carbon and nitrogen content of township waste is high, and direct combustion causes a large amount of CO2 and NOx emissions. The biomass carbon after pyrolysis can reduce the NO in the combustion flue gas to N2, which can reduce NOx emissions while using carbon resources. Using 6 typical components in 4 kinds of rural solid waste (including paper, plastic, wood and textile) as experimental materials, the pyrolysis and decoupling combustion experiments are carried out in a fixed-bed reactor to investigate the effect of decoupling combustion on NOx emission. The experimental results showed that when the pyrolysis temperature was 700 ℃ and the particle size were 1.6–2.5 mm, the concentration of reducing gas in pyrolysis gas was higher and the reduction rate of NO in the char reached over 60%. By comparing the N conversion of decoupling combustion with that of normal combustion and air staged combustion, the NOx emission reduction rates of the decoupling combustion were 44.1% and 18.1%, respectively. Therefore, the decoupling combustion of rural solid waste based on pyrolysis is an effective way to control NOx emission, which is conducive to the clean and efficient transformation and utilization of rural solid waste.
A research paper
Pyrolysis behavior of antibiotic residues and the mechanism of nitrogen evolution
DU Jia-xing, LI Chen-xu, ZHOU Xing-xing, WAN Gan, XU Lin-lin, WANG Ben, LI De-nian, SUN Lu-shi
 doi: 10.19906/j.cnki.JFCT.2023003
Abstract(33) HTML(9) PDF 4942KB(8)
The pyrolysis experiments of penicillin residues at different temperatures (300–700 ℃) were carried out on a fixed bed to study the yield of three-phase products and the morphology and distribution of nitrogen at different pyrolysis temperatures. The mechanism of the pyrolysis reaction of amino acids (aspartic acid, histidine and glutamic acid) contained in the bacterial residues and 2, 5-Piperazinedione (DKP) was investigated by ReaxFF molecular dynamics simulations. The results show that the yield of gas increased with the increase of temperature, while the char shows a declining trend. The yield of oil increased to a maximum of 42.3 wt.% at 500 ℃ and then decreased as temperature increased. The pattern of nitrogen content in the product with temperature was consistent with the trend of yield. Compared with H2 and hydrocarbon gases, CO2 and CO are more easily produced at low temperatures. Amides are the main nitrogenous compounds in oil, and the proportion of amides gradually decreases as the pyrolysis temperature increases. The deamination reaction of amino acids is the main source of NH3, and dehydration cyclization occurs between amino acid molecules to produce DKP-like compounds. Gases such as NH3, HCN, HNCO and R-NH, R-NH-R radicals are generated during the pyrolysis of DKP. Nitrogen-containing radicals combine with other radicals or undergo cyclization to form amides, ketones and other compounds present in oil and char.
Morphology Effect of Nano-hydroxyapatite as Support for Loading Ni in Methane Dry Reforming
WANG Yan-Bo, HE Lei, LI Wen-Cui
 doi: 10.1016/S1872-5813(23)60332-9
Abstract(62) HTML(14) PDF 4149KB(15)
Methane dry reforming (MDR) can simultaneously convert methane and carbon dioxide, two major greenhouse gases, into syngas (CO and H2), which can further produce fuels and chemicals through Fischer-Tropsch process. It is an important reaction for the utilization of carbon-containing resources with low carbon footprint. The design of efficient and stable MDR catalyst is one of the bottlenecks for industrial application. The properties of supports affect the stability of the active components and the carbon deposition-elimination rates, thus influencing the activity and stability of the catalyst. In this paper, hydroxyapatite (HAP) with nanorod, nanosheet and nanowire morphologies were synthesized with different Ca, O and P distributions over the surface. After loading 1.25wt% of nickel, Ni/HAP-R, Ni/HAP-S and Ni/HAP-W catalysts were obtained and applied for MDR studies. Among them, the Ni/HAP-R catalyst showed best performance. The geometric structure, electronic properties and surface acidity and alkalinity of the catalyst were characterized by XRD, N2 sorption, FT–IR, XPS and CO2–TPD. It proved that HAP-R possesses the larges surface area, thus, beneficial for Ni dispersion to obtain high MDR activity. Meanwhile, it was rich in Ca–O–P which can accelerate CO2 activation for coke elimination. TPSR experiments further confirmed that the deep cracking of methane on Ni/HAP-R catalyst was inhibited, but can be accelerated in the presence of CO2 to produce CO and H2. In this case, Ni/HAP-R catalyst showed excellent anti-coking performance. This study provides inspiration for the design and synthesis of highly stable heterogeneous catalysts.
A research paper
Hydrogen generation from hydrous hydrazine over Rh/g-C3N4 nanocatalysts
QIU Xiao-kui, SUN Jia-li, HUA Jun-feng, ZHENG Jun-ning, WAN Chao, XU Li-xin
 doi: 10.19906/j.cnki.JFCT.2022093
Abstract(40) HTML(9) PDF 6880KB(3)
As an ideal hydrogen storage material, hydrous hydrazine (N2H4·H2O) has attracted the attention of many researchers. Hydrous hydrazine is relatively stable at room temperature, and the development of efficient and highly selective catalysts under mild conditions is the key to realizing hydrogen production from the decomposition of hydrous hydrazine. In this paper, g-C3N4 obtained by calcining melamine at high temperature in static air is used as the carrier, and the precious metal Rh is used as the active component. The Rh nanoparticles are supported on the g-C3N4 support by a simple impregnation reduction method to prepare high activity and high selectivity. Various characterization methods were used to study the microstructure and composition of the catalyst. In addition, the effect of reaction temperature and NaOH concentration on the catalytic decomposition of hydrous hydrazine was also investigated. The results show that the excellent catalytic activity of the catalyst stems from the fact that the g-C3N4 support provides anchor sites for the metal Rh and the support and the strong metal−support interactions. The catalytic activity of the catalyst increased with the increase of the reaction temperature, and the Rh/g-C3N4 catalyst had the highest catalytic activity when the NaOH concentration was 0.75 mol/L. The Rh/g-C3N4 catalyst has an activation energy of 30.7 kJ/mol and TOF value of 1466.4 h−1 for catalyzing the decomposition of hydrous hydrazine for hydrogen production. After 5 cycles, the catalyst still maintains a good catalytic activity, indicating that the catalyst has a good cyclic stability.
A research paper
Study of grain size effect of lanthanum oxide catalyzed methane oxidation coupling reaction
ZHANG Qi, NIU Peng-yu, JIA Li-tao, LIN Ming-gui, LI De-bao
 doi: 10.19906/j.cnki.JFCT.2022089
Abstract(38) HTML(17) PDF 3533KB(10)
La2O3 catalysts with different grain sizes were prepared under hydrothermal condition. The structure activity relationship of La2O3 catalysts with different grain sizes were investigated by using in-situ XRD, Raman, FT-IR and H2-TPR,O2-TPD. The results show that the La−O bond of the La2O3 catalyst shows a significant elongation with increasing temperature, which affects its adsorption and dynamic storage of O2. When increasing the grain size up to 57.4 nm, the oxygen storage capacity of the La2O3 catalyst started to decrease, accompanied by the enrichment of surface oxygen species, especially superoxide species, on the catalyst surface, which led to the over-oxidation of CH4 and products and reduced the C2 + hydrocarbons selectivity. The L-La2O3 catalyst with a grain size of 52.3 nm has a suitable content of surface oxygen species and a high oxygen storage capacity at 750 ℃. It exhibited the best C2 + hydrocarbon selectivity up to a CH4/O2 of 3 and a vacancy rate of 1.6 × 105 mL/(g·h).
A research paper
Bimetallic oxynitride-Co single atom composite electrocatalyst synergistically improve oxygen reduction reaction in wide pH range
ZHAO Jiang-hong, QIN Yu-peng, WANG Qian-liang, QIAO Ze-yu, XUAN Jia-qi, ZHOU Wei
 doi: 10.19906/j.cnki.JFCT.2022095
Abstract(34) HTML(14) PDF 19913KB(3)
The lack of high performance and low cost oxygen reduction electrocatalysts, especially operating in the wide pH range, is one of the key obstacles restricting the large-scale applications of new energy conversion technologies such as fuel cells and metal-air batteries. In this work, based on the synthesis mechanism of conventional polymer-derived carbon materials, a bimetallic oxy-nitride (ComTinOxNy)-Co single atom (Co-NC) composite catalyst was prepared by an associated hydrothermal polymerization-pyrolysis method through selecting suitable precursor molecules and simultaneously introducing TiO2 nanoparticle in the process of polymerization. The bimetallic cobalt-titanium oxy-nitride Co-NC composite catalyst exhibits better ORR activity in a wide pH range (0−13) than the conresponding pure N-doped carbon nanotubes, titanium oxy-nitride/N-CNTs and Co-NC catalysts, providing a new idea for the development of ORR electrocatalysts with high performance and low cost.
Mechanisms of Brönsted and Lewis acids of zeolite on pentenes conversion by in situ DRIFTS
YI Feng-jiao, CHEN Hui-min, YANG Yong, CAO Jing-pei
 doi: 10.19906/j.cnki.JFCT.2022083
Abstract(56) HTML(24) PDF 4019KB(4)
Zeolites have been extensively used in the chemical and petrochemical industries owing to their tunable acidities and unique pore structures. Beta zeolite with Brönsted and Lewis acids and AlCl3@Si-Beta with only Lewis acid were prepared by hydrothermal synthesis and gas-phase impregnation methods, respectively. Mechanisms differences of Brönsted and Lewis acids on four pentene isomers transformation were investigated by in situ diffraction infrared Fourier transform spectrum (DRIFTS). The results suggested that Brönsted in Beta played a main role in isomerization and oligomerization reactions which all followed classical carbenium ion mechanisms. On the contrary, Lewis acid in AlCl3@Si-Beta without hydrogen proton or hydroxyl catalyzed α-pentene double-bond migration to produce β-pentene and cis-trans isomerization reaction of 2-pentene by AB-AD mechanism with allyl-like species as intermediates, and cannot catalyze pentenes skeletal isomerization and oligomerization reactions.
A research paper
Morphology study of nickel and vanadium in asphaltene s via hydropyrolysis
ZHENG Fang, WANG Yan-bin, HUO Da, WANG Chun-yan, CAO Qing, HE Jing, SHI Quan
 doi: 10.1016/S1872-5813(23)60333-0
Abstract(22) HTML(14) PDF 758KB(6)
The morphology of nickel and vanadium compounds in the asphaltenes were investigated via hydropyrolysis with the help of inductively coupled plasma mass spectrometer (ICP MS), ultraviolet-visible (UV-Vis), high-temperature gas chromatography atomic emission detection (HT GC-AED), and positive-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (+ESI FT-ICR MS). The results showed that the toluene soluble yields of products decreased from 64% to 19% as the hydropyrolysis temperature increased from 330℃ to 410℃, while the abundance of nickel and vanadium compounds detected by GC-AED increased significantly. The molecular composition distribution of nickel and vanadyl porphyrins showed rhythmic changes in the hydropyrolysis treated asphaltenes with different temperatures.
A research paper
Mechanistic study on the reaction of CO2 hydrogenation to methanol over Cu-Mn-La-Zr catalysts prepared by different methods
WANG Shi-qiang, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui
 doi: 10.1016/S1872-5813(22)60079-3
Abstract(65) HTML(13) PDF 1005KB(15)
The reaction mechanisms of the Cu-Mn-La-Zr catalysts prepared by co-precipitation (CMLZ-CP), sol-gel (CMLZ-S), and hydrothermal (CMLZ-H) methods were investigated by in-situ DRIFT and H2-TPD characterization. Surface hydroxyl groups were found to contribute to the CO2 hydrogenation to methanol, and all catalysts followed the formate (HCOO*) and carboxylate (COOH*) paths. For CMLZ-CP and CMLZ-H catalysts, the carboxylate path was preferred. While for CMLZ-S catalyst, the formate path was dominate. The CMLZ-CP catalyst had the strongest ability to activate H2 thus exhibiting the highest CO2 conversion and methanol yield. While the higher percentage of medium to strong basic sites and oxygen defects of the CMLZ-H catalyst favored the hydrogenation of intermediate species to methanol, thus exhibiting the highest methanol selectivity.
Preparation of NiPt/SBA-15 nanocatalyst and its catalytic performance for the dehydrogenation of hydrous hydrazine
LIANG Yu, LI Gui, ZHENG Jun-ning, XU Li-xin, YE Ming-fu, WAN Chao
 doi: 10.19906/j.cnki.JFCT.2022072
Abstract(45) HTML(16) PDF 3031KB(8)
As the most promising hydrogen storage material, hydrous hydrazine (N2H4·H2O) has attracted extensive attention and interest of researchers. In this paper, NiPt bimetallic supported SBA-15 (mesoporous silica) catalysts with different metal ratios were prepared by a simple impregnation reduction method, and their catalytic hydrous hydrazine dehydrogenation performance was studied. The research results show that Pt and Ni form an alloy during the preparation of the catalyst, the electronic synergistic effect of the two metals can effectively promote the catalytic performance of the catalyst, and the interaction between SBA-15 and the metal active components helps to improve the catalytic performance of the catalyst. Catalytic performance and cycling stability of catalysts. The activation energy of the Pt6Ni4/SBA-15 catalyst is 45.6 kJ/mol, TOF value is 2123.3 h−1, which are better than most of the reported catalysts.
A research paper
Effect of different valence metals doping on methane activation over La2O3(001) surface
ZHANG Jia-yu, SUN Na, LING Li-xia, ZHANG Ri-guang, JIA Li-tao, LI De-bao, WANG Bao-jun
 doi: 10.1016/S1872-5813(23)60343-3
Abstract(14) HTML(5) PDF 2974KB(1)
La2O3 as a catalyst is used for oxidative coupling of methane (OCM) reactions due to its excellent stability and high C2 selectivity, but poor activity on methane dissociation limits its wide application. Different valence metals are doped on the La2O3(001) surface to improve the methane conversion activity, and the activation of methane on metal-doped La2O3(001) surfaces has been investigated via the density functional theory (DFT) calculations. The relationship between the valence states of doped metals and the methane conversion activities shows that doping low valence metals (Li, Na, K, Mg, Ca, Sr and Ba) and equivalent metals (Al, Ga, In) can significantly improve the conversion activity of methane. Among them, the activation energy of methane on the Li-La2O3(001) surface is the lowest, which is only 13.0 kJ/mol. However, doping of high valence metals (Zr, Nb, Re and W) cannot improve the CH4 dissociation activity. Furthermore, the relationships between surface oxygen vacancy formation energies, acid-base properties and the activation energies of CH4 have also been investigated. The results show that with the increase of metal valence state, the oxygen vacancy formation energy increases, while the dissociation activity of CH4 decreases. The introduction of alkali and alkaline earth metals increases the alkalinity of La2O3(001) surface, and the alkalinity of La2O3(001) doped with the alkali metal is stronger than that with the alkaline earth metal, exhibiting higher dissociation activity of CH4. Our research may provide a guide for improving methane conversion activity on La2O3 catalysts.
A research paper
Effects of ball milling medium on Cu-Al spinel sustained release catalyst for H2 generation from methanol steam reforming
LIU Ya-jie, QIN Fa-jie, HOU Xiao-ning, GAO Zhi-xian
 doi: 10.1016/S1872-5813(23)60342-1
Abstract(18) HTML(6) PDF 961KB(6)
Using pseudo-boehmite and ultrafine copper hydroxide as the raw materials with n(Cu/Al) = 1∶3, the effects of ball milling medium on the Cu-Al spinel sustained release catalysts prepared via the solid-state reaction method are explored. The obtained catalysts are characterized by XRD, BET, and H2-TPR techniques, and their catalytic properties in methanol steam reforming (MSR) are evaluated. The results demonstrate that Cu-Al spinel solid solution can be synthesized by both dry and wet mechanical ball milling methods, and more Cu2 + ions are found to be incorporated into the spinel lattice through the latter method. The crystalline sizes of as-synthesized spinels are similar; however, the specific surface areas and pore volumes are different as well as their reduction properties. Compared with the dry milling method, the wet ball milling method can facilitate the solid phase reaction, generating catalysts with solely spinel crystalline phase, higher specific surface area, and larger pore volume. Furthermore, catalysts derived from the wet milling method demonstrate improved catalytic activity and stability, and lower CO selectivity in MSR. The highest activity is obtained over CuHAl-Ac-950 prepared using ethanol (95%) as the ball milling medium.
A research paper
Direct synthesis of LPG from syngas over Cu modified FeMg@SiO2 nano-level core@shell catalyst
 doi: 10.1016/S1872-5813(22)60064-1
Abstract(43) HTML(16) PDF 5502KB(8)
Direct synthesis of liquefied petroleum gas from syngas via Fischer-Tropsch synthesis route was systematically investigated over a nano-level core@shell catalyst. We introduced an incorporation of FeMg catalyst into mesoporous silica shell, with a further modification of Cu particles on the silica surface. The modified Cu/FeMg@SiO2 nano core-shell catalysts were synthesized by the combination of co-precipitation, modified sol-gel and facile impregnation methods. The as-synthesized catalysts’ physicochemical property was characterized by XRD, TEM, N2 adsorption-desorption, H2-TPR, XPS and CO2-TPD techniques. The catalytic performance of Cu/FeMg@SiO2 catalyst shows a high CO conversion of 96.6%, rather low CO2 selectivity of 21.9% and considerable LPG selectivity of 37.9%. The catalytic results indicate that the SiO2 shell restrains the formation of CH4 and contributes to increasing long-chain products. Meanwhile, the enhanced CO conversion of Cu/FeMg@SiO2 was ascribed to the active metal Cu dispersed on SiO2 shell, which also promoteolefin hydrogenation and cracking of C5+ hydrocarbons products. The proposed catalyst preparation method will provide a new strategy for the synthesis of nano level catalyst with combinations of metal- and zeolite-based catalyst.
Preparation of highly dispersed silicon spheres supported cobalt-based catalysts and their catalytic performance for Fischer-Tropsch synthesis
ZHANG Meng, LIU Jia, ZHANG Yu-hua, WANG Li, LI Jin-lin, HONG Jing-ping
 doi: 10.1016/S1872-5813(22)60078-1
Abstract(19) HTML(10) PDF 1745KB(3)
A series of silicon spheres supported cobalt catalysts were prepared by incipient wetness impregnation followed by decomposition under treatment of glow discharge plasma with different intensities. The catalysts were characterized by X-ray powder diffraction, N2 physical adsorption-desorption, H2 temperature-programmed reduction, transmission electron microscope and Fourier-Transform Infrared spectroscopy. The Fischer-Tropsch synthesis performance were tested on a fixed bed reactor. The influence of plasma treatment on cobalt dispersion, reducibility and cobalt-support interaction were analyzed and discussed. The results showed that the plasma-treated catalysts had better catalytic performance than the calcined sample. The Co/SP-P650W catalyst showed the highest reaction activity due to the proper cobalt dispersion and higher cobalt reducibility.
Microwave assisted synthesis of ZnO-TiO2 and its visible light catalytic denitrification activity
WANG Shu-qin, LI Xiao-xue, LI Dan
 doi: 10.1016/S1872-5813(22)60070-7
Abstract(30) HTML(14) PDF 1752KB(3)
Comparing the composite TiO2 prepared by hydrothermal sol gel method and microwave-assisted sol gel method, the microwave-assisted sol gel method with shorter time and better crystallinity was finally used to prepare ZnO-TiO2 materials with different composite ratios. The specific surface area, pore volume and pore size of ZnO- TiO2 composite are significantly larger than those of TiO2. The surface acidity of ZnO-TiO2 composite is stronger. The band structure is conducive to the efficient separation of electrons and holes, and the catalytic reduction activity and selectivity are stronger. The best composite ratio of ZnO and TiO2 is optimized to be 0.2 through photocatalytic denitration experiments. For NOx with an initial concentration of 6.83 mg/m3, under the light source condition irradiated by 65 W energy-saving lamp, the visible photocatalytic removal efficiency is as high as 85%. When the NOx concentration is increased to 13.67 mg/m3 and the ammonia nitrogen ratio is 1∶1, the denitration efficiency is as high as 96%, which is 43% higher than that of pure TiO2. According to mechanism analysis, the whole reaction can be divided into adsorption and photocatalysis. Adsorption is the speed control step of the reaction. NO is oxidized to NO2 under the action of adsorbed oxygen, and photogenerated electrons can further reduce NO2 to N2. After NH3 is introduced, NH3 and photogenerated electrons work together to improve NOx removal efficiency.
A research paper
Preparation and Characterization of Ni modified MoS2 for Electrocatalytic Hydrogen Evolution
HAN Jia-qi, WU Hong-jun
 doi: 10.19906/j.cnki.JFCT.2022092
Abstract(33) HTML(23) PDF 5082KB(5)
Developing highly active and low cost hydrogen evolution electrocatalysts is expected to improve the efficiency of water electrolysis hydrogen production, achieve large-scale hydrogen production, and promote the development and utilization of hydrogen energy is imminent. Molybdenum disulfide (MoS2) has shown a certain potential in the field of hydrogen evolution catalysis, and its modification to improve the catalytic activity and replace the platinum-based catalyst has become a research hotspot in recent years. A simple one-step solvothermal method was used to successfully synthesize a Ni-doped electrocatalytic hydrogen evolution (HER) catalyst Ni@MoS2, which has excellent electrocatalytic hydrogen evolution activity and good stability. The 20Ni@MoS2 as prepared at 240 ℃ exhibits enhanced HER performance with a low overpotential of 190 mV at 10 mA/cm2 and Tafel slope of 162 mV/dec in acidic medium.
Study on the activation mechanism of O-enhanced methane adsorbed on Pd-Cu catalyst
ZHANG Jia-dong, NIU Jun-tian, LIU Hai-yu, FAN Bao-guo, JIN Yan
 doi: 10.19906/j.cnki.JFCT.2022091
Abstract(24) HTML(11) PDF 1105KB(2)
Compared with traditional combustion, methane catalytic combustion has the advantages of low combustion temperature, clean and high efficiency, and it has good application prospects in natural gas vehicles, solid oxide fuel cell and other fields. In order to reveal the mechanism of dehydrogenation of methane on Pd-Cu clusters with different doping ratios, the density functional theory (DFT) is used to calculate the direct dehydrogenation and O-assisted dehydrogenation of CH4* in different clusters. The calculation results show that the doping of Pd atoms increases the adsorption capacity of Cu(111) surface, and in the process of direct dehydrogenation, the doping of Pd not only reduces the energy barrier from 2.56 eV to 2.43 eV, but also changes the rate determining step from CH*→C* + H* to CH4*→CH3* + H*. Pre-adsorbed O can significantly reduce the energy barrier of methane dehydrogenation, the rate determining steps are CH4* + O*→CH3* + OH*. The highest energy barrier of O-assisted dehydrogenation of CH4* is Cu(111)(1.56 eV)>Pd6Cu(111)(1.44 eV)>Pd2Cu(111)(1.38 eV) on three clusters, which indicates that the addition of Pd has improved the performance of direct dehydrogenation and O-assisted dehydrogenation.
A research paper
The effect of crystal plane on Fe3O4 carbonization
LI Si-qi, WEI Xu-song, WANG Hong, QING Ming, SUO Hai-yun, LÜ Zhen-gang, GUO Hui-chuang, LIU Ying, YU Xin, YANG Yong, LI Yong-wang
 doi: 10.19906/j.cnki.JFCT.2023017
Abstract(30) HTML(11) PDF 1523KB(5)
In the Fischer-Tropsch synthesis reaction, Fe-based catalysts are widely used in large-scale indirect coal liquefaction industry due to their low price, high activity, and low CH4 selectivity. The catalytic performance is closely related to the catalyst particle size, surface structure and composition. Since reductive carbonization is a key step in the activation of iron-based catalysts, in this work, Fe3O4-O (expose the {111} crystal planes) with different particle size, and similar particle size but exposing different crystal planes, {111} and {110} (Fe3O4-RD), have been prepared to explore the effect of particle size and surface structure on the carbonization process. The results show that the 50 nm Fe3O4-O particles changed more significantly than the one with large particle size (2–10 μm) after carbonization. In situ XRD was used to monitor the phase change of Fe3O4 with exposing different surface planes during carbonization, the results show that 150 nm Fe3O4-O and Fe3O4-RD particles behave differently in carbonization rate and have different iron carbide concentration in the end, which indicates the carbonization process can be affected by exposed crystal planes. TEM analysis reveals that Fe3O4@FexC core-shell structure formed after carbonization.
A research paper
Study on the performance of hydrotalcite-based ozone decomposition catalyst
MA Jia-chuan, GUO Ming-xing, WANG Sheng, WANG Shu-dong
 doi: 10.1016/S1872-5813(23)60337-8
Abstract(21) HTML(10) PDF 6597KB(4)
Ozone in the indoor environment is seriously harmful to human health, and catalytic decomposition method is one of the most effective ozone purification technologies. The development of ozone decomposition catalyst with superior activity and stability is the bottleneck especially under high humidity, high space velocity and ambient temperature. Layered double metal hydroxide (LDH) has a unique two-dimensional layered structure and excellent water resistance. In this paper, Ni3Fe, Ni3Co, Ni3Mn and Co3Fe hydrotalcite-structured catalysts were prepared by coprecipitation method. And their ozone catalytic decomposition performance was tested under 30 ℃, 600,000 mL/(g·h), low humidity RH < 5% and high humidity RH > 90%. The results show that Ni3Co-LDH exhibits excellent ozone decomposition performance, and the ozone conversion rate is 88% and 77% under low humidity and high humidity, respectively. Combined with XRD, BET, SEM, XPS, Raman, FT-IR, TG, and other characterizations, the intrinsic mechanism of the excellent ozone decomposition performance of LDH catalysts was revealed. The paper provides new ideas for the development of transition metal ozone decomposition catalysts.
Progress in thermal reaction processes of biomass with laser-induced fluorescence spectroscopy
ZHAO Zheng, SU Sheng, SONG Yawei, Liu Yushuai, CHEN Yifeng, JIA Mengchuan, XU Kai, WANG Yi, HU Song, XIANG Jun
 doi: 10.1016/S1872-5813(23)60338-X
Abstract(20) HTML(9) PDF 4785KB(0)
A thorough understanding of the pyrolysis and combustion characteristics of biomass and the generation characteristics of alkali metals is the theoretical basis for the clean and efficient utilization of biomass. Due to the low measurement accuracy and time lag, traditional measurement methods have insufficient understanding of the biomass thermal reaction process. Laser induced fluorescence (LIF) technology has the advantages of non-disturbance, real-time in-situ measurement, strong component selectivity, good sensitivity, and high spatial and temporal resolution. It has been used in more and more studies on biomass thermal reaction processes. This paper reviews the main LIF technologies in recent years and reviews the combustion process and combustion process of biomass pyrolysis processes, the progress of the application of alkali metal release features, and analyzes the different reaction conditions or volatile material pyrolysis processes, the generation and evolution behavior and their forming mechanism. This paper expounds the biomass combustion flame structure in the process of information and the release of alkali metal migration characteristics. Finally, some shortcomings in the current research and future research directions are put forward.
Char structure evolution and behaviors of sodium species during catalytic gasification of sodium-rich direct coal liquefaction residue under CO2 atmosphere
LI Pei, ZHU Chao-chao, HAN Lu, LI Xiao, FENG Xiao-bo, YAO Qin, YU Shi, MENG Xian-liang, WANG Peng, WEI Shuai
 doi: 10.1016/S1872-5813(22)60077-X
Abstract(25) HTML(14) PDF 3944KB(6)
In this work, to better understand catalytic gasification process of direct coal liquefaction residue rich in sodium species, char structure evolution and behaviors of sodium species during gasification under CO2 atmosphere were investigated in detail by N2 adsorption and desorption, FT-IR, XRD, SEM, and Raman analyses. The results show that sodium species developed pore structure of direct coal liquefaction residue during gasification, especially expanded mesoporous structures which increased from 0.05 to 0.16 cm3/g at maximum. With the increase of gasification time, different crystalline compounds were formed in chars. Most of the mineral matters identified by XRD were calcium-containing ones, whereas no obvious sodium-containing crystalline compounds were found. This was because that most of sodium species volatilized at high temperature and the crystalline forms of sodium-containing compounds had defects. Compared with sodium species, calcium species were more prone to react with aluminosilicates, which happened to make sodium species remain active during gasification process. The ratio of (GR + VL + VR)/D rose initially and then decreased, which could be explained as the dissociation of the large aromatic and the rearrangement of small aromatic rings into large aromatic structures. Moreover, release ratio of sodium species was closely related with gasification time and 49.8% of them released in the initial stage of gasification process (within 15 min). Compared with that of direct coal liquefaction residue reloaded with water-soluble sodium species, the release ratio of sodium species in the original direct coal liquefaction residue was on a lower level (85.2% versus 89.7%).
Fe-doped Co3O4 anchored on hollow carbon nanocages for efficient electrocatalytic oxygen evolution
LUO Jia-bing, WANG Xing-zhao, ZHANG Jun, ZHOU Yan
 doi: 10.1016/S1872-5813(22)60080-X
Abstract(46) HTML(22) PDF 9673KB(11)
In this work, a Fe-doped Co3O4 OER electrocatalyst supported by an N-doped hollow nanocage carbon framework (Fe-Co3O4/NC) was successfully prepared by anion exchange and annealing in an air atmosphere strategy. XRD and HRTEM characterizations confirm that Fe the incorporation of Fe into the lattice of Co3O4. XPS characterization clarifies that the valence state of Co increases after the introduction of Fe, which originates from the electrons transfer from Co2+/Co3+ to Fe3+ and is induced by the valence electron configuration of cations. It simulates Co sites in situ derived into CoOOH active species during the OER process, which is confirmed by the HRTEM and XPS characterization after the OER stability test. Electrochemical performance tests show that the Fe-Co3O4/NC electrocatalyst only exhibits 275 mV overpotential to achieve a current density of 10 mA/cm2 and stably maintains for 20 h at 100 mA/cm2. Together with 20% Pt/C electrocatalyst, the composed two-electrode system only needs 2.041 V applied potential to achieve 100 mA/cm2 for total water splitting in a self-made membrane electrode device, which has industrial application prospects.
A research paper
Recycling of red mud to Fe/C-based composite microwave absorbents by coal gasification semi-coke
LIANG Li-ping, LIU Xue-qin, GAO Xu-zhou, SHI Shu-ping, SU Ning-jing, LI Guo-min
 doi: 10.19906/j.cnki.JFCT.2022073
Abstract(38) HTML(12) PDF 2109KB(5)
Fe/C-based composite microwave absorption (MA) materials were prepared by high temperature solid phase reaction between coal hydrogasification semi-coke (SC for short) and solid waste red mud (RM). In order to optimize MA performance, initial system composition was changed. It was found that, under an argon atmosphere and reaction temperature of 900 ℃, the composites obtained from systems with mass ratio of SC to RM (MRSR) at 0.4∶1−0.7∶1 all showed excellent performance, and that corresponding to MRSR of 0.6∶1 was the best. At a coating thickness of 1.5 mm, the simulated minimum reflection loss and effective absorption bandwidth could reach −48.3 dB and 4.6 GHz, respectively. The strong intrinsic attenuation ability mainly resulted from the dielectric loss due to the presence of graphite carbon as well as a large number of phase boundaries and defects. And the impedance matching between material and free space was attributed to the effective regulation on electromagnetic parameters of the initial system composition. Moreover, the solid phase combination reaction among Na2O, Al2O3 and SiO2 could weaken the strong alkalinity caused by RM.
Hollow N-doped carbon spheres with anchored single-atom Fe sites for efficient electrocatalytic oxygen reduction
WANG Min-min, FENG Chao, LIU Yun-qi, PAN Yuan
 doi: 10.1016/S1872-5813(22)60067-7
Abstract(34) HTML(25) PDF 5717KB(11)
We anchored atomically dispersed Fe-N4 sites on hollow N-doped carbon spheres (Fe SAs/HNCSs-800) for electrocatalytic ORR; the obtained material exhibited electrocatalytic activity and stability comparable to that of commercial Pt/C, with an onset potential of 0.925 V and a half-wave potential of 0.867 V. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy results confirmed the presence of highly dispersed Fe single atoms in Fe SAs/HNCSs-800. The results of experiments and theoretical calculations show that the single-atom dispersed Fe-N4 serve as the ORR active sites, and the adjacent C defects can effectively regulate the electronic structure of Fe atoms and improve the electrocatalytic ORR activity.
Synthesis of polyethylnaphthalenes base oil catalyzed by ionic liquid and its lubricating properties
LI Yuan-yuan, TANG Qiong, CHEN Chen, ZUO Zhi-jun, LIU Lei, DONG Jin-xiang
 doi: 10.19906/j.cnki.JFCT.2022087
Abstract(73) HTML(20) PDF 5920KB(8)
The resources endowment characteristics of rich coal, lean oil and poor gas in China, synthesis of high value-added chemicals from coal-based raw materials can help reduce the dependence on foreign petroleum. Polyethylnaphthalenes lubricating base oil are synthesized by alkylation of cooking naphthalene with ethylene using organic ammonium salt/metal chloride ionic liquid as catalyst. It is found that the AlCl3/Et3NHCl ionic liquid showed better active in the naphthalene alkylation with ethylene by regulating the composition of anions and cations in ionic liquids. Two different compositions of polyethylnaphthalenes base oils PEN-1 (92.9% of mono- and di-ethylnaphthalenes) and PEN-2 (91.3% of polyethylnaphthalenes) were synthesized by optimizing reaction conditions (catalyst dosage, reaction time and temperature). The lubrication test results show that PEN-2 base oil with a large number of alkyl side chains exhibits good tribological properties and shows better wear resistance than the commercial alkylnaphthalenes base oil AN5, showing a good application prospect.
The performances and structure evolution of Pt-based catalysts for selective hydrogen combustion under propene-rich conditions
SUN Huai-lu, LI Kai-xin, YU Wen-long, DING Jun-wei, SHAN Yu-ling
 doi: 10.1016/S1872-5813(23)60336-6
Abstract(46) HTML(23) PDF 950KB(8)
In the present study, the kinetic behaviour and active sites evolution processes of Pt-based catalysts were investigated. It was found that highly selective hydrogen combustion could be achieved over Sn modified Pt-based catalysts in presence of both propane and propene (over 98%). The stability tests, kinetic study and catalyst characterization revealed that the existence of oxygenated species is the reason for accelerated coking reactions. The formation of graphitized cokes serving as additional unselective active sites and the oxidation of tin in PtSn alloy phases are the primary reasons causing the catalytic selectivity loss during long-run tests under propene-rich condition.
A research paper
Effect of hydrothermal synthesis time on the performance of Cu/Ce-Zr catalysts for catalytic water-gas shift reaction
KANG Yu-shu, WANG Li-bao, LI Yong-zhi, BAI Jin, ZHANG Cai-shun, LIU Dao-sheng, ZHANG Lei, GAO Zhi-xian
 doi: 10.19906/j.cnki.JFCT.2022074
Abstract(87) HTML(31) PDF 1514KB(3)
Ce-Zr oxide support was hydrothermally synthesized from metal nitrates of cerium and zirconium as the raw materials using citric acid instead of alkali precipitant, and then Cu/Ce-Zr catalyst was prepared by the impregnation method. The support and catalyst samples were characterized by XRD, BET, H2-TPR, XPS techniques, and the effects of different hydrothermal time on the structure, properties and performance in water-gas shift reaction were investigated. The results show that the catalyst activity is mainly related to the Cu specific surface area, reduction temperature of CuO and the number of oxygen vacancies on the catalyst surface. Among them, the Cu/Ce-Zr catalyst with hydrothermal time of 12 h has a large Cu specific surface area, a lower reduction temperature of CuO, and a large number of oxygen vacancies, so it shows a good catalytic activity. When the reaction temperature is 320 ℃, the molar ratio of water to gas (W/M) is 2, and the gas space velocity GHSV=6600 h−1, the CO conversion rate is 96.9%, which is close to the thermodynamic equilibrium value of 97.1%.
Research note
Fischer-Tropsch synthesis performance of cobalt-based catalysts supported on bimodal porous SiO2 with high specific surface area
HU Xue-qi, LÜ Shuai, ZHAO Yan-xi, ZHANG Yu-hua, LIU Cheng-chao, LI Jin-lin
 doi: 10.19906/j.cnki.JFCT.2022077
Abstract(54) HTML(23) PDF 1966KB(6)
The structure of the supports can significantly affect the Fischer-Tropsch catalyst activity and selectivity. The porous structure can improve the mass transfer of reactants, enhance the CO conversion activity and C5 + product selectivity; the high specific surface area is beneficial to disperse the loaded metal, improve the catalyst metal utilization efficiency and catalyst stability. However, it is relatively difficult for supports to obtain high specific surface area and macropore structure characteristics simultaneously. A mesoporous (2.9 nm) -macroporous (63.8 nm) bi-porous silica (BP-SiO2) support with a high specific surface area of 1103.2 m2/g was synthesized by the structure-directed hydrolysis method, and its catalytic performance for Fischer-Tropsch synthesis was investigated. The results showed that compared to the Co/SBA-15 catalyst with equivalent mesopore diameter, the catalyst Co/BP-SiO2 showen CO conversion rate nearly increased by 33.3%, CH4 selectivity reduced by 30.1%, improved C5 + selectivity and stability.
A research paper
Preparation of Rh/CeOx-C3N4 catalyst and its catalytic dehydrogenation of hydrazine hydrate
ZHENG Jun-ning, WU Hui, LIU Yong, LI Gui, XU Li-xin, YE Ming-fu, WAN Chao
 doi: 10.19906/j.cnki.JFCT.2022082
Abstract(35) HTML(15) PDF 1692KB(5)
The development of a catalyst with high efficiency and high selectivity under mild conditions is the key to realize the application of hydrogen production by decomposition of hydrazine hydrate (N2H4∙H2O). In this paper, CeOx was doped into the catalytic system and cerium-doped carbon nanomaterial was prepared by roasting at high temperature in N2 atmosphere as the carrier. Rh/CeOx-C3N4 catalyst was synthesized by loading the active component Rh onto CeOx-C3N4 carrier through impregnation reduction method, and its influence on catalytic performance of hydrazine hydrate dehydrogenation was investigated. The results showed that there was a synergistic effect between the active component Rh and CeOx in Rh/CeOx-C3N4 catalyst, and the doping of CeOx effectively dispersed and stabilized the metal active component, providing more active sites for catalytic reaction. Therefore, the catalyst has good catalytic activity for the dehydrogenation of hydrazine hydrate. The prepared Rh/CeOx-C3N4 catalyst showed the best catalytic activity for hydrazine hydrate, and the initial conversion TOF was up to 1959.24 h−1. After 5 cycles, the catalytic activity remained good, indicating good durability.
Preparation of Fe/Zr-SBA-15 catalyst and its oxidative desulfurization performance
WANG Hao, KONG Li-ming, ZENG Yong-ping
 doi: 10.19906/j.cnki.JFCT.2022088
Abstract(36) HTML(16) PDF 2666KB(4)
To improve the oxidative desulfurization performance, the modified SBA-15 (Fe/Zr-SBA-15) with different Fe/Zr molar ratios were synthesized by direct hydrothermal method. The samples were characterized by XRD, N2 adsorption and desorption, TEM and UV-Vis. Zr is incorporated into the framework of SBA-15. Apart from little aggregated iron oxides, most of the Fe species were well dispersed in Fe/Zr-SBA-15. The influence of the reaction temperature, amount of oxidant and dosage of catalyst on the conversion of DBT were investigated using Fe/Zr-SBA-15-1.0 as catalyst, H2O2 as oxidant and acetonitrile as extractant. The removal rate of DBT reached 97.1% under the conditions of reaction temperature 50 ℃, O/S molar ratio of 4 and catalyst dosage of 6 g/L. The synergistic effect of Fe and Zr plays important role, with Fe3 + acting as the oxidation activity center and Zr4 + as the center of adsorption. In addition, the removal rate of DBT could still reach 91.3% after 4 cycles and Fe/Zr-SBA-15 showed good stability.
Study on the catalytic oxidation of toluene over M/ZSM-5 (M=Cu, Mn, Fe, Ce, Ti) catalysts
PENG Xin-yu, LIU Li-jun, SHEN Bo-xiong, BIAN Yao, SU Li-chao
 doi: 10.1016/S1872-5813(22)60069-0
Abstract(53) HTML(31) PDF 3641KB(18)
A series of metal oxide catalysts were prepared by impregnating Cu, Mn, Fe, Ce and Ti with ZSM-5 molecular sieve as the support. The physicochemical properties of the catalysts were characterized by SEM, XRD, N2 adsorption/desorption, XPS, H2-TPR, and the catalytic oxidation of toluene was investigated. The results showed that Cu/ZSM-5 had rough surface, uniform distribution of metal, good pore size structure, superior low-temperature reducibility and abundant adsorbed oxygen species. Cu/ZSM-5 with 5 wt.% loading exhibited excellent catalytic activity for toluene oxidation and the best sulfur resistance performance, with T90 (GHSV=24000 h−1) being 224 ℃ in SO2 environment. In situ DRIFTS experiments revealed that the degradation of toluene follows the following path: toluene was first adsorbed on the surface of the catalyst to form adsorbed toluene, then it was converted into benzaldehyde and benzoic acid successively under the action of the catalyst. And small molecule organics such as maleic acid and carboxylic acid were formed through ring opening reaction, and finally was oxidized to CO2 and H2O.
A research paper
Preparation and characterization of low-temperature coal tar toughened phenolic foams
CHENG Jin-yuan, LI Zhan-ku, YAN Hong-lei, LEI Zhi-ping, YAN Jing-chong, REN Shi-biao, WANG Zhi-cai, KANG Shi-gang, SHUI Heng-fu
 doi: 10.1016/S1872-5813(22)60072-0
Abstract(17) HTML(8) PDF 11522KB(0)
Efficient utilization of low-temperature coal tar is important for coal pyrolysis or coking. The low-temperature coal tar is rich in phenols with different reactive sites, resulting in a much higher substitution rate (40%) of phenol than high-temperature coal tar and its distillations. In this study, coal tar-based phenolic foam (CPF) was prepared using low-temperature coal tar as raw material to partially replace phenol. The chemical structure, apparent morphology, compressive strength, thermal stability, flame retardancy and thermal insulation properties of CPFs were characterized. The results show that CPFs have similar chemical structures to conventional phenolic foam. Comparing with conventional phenolic foam, the compressive strength of 30%CPF and 40%CPF increases by 18.3% and 55.9%, and the pulverization rate decreases by 22.9% and 50.8%, respectively. The results indicated that toughness was significantly strengthened due to the incorporation of aliphatic structures such as alkylphenols. In addition, the thermal stability of CPFs in the low temperature stage also improves. Although the limited oxygen index of CPFs decreases and thermal conductivity of CPFs increases, they still maintain good flame retardancy and thermal insulation properties. The obtained results prove that low-temperature coal tar can significantly replace phenol to prepare phenolic foam with good performance, which provides a new idea for the high-value utilization of low-temperature coal tar.
A research paper
CO2 hydrogenation to C5 + isoalkanes on ZnZr/HZSM-5 composite catalyst
MA Xiao-ling, WANG Xiao-xing, SONG Fa-en, MA Zi-xuan, TAN Yi-sheng
 doi: 10.19906/j.cnki.JFCT.2022085
Abstract(28) HTML(16) PDF 13692KB(6)
CO2 hydrogenation into value-added chemicals or liquid fuels is one of the effective ways to reduce its greenhouse effect. Although most of the efforts have been made in the preparation of isoalkanes and gasoline by CO2 hydrogenation on composite catalysts of metal oxides and zeolites, there are still problems in the selectivity of products, such as low selectivity of C5 + hydrocarbons and isoalkanes in C5 + hydrocarbons and high selectivity of by-product CO. Herein, we report an efficient strategy that zinc-zirconium oxide (ZnZr) is effectively coupled with HZSM-5 zeolite . The effects of SiO2/Al2O3 ratio of HZSM-5 zeolite and Zn/Zr ratio on the performance of CO2 hydrogenation to C5 + isoalkanes over the composite catalyst were investigated, respectively. The results show that ZnZr-4/HZSM-5 prepared by SiO2/Al2O3 = 130 and Zn/Zr = 1∶5 manifests the optimal performance of CO2 hydrogenation to C5 + isoalkanes, with CO2 conversion of 17% and CO selectivity of 25%, as well as the selectivity of C5 + hydrocarbons and isoalkanes in C5 + hydrocarbons up to 60% and 89%. Moreover, ZnZr/HZSM-5 composite catalyst shows excellent stability with time on stream for 120 h without losing activity. A suitable coupling between ZnZr and HZSM-5 zeolite is critical for highly selective synthesis of C5 + isoalkanes by CO2 hydrogenation.
Role of Ionic Liquids in Photo/Electrocatalytic Reduction of CO2
ZHANG Xiaoya, WANG Huan, AN Weijia, LIU Li, CUI Wenquan
 doi: 10.19906/j.cnki.JFCT.2022090
Abstract(65) HTML(33) PDF 5713KB(17)
Reducing CO2 into energy fuel is an effective way to alleviate the energy crisis and greenhouse effect. In recent years, domestic and foreign scholar have carried out extensive research on the photo(electro)catalytic reduction of CO2. However, the photo(electro)catalytic reduction of CO2 still has some problems, such as low visible light response, high recombination rate of photo-generated electrons and holes, small CO2 adsorption and poor selectivity of products, which restrict the rapid development of this field. As a new type of green solvent, ionic liquids (ILs) have high thermal stability and strong CO2 adsorption. It can be used as reaction medium or co-catalyst in the photo(electro)catalytic reduction of CO2 chemical reactions, so they have been widely studied. In this paper, the research status and roles of ionic liquids in photo(electro)catalytic reduction of CO2 in recent years are analyzed and reviewed, and the development prospect of ILs in this field is prospected.
A research paper
Correlation mechanism between structure and gasification characteristics of typical municipal solid waste (MSW) disposable bamboo chopsticks hydrochar
ZHOU Zhi-chao, WANG Jiao-fei, BAI Yong-hui, LÜ Peng, SONG Xu-dong, SU Wei-guang, YU Guang-suo, DING Lu
 doi: 10.19906/j.cnki.JFCT.2022084
Abstract(49) HTML(14) PDF 2871KB(11)
Due to the complex composition, large fluctuation of material characteristics and low energy density of MSW, the gasification characteristics of its hydrochars are not well understood. Therefore, it is of great significance to study the gasification characteristics of single component hydrochars. In this paper, a typical component of MSW, disposable bamboo chopsticks (DBC), was used as raw material to study the effect of hydrothermal carbonization (HTC) conditions on the structural properties and gasification reaction characteristics of DBC hydrochars. The results showed that HTC improved the energy quality of DBC, the HHV of DBC-230-60 sample was 1.62 times of that of DBC, and H/C and O/C decreased from 1.57 and 0.76 of original sample to 1 and 0.33 of DBC-230-60. The results of characterization also demonstrate that the aromatization degree of hydrochar and hydrochar semicoke is higher than that of the DBC original one. The specific surface area of hydrochar is lower than that of DBC original sample, but hydrochar semicoke is higher than that of DBC original sample semicoke Compared with hydrothermal time, hydrothermal temperature had the more significant effect on the structure and gasification reactivity of hydrochar. Higher hydrothermal temperature increases the aromatization degree of hydrochar and decreases the gasification reactivity of hydrochar. The gasification reactivity of hydrochar is worse than that of DBC original sample, mainly because the increase of the degree of semicoke arbulization of hydrochar has a greater negative effect on the gasification reactivity than the abundance of pore structure.
Preparation and Electrochemical Properties of La0.5Sr0.5Co0.2Fe0.8O3 Oxides as Bifunctional Catalysts for Reversible Single-Component Cells
LIU Fei, YANG Bei-bei, MA Xin-yu, LI Ping, YAN Fei, FU Dong
 doi: 10.19906/j.cnki.JFCT.2022080
Abstract(25) HTML(9) PDF 7889KB(2)
La0.5Sr0.5Co0.2Fe0.8O3 (LSCF) perovskite materials are prepared by hard template method with SBA-15 as the template in methanol and ethanol solvents and the electrochemical properties of LSCF are investigated. It is found that LSCF prepared with ethanol solvent has larger specific surface area and more oxygen vacancy concentration, which in turn exhibits higher electrical conductivity and better catalytic activity towards oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR). This is because the LSCF prepared by the ethanol solvent has more Co2 + /Co3 + and Fe2 + /Fe3 + electron pairs, which promotes the electronic conduction of the material. In addition, for HOR, the rate determining step (RDS) is the transfer of adsorbed H to the reaction site, and for ORR, the RDS is the reduction of the adsorbed oxygen atom on LSCF. In addition, the reversible single-component cell (RSCC) composed of LSCF prepared by ethanol solvent shows better performance for discharge and water electrolysis. The maximum power density (Pmax) of the RSCC is 232.9 mW/m2, and the current density at 1.3 V is −398.3 mA/cm2 at 700 ℃.
A research paper
Study on reaction path and coke formation of decalin on acid catalyst
WANG Yong-chao, YAN Jia-song, WANG Ruo-yu, Li Rui, WANG Shi-hao
 doi: 10.19906/j.cnki.JFCT.2022081
Abstract(41) HTML(16) PDF 2453KB(3)
A small fixed fluidized bed device (ACE Model C) was used to study the cracking reaction path and coke formation mechanism of Model compound decaphthalene over Y molecular sieve catalyst at the reaction temperature of 460−540 ℃. The results show that in the initial stage of decalin cracking, H + attacking C−H bond and C−C bond with tertiary carbon atoms on decalin to form non-classical five-coordinated tertiary positive carbon ions is the most important initiation reaction. Decalin cracking products are mainly propylene, propane, isobutane, isopentane, methylcyclopentane, toluene, dimethyl benzene, etc. The yield of the products on the catalyst from large to small is: non-aromatic hydrocarbons, monocyclic aromatic hydrocarbons, bicyclic aromatic hydrocarbons; The mechanism of coke production catalyzed by decalin is carbocation mechanism. With the increase of reaction temperature and molecular sieve acid content, the bilayer hydrogen transfer and dehydrogenation condensation ability are enhanced, and the coke yield and conversion are also increased.
A research paper
Experimental study on pre-hydrogenation of catalytic slurry oil and co-carbonization of middle distillate and high boiling point distillate
WANG Feng, ZHANG Zheng, LI Ze-liang, LI Ke-qi, LIU He, CHEN Kun, GUO Ai-jun
 doi: 10.1016/S1872-5813(22)60076-8
Abstract(30) HTML(11) PDF 6989KB(3)
A catalytic slurry oil (SO) was treated by moderate pre-hydrotreating, the structural compositions, the thermal stability, the distillate oil yield, and the coking behavior of SO before and after hydrotreating were analyzed. The carbonization performance as well as the co-carbonization performance of the middle distillate (350−500 ℃) and the high boiling point distillate (500−550 ℃) derived from the hydrogenated SO (HSO) were investigated. The results showed that the content of naphthenes and hydrogenated aromatics of HSO increased, while the olefin content decreased, the olefinic hydrogen content of HSO decreased from 2.71% to 0.97%. Thus, the thermal stability of HSO was fundamentally improved. Additionally, compared with SO, the yields of middle distillate and high boiling point distillate of HSO were increased by 25.8% and 23.1, respectively. More importantly, there was no significant coke formation behavior during distillation of HSO. The carbonization experiment results showed that the anisotropic textural structure of the coke obtained from the middle distillate derived from HSO was the large flow domain structure, and the coke had the lowest coefficient of thermal expansion (CTE) value of 2.25 x 10−6/℃. The carbonization performance of the high boiling point distillate derived from HSO was poor, while co-carbonization with the middle distillate significantly improved the carbonization performance of the high boiling point distillate. The anisotropic textural structure of the coke derived from carbonization of combined fraction was the large flow domain structure and the CTE value was less than 2.30 × 10−6/℃ when the mass ratio of aromatic fraction and middle fraction was not higher than 2∶1.
A research paper
Investigation of the surface acidity and redox on the CeO2-WO3 catalyst for Selective Catalytic Reduction with NH3
KANG Hai-yan, MO Du-juan, ZHANG Xue-jun, ZHANG Meng-ru, GAO Hong-run, MAO Yan-li, LI Hai-yang, SONG Zhong-xian
 doi: 10.19906/j.cnki.JFCT.2023005
Abstract(77) HTML(17) PDF 18317KB(18)
CeO2-WO3 catalysts were successfully prepared by in situ synthesis and used in the denitrification reaction. The best activity of CW-550 catalyst was achieved at a roasting temperature of 550 ℃, and the denitrification activity of CW-550 reached over 90% at 200 ℃. The superior catalytic performance of CW-550 catalyst can be attributed to the large specific surface area, more Ce3 + species, abundant surface acidity and superior redox performance. The increased Ce3 + facilitates the formation of oxygen vacancies and promotes redox performance. The introduction of WO3, into CeO2 can enhance the amounts of Brönsted acid, which contributes to the improvement of the adsorption and activation of ammonia, resulting in the excellent catalytic performance. The NH3-adsorbed species can react with gaseous NO, However, both of NH3-adsorbed and NO-adsorbed sepcies cannot participate in the SCR reaction effectively. Therefore, the SCR reaction of CW catalysts mainly follows the Eley-Rideal mechanism.
Catalytic performance of Cu/Hβ catalysts for selective catalytic reduction of NO by NH3
SUN Jin-chang, REN Cui-tao, ZHAO Ming-xin, TIAN Chun-yu, CHI Yao-ling, ZHAO Tian-tian, WANG Hong
 doi: 10.1016/S1872-5813(22)60071-9
Abstract(89) HTML(64) PDF 1315KB(5)
A series of Cu(x)/Hβ catalysts were prepared by the impregnation method and the effect on the performance of the catalysts for the selective catalytic reduction of NO with NH3 (NH3-SCR) was investigated. Characterization techniques such as XRD, N2 adsorption-desorption, NH3 temperature programmed desorption (NH3-TPD), NO-TPD, H2 temperature programmed reduction (H2-TPR), energy dispersion X-ray spectrum (EDS) and X-ray photoelectron energy spectrum (XPS) were used to investigate the physical and chemical properties of the catalysts and the reason of the decrease of catalyst activity in the presence of SO2. It is shown that the catalyst (Cu(3)/Hβ), the Cu loading is 3 wt% and Cu(2)/Hβ, the Cu loading is 2 wt%, exhibited the better catalytic activity when the initial reaction material contains no SO2 and SO2, and T95 is 169 and 225 oC, respectively. The analysis results of the catalyst before and after the reaction showed that the main reason for the decrease of catalyst activity in the presence of SO2 is that the ammonium sulfur salt which is formed by the reaction of SO2 and NH3 in the low reaction temperature covers the catalyst active center.
Progress in thermal catalysis hydrogenation of CO2 to ethanol
MAO Yu-zhong, ZHA Fei, TIAN Hai-feng, TANG Xiao-hua, CHANG Yue, GUO Xiao-jun
 doi: 10.1016/S1872-5813(22)60065-3
Abstract(137) HTML(71) PDF 6099KB(41)
As one of the carbon reduction ways, chemical conversion of CO2 is continuously being concerned. The breakthroughs through thermal catalysis conversion have been carried out in recent years. However, there are still problems such as low ethanol selectivity and yield, and more by-products are produced. In this study, the progress in thermal catalysis of CO2 hydrogenation to ethanol was reviewed. The performance of catalysts with different supports of zeolites, metal oxides, perovskites, silicon dioxide, organic frameworks and carbon-based materials were mainly discussed. The influence of the synergistic effect between different metals on the CO2 conversion and the promotion effect of the intervention of various active species on the reaction were analyzed. The catalyst systems that can effectively promote the coupling of C–C bond, and have appropriate CO2 adsorption and activation performance were summarized. Based on above discussion, the conditions of CO2 hydrogenation to ethanol were summarized, and the reaction mechanism was discussed. The study is beneficial to design the catalysts, optimize the reaction conditions and understand the mechanism of CO2 hydrogenation to ethanol in the future.
Effect of molten salt on re-pyrolysis behaviors of heavy bio-oil
CHEN Tao, LUO Ze-jun, WANG Chu, ZHU Xi-feng
 doi: 10.1016/S1872-5813(22)60068-9
Abstract(38) HTML(6) PDF 790KB(5)
The effects of KCl-ZnCl2 molten salt on the pyrolysis characteristics and pyrolysis products of heavy bio-oil at 400 ℃, 500 ℃ and 600 ℃ were studied. The results showed that molten salt increased the solid yield of heavy bio-oil pyrolysis and decreased the gas yield. Some compounds such as phenol, cresol, ethylphenol and 4-propylphenol had good enrichment effect, especially the relative concentration of cresol increased from 8.82% to 20.85% at 400 ℃, while the relative concentration of phenol increased from 2.18% to 8.62% at 600 ℃. During the formation of char, molten salt reduced the content of carbon and increased the content of oxygen, increased the BET surface area and total pore volume of pores. Molten salt promoted the formation of solid products’ pore structure and increased the average pore diameter.
A research paper
Hydrogenation of dimethyl oxalate to ethylene glycol over the Cu-M/ZnO (M=Zr4 + , Al3 + , Mg2 + ) catalysts: Role of the dopants in the structure and catalytic features
KONG Xiang-peng, YOU Xin-ming, YUAN Pei-hong, Wu Yue-huan, WANG Rui-hong, CHEN Jian-gang
 doi: 10.1016/S1872-5813(22)60073-2
Abstract(52) HTML(23) PDF 4158KB(13)
The Cu-M/ZnO catalysts (M = Zr4 + , Al3 + and Mg2 + ) for dimethyl oxalate (DMO) selective hydrogenation to ethylene glycol (EG) have been synthesized by the co-precipitation method. The texture properties of the as-synthesized catalysts were systematically characterized by the N2-physisorption, N2O-titration, XRD, H2-TPR, CO2-TPD, SEM, FT-IR and XPS focusing on the functions of the dopants. It is found that the incorporated dopants can significantly promote the Cu dispersion. Particularly, a trace of Mg2 + dopants can effectively strengthen the interaction between Cu and ZnO phases by embedding into the ZnO lattice, while the Cu/ZrO2 interaction could be reinforced with the Zr4 + dopant introduced. For DMO gas-phase hydrogenation, the EG yield of the Cu/ZnO catalyst increased from 75.0% to 85.0% and 90.0% in presence of Zr4 + and Al3 + dopants, respectively. Particularly, the EG selectivity of Cu-Mg/ZnO catalyst can reach up to 95.0% with DMO completely converted for more than 100 h. The correlation between the catalytic behavior and physicochemical features suggested that the Cu + sites should be vital for the catalytic behavior of the Cu/ZnO based catalysts with adequate Cu0 sites. Additionally, the strengthened Cu/oxide interaction favors the outstanding stability of the Cu-Zr/ZnO and Cu-Mg/ZnO catalyst in DMO hydrogenation.
A research paper
Preparation of B/N co-doped porous carbon sheets and their potassium storage properties
HAN Na, ZHANG Dong-dong, WU Ting-ting, YANG Lei, LI Hong-qiang, HE Xiao-jun
 doi: 10.19906/j.cnki.JFCT.2022075
Abstract(81) HTML(27) PDF 16782KB(10)
In recent years, potassium ion batteries have become one of the important electrochemical energy storage devices in the new energy field because of their high energy, power density and excellent cycle stability. Among them, the physicochemical properties and structure of anode materials are the key factors affecting their electrochemical properties. In this paper, two-dimensional B/N co-doped porous carbon sheets (BNCSs) were prepared by one-step carbonization using glycine as carbon source and nitrogen source, boric acid as template and boron source. The boric acid template can be removed by water washing, and the synthesis method is green and environmentally friendly. The short pores in BNCSs shorten the transport distance of potassium ions, and the abundant micropores provide a large number of potassium storage active sites. In addition, the higher B/N doping in BNCSs increases the defect degree of carbon matrix, expands the carbon layer spacing, and is conducive to the adsorption, insertion and de-insertion of potassium ions. The measurement results of potassium ion half cell performance indicate that BNCS800 electrode shows high specific capacity (310 mAh/g at 0.05 A/g), excellent rate performance (100 mAh/g at 2 A/g) and good cycle stability (after 1000 cycles at 1 A/g, the capacity retention is 75.9%). This work provides a simple strategy for preparing cathode materials with high capacity and long life.
A research paper
Effects of Ce0.8Cu0.2O2 oxygen carrier-coupled S-1 molecular sieve on chemical-looping performance
HOU Kai-yuan, WANG Yu-hao, JIANG Li-hong, FAN Hao-xi, ZHENG Yan-e
 doi: 10.19906/j.cnki.JFCT.2022079
Abstract(44) HTML(24) PDF 4072KB(3)
Ce0.8Cu0.2O2 oxygen carrier has excellent performance in chemical-looping reforming of methane coupled with CO2 reduction technology. Addition of different mass of S-1 molecular sieve to Ce0.8Cu0.2O2 oxygen carrier, and the oxygen resistance was characterized by XRD, BET, XPS, SEM, TEM and CH4-TPR&CO2-TPO. The physicochemical properties and reactivity of the carrier were studied. The effect of S-1 molecular sieve on the performance of Ce0.8Cu0.2O2 oxygen carrier in chemical-looping reforming of methane coupled with CO2 reduction was systematically investigated. Compared with Ce0.8Cu0.2O2 oxygen carrier alone, the specific surface area of the composite oxygen carrier increased from 15.44 m2 /g to 73.27 m2 /g after adding 0.3 g S-1 molecular sieve. At the same time, the thermal stability and structural stability have been greatly improved. The CH4 conversion rate of composite oxygen carrier with 0.3 g S-1 molecular sieve increased from 38.93% to 56.03%, and the CO yield increased from 1.18 mmol/g to 2.16 mmol/g during CO2 reduction.
A research paper
Preparation of dimethyl carbonate from methanol and propylene carbonate over Ca-Zr catalyst modified by transition metals
CHEN Mei-juan, YANG Jin-hai, ZHAO Ning, XIAO Fu-kui
 doi: 10.1016/S1872-5813(22)60075-6
Abstract(37) HTML(12) PDF 1424KB(8)
A series of Ca-Zr catalysts modified by different transition metals prepared by sol-gel method were studied for low temperature transesterification of methanol with propylene carbonate (PC) to dimethyl carbonate (DMC). The order of DMC selective of the catalyst was Co-Ca-Zr>Cu-Ca-Zr>Ca-Zr>Fe-Ca-Zr>Ni-Ca-Zr>Zn-Ca-Zr. Among them, the highest PC conversion (84.3%) and DMC selectivity (94.5) was obtained over Co-Ca-Zr catalyst under the reaction conditions of 35 ℃, reaction time of 2 h, methanol to PC molar ratio of 15, and catalyst dosage of 4%. The physicochemical properties of the catalysts were characterized by means of XRD, FT-IR, XPS and CO2-TPD. The results showed that the surface basic content and the percentage of strong basic sites of the catalyst were the main factors affecting the catalytic activity. Increasing the basicity of catalyst might lead to increased PC conversion but decreased selectivity of DMC. The catalyst modified with Co had the lowest surface basic content, the highest percentage of strong basic sites and thus the highest PC conversion and DMC selectivity.
2023, 51(4): 1-8.  
Abstract(10) HTML(3) PDF 31482KB(12)
CO2 valorization through methyl N-phenylcarbamate synthesis
XUN Jia-yao, SONG Qing-wen, ZHANG Qian-xia, HAN Li-hua, ZHANG Kan, ZHANG Jian-li, LIU Ping
2023, 51(4): 415-427.   doi: 10.1016/S1872-5813(22)60047-1
Abstract(120) HTML(40) PDF 798KB(26)

Methyl N-phenylcarbamate (MPC) is an important intermediate for the synthesis of diphenylmethane diisocyanate (MDI), and its preparation using CO2 or its equivalents/derivatives as carbon source represents a green and sustainable manner for fine chemicals synthesis. This review will highlight the development of MPC synthetic methods from the viewpoint of chemical fixation of CO2. The contents mainly include the introduction of MPC synthesis through CO2 equivalents (urea or phenyl urea) alcoholysis, dimethyl carbonate (DMC) aminolysis, and the coupling of DMC and diphenyl urea. Furthermore, one-pot synthesis of carbamates/MPC from aliphatic amines/aniline, CO2 and alcohols is highlighted which represents one of the most promising schemes in direct CO2 utilization. What is more, the reaction mechanisms and selection of catalysts are also discussed in detail. The advances will provide important theories on further improving the efficiency of green catalysis and sustainable chemical processes.

Research progress on the reaction pathway of CO2 methanation
FU Hao, LIAN Hong-lei
2023, 51(4): 428-443.   doi: 10.19906/j.cnki.JFCT.2022063
Abstract(181) HTML(72) PDF 18411KB(47)

CO2 methanation is a very complex heterogeneous catalytic process, in which a variety of intermediates are produced. There are still many controversies and contradictions in the exploration of the reaction pathway of CO2 methanation. In-depth and systematic study of the evolution process of the intermediates formed on the catalyst surface in CO2 methanation will help to further optimize the design of catalyst from the perspective of mechanism, thereby improving the catalytic performance. This paper summarises recent work on the CO2 methanation reaction pathway based on in situ infrared spectroscopy, focusing on the influence of the active metal, carrier, additives and synthesis method of the supported catalyst on the CO2 methanation reaction pathway and the resulting positive effects on catalyst performance. In addition, the controversial points faced at the current stage, such as the activation sites of reaction gases CO2 and H2, the active sites of catalysts and the feasible research methods in the future are discussed in detail.

Research progress on catalytic reforming of bio-oil and its derivatives for hydrogen production
LI Guo, ZHANG An-dong, WAN Zhen, LI Zhi-he, WANG Shao-qing, LI Ning, ZHANG Peng
2023, 51(4): 444-457.   doi: 10.19906/j.cnki.JFCT.2022061
Abstract(114) HTML(36) PDF 21543KB(21)

Hydrogen is considered to be one of the most desirable clean energy sources and plays an important role in petroleum, chemical, metallurgical, petrochemical, food and fertilizer industries. Steam catalytic reforming of bio-oil for hydrogen production is considered as a promising and economically viable sustainable green hydrogen production technology, which has received a lot of attention from researchers. This paper presents a review of recent research in this field, focusing on the catalytic reforming of bio-oils (bio-crude oil, aqueous bio-oil and heavy bio-oil/tar), bio-oil model compounds (carboxylic acids, alcohols, phenols, etc.) and other bio-oil derivatives for hydrogen production, including the reforming reaction mechanism, reforming process and catalysts. The development of energy-efficient and efficient catalytic reforming reactors and stable and highly active reforming catalysts are the main focus of current and future research and promotion in the field of catalytic reforming of bio-oil for hydrogen production.

Research progress on the in-situ characterizations of iron-based FTS catalysts pretreatment process
HAN Yu-jing, WANG Hui-xiang, WANG Lian-cheng, HUANG Dong-mei, WANG Peng-fei, LÜ Bao-liang
2023, 51(4): 458-472.   doi: 10.19906/j.cnki.JFCT.2022067
Abstract(145) HTML(49) PDF 36863KB(40)

Fe-based Fischer-Tropsch synthesis (FTS) catalysts usually exist as the oxide precursor α-Fe2O3, which have different catalytic activities after being transformed to FexCy under different pretreatment conditions, so it is critical to study the pretreatment process of α-Fe2O3 for whole FTS reaction. However, the phases of Fe-based catalysts in such a process are highly dynamic and complex, and conventional characterizations cannot capture the accurate real-time information in the pretreatment reaction. Therefore, it is necessary and desired to apply various in-situ characterizations in this process, because they can obtain the dynamic changes of phase, morphology, surface structure and properties of the catalyst. And then a relationship between the pretreatment process and the subsequent catalytic performance of FTS will be effectively and reasonably established. This review presents a systematic summary of the experimental and data processing methods in in-situ characterizations of X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy and Raman spectroscopy during the pretreatment of Fe-based FTS catalysts. These characterizations can clarify the complex structure and surface property changes of catalyst precursors and thus will facilitate the design and development of more efficient Fe-based FTS catalysts.

Effect of crystal structure of ZrO2 catalyst on isobutene synthesis from CO hydrogenation
WU Xue-mei, TAN Ming-hui, GENG Hai-lun, ZHAO Sheng-ying, XU Bing, TAN Yi-sheng
2023, 51(4): 473-481.   doi: 10.1016/S1872-5813(22)60050-1
Abstract(78) HTML(47) PDF 1236KB(26)

ZrO2 catalysts with different crystal structures show different catalytic performance in isobutene synthesis from CO hydrogenation reaction. Although monoclinic ZrO2 has the best catalytic performance in isobutene synthesis from syngas, its isosynthesis active sites are still not well understood. To better understand the critical parameters that influence syngas to isobutene reactions over ZrO2 catalysts, we prepared a series of ZrO2 catalysts with distinct crystal structures and investigated their catalytic performance of CO hydrogenation to isobutene. Compared with tetragonal and amorphous ZrO2 catalysts, there are more coordinatively unsaturated Zr and O sites on the surface of monoclinic ZrO2 catalyst. The coordinatively unsaturated Zr sites are the active sites of CO adsorption and activation, which is beneficial to CO conversion. The coordinatively unsaturated O sites provide more basic sites for isobutene formation. Furthermore, the coordinatively unsaturated Zr and O sites on monoclinic ZrO2 catalyst surface may inhibit electron transfer to formate species formed during reaction, resulting in weak adsorption on catalyst surface of formate species. The weakly adsorbed formate species on the surface of monoclinic ZrO2 catalyst is favorable for the synthesis of isobutene from CO hydrogenation reaction.

Conversion of the CO and CO2 mixture to alcohols and hydrocarbons by hydrogenation under the influence of the water-gas shift reaction, a thermodynamic consideration
GUO Shu-jia, WANG Han, QIN Zhang-feng, LI Zhi-kai, WANG Guo-fu, DONG Mei, FAN Wei-bin, WANG Jian-guo
2023, 51(4): 482-491.   doi: 10.1016/S1872-5813(23)60346-9
Abstract(94) HTML(21) PDF 1034KB(29)

Due to the intervention from the water-gas shift (WGS) reaction (or the reverse one (RWGS)), the hydrogenation of CO (or CO2) into alcohols and hydrocarbons often displays rather high selectivity to CO2 (or CO), which makes it rather puzzling to evaluate such conversion processes by using the relatively low selectivity to the target products. Herein, a thermodynamic consideration is made to elaborately evaluate the effect of the WGS/RWGS reaction on the hydrogenation of CO, CO2, and their mixture to typical alcohols (e.g. methanol) and hydrocarbons (e.g. ethene). The results indicate that for the hydrogenation of CO (or CO2), although the WGS (or RWGS) reaction, acting as a communicating vessel connecting CO and CO2, may have a severe influence on the equilibrium conversion of CO (or CO2), forming a large amount of CO2 (or CO), it only has a relatively minor impact on the C-based equilibrium yield of the target alcohol/hydrocarbon product. The hydrogenation of CO shows a higher C-based equilibrium yield for the target product than the hydrogenation of CO2, while the overall C-based equilibrium yield of target product for the hydrogenation of the CO and CO2 mixture just lies in between. For the hydrogenation of the CO and CO2 mixture, although the equilibrium conversion of CO and CO2 may vary greatly with the change in the feed composition, the relation between the overall C-based equilibrium yield of the target product and the feed composition is rather simple; that is, the overall C-based equilibrium yield of alcohol/hydrocarbon product decreases almost lineally with the increase of the CO2/(CO + CO2) molar ratio in the feed. These results strongly suggest that the mixture of CO and CO2 is credible in practice for the production of alcohols and hydrocarbons through hydrogenation, where the overall C-based yield should be used as the major index for the hydrogenation of CO, CO2, and their mixture.

Study of the reaction mechanism based on the formation of the first carbocyclic ring from propargyl and diacetylene
ZHANG Wei, NING Shuo, MAO Shi-di, YANG Xi-li, CHEN Zhao-hui, MENG Li-ping
2023, 51(4): 492-501.   doi: 10.1016/S1872-5813(22)60054-9
Abstract(50) HTML(11) PDF 17099KB(7)

The formation of the first carbon ring is a crucial rate-controlling step in developing polycyclic aromatic hydrocarbons (PAHs). It is vital to investigate the mechanism of the creation of the first carbon ring to inhibit the formation of PAHs. To explore the growth process of the first carbocyclic ring, this work used the average localized ionization energy (ALIE) and electrostatic potential (ESP) to predict the reaction sites. Moreover, the reaction paths and chemical kinetic parameters for the generation of the first carbocyclic ring from propargyl (C3H3) + diacetylene (C4H2) are calculated based on the density functional theory  (DFT) method and transition state theory (TST). The results showed that the addition reaction of C3H3 +C4H2 can form five-, six- and seven-membered ring molecules, in which the five-membered ring formation is fastest and the six-membered ring formation is slowest. During the formation of the first carbon ring, the activation energy required for the H transfer and cyclization reactions is large, and the reaction rate is slow, which determines the formation rate of the first carbon ring. The rate of H-transfer reaction on each carbon ring depends on the number of C atoms of the carbon ring, with the five-membered ring being the fastest and the six-membered ring the slowest. This paper improves the reaction kinetics and thermodynamic data of the first carbon ring formation during the combustion of hydrocarbon fuels, which offers a powerful theoretical basis for predicting the generation of PAHs.

Regeneration characteristics of Ca-poisoned commercial selective catalytic reduction denitrification catalyst
XU Xin-rong, WU Hao, YU Le-meng, ZHUANG Ke, TANG Guang-hua, YANG Hong-min
2023, 51(4): 502-510.   doi: 10.19906/j.cnki.JFCT.2022068
Abstract(57) HTML(30) PDF 1756KB(12)

Alkaline earth metal calcium is a typical poison in coal-fired power plants, which will result in deactivation of SCR catalyst. The ATMP (amino trimethylene phosphonic acid) and PBTCA (2-phosphonobutane-1,2,4-tricarboxylic acid) complexing agents were employed for the regeneration of a poisoned by calcium V2O5-WO3/TiO2 catalyst. The physical and chemical properties and regeneration denitration performance of the catalyst before and after regeneration were investigated by BET, NH3-TPD, H2-TPR, XPS and experiments. The results indicated that the ATMP and PBTCA exhibited efficient regeneration performance, and the NOx conversion of regenerating catalysts recovered from 25.8% to 89.8% and 88.1% at 400 ℃, respectively. Compared with the regeneration by dilute sulfuric acid, the ATMP and PBTCA exhibited a higher calcium removal rate with lower vanadium loss (less than 5%). The utilization of the ATMP and PBTCA can effectively restore the Brønsted acid sites, active vanadium V5 + and the surface chemisorbed oxygen Oα on the catalyst surface, which leads to the overall activity of the catalyst reaching an optimal level. Therefore, it has a great potential to apply ATMP and PBTCA complexing agents in the regeneration of deactivated SCR denitration catalysts.

Preparation and electrochemical stability of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials
LI Ning, LI Song-bo, AN Sheng-li, DU Xu, XUE Liang-mei, NI Yang
2023, 51(4): 511-518.   doi: 10.1016/S1872-5813(22)60057-4
Abstract(42) HTML(8) PDF 1539KB(11)

A series of Co-doped La1.5Sr0.5Ni1−xCoxO4+δ cathode materials ( x =0, 0.2, 0.4 and 0.6) were synthesized by sol-gel method and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), coefficient of thermal expansion (CTE) measurement and scanning electron microscope (SEM). The results suggest that all La1.5Sr0.5Ni1−xCoxO4+δ samples have a single pure phase with the perovskite-like structure and the doping with the Co element can increase the CTE value. Using La1.5Sr0.5Ni1−xCoxO4+δ as the cathode materials in the solid oxide fuel cell (SOFC), their electrical conductivity and electrochemical impedance spectroscopy were measured. The results indicate that the conductivity increases with the increase of Co doping amount and the La1.5Sr0.5Ni0.6Co0.4O4+δ sample with x = 0.4 displays the highest conductivity of 51.21 S/cm at 800 ℃; however, a higher content of Co (x > 0.4) leads to a decrease of the conductivity. In addition, La1.5Sr0.5N0.6Co0.4O4+δ exhibits the lowest polarization resistance of 4.180 Ω·cm2 in electrochemical impedance spectrum at 700 ℃, displaying its excellent electrochemical properties as the cathode materials.

XRD characterization of structural evolution in low-middle rank coals
LI Xia, ZENG Fan-gui, WANG Wei, DONG Kui
2016, 44(7): 777-783.  
[Abstract](368) [FullText HTML](205) [PDF 2169KB](40)
通过对28个最大镜质组反射率0.30%-2.05%镜煤样品的X射线衍射(XRD) 分析, 获得XRD结构参数, 得到这些参数随反射率增大呈现的阶段性规律。在镜质组反射率小于1.0%阶段, LaLc急剧增加, d002迅速减小, 含氧官能团的脱落和脂肪长度支链化程度减小占主导; 在1.0%-1.6%阶段, La持续增加, d002先增加后减小, Lc先减小然后趋于平稳, 芳香体系脱氢和调整空间位阻同时进行; 在1.6%-2.0%阶段, d002持续减小, LcLa的增大, 煤结构演化以芳构化为主。XRD结构参数演化与第一、二次煤化作用跃变关系密切。
Structural analysis of functional group and mechanism investigation of caking property of coking coal
LI Xiang, QIN Zhi-hong, BU Liang-hui, YANG Zhuang, SHEN Chen-yang
2016, 44(4): 385-393.  
[Abstract](312) [FullText HTML](275) [PDF 1138KB](36)
以11种炼焦煤为研究对象,分别进行FT-IR和黏结指数G测试。采用PeakFit软件对FT-IR谱峰进行分峰拟合和定量计算,研究炼焦煤特征官能团含量与其黏结性间的关系。结果表明,煤黏结性大小与其FT-IR吸收峰密切相关,特别是3 000-2 800和3 700-3 000 cm-1两个吸收带;脂肪族结构是煤黏结性形成的主要决定因素,通常脂肪链越短或支链化程度越高,越有利于煤的黏结性形成;含-OH(或-NH)的氢键缔合结构可以与脂肪链协同作用,共同决定煤的黏结性能。不论煤分子有多大,只要是结构单元缩合度较小而作为桥键的脂肪链较多的结构形式,在热解过程中就会生成大量适度分子量、以结构单元为基元的液相物质。氢键是煤中主要的分子间作用形式,当若干形成氢键的官能团聚集缔合时,其相互作用会更强,甚至会形成类似超分子的结构;在形成胶质体阶段,这类氢键缔合的结构也会被打破,并形成以胶质体液相为主的物质。这些液相物质的存在,有利于胶质体的流动、黏连和固化成为半焦,从而最终获得优越的黏结性。
Effect of Na2O on mineral transformation of coal ash under high temperature gasification condition
CHEN Xiao-dong, KONG Ling-xue, BAI Jin, BAI Zong-qing, LI Wen
2016, 44(3): 263-272.  
[Abstract](194) [FullText HTML](175) [PDF 1275KB](22)
利用XRD和FT-IR考察了高温弱还原气氛下Na2O对两种硅铝含量不同的煤灰中矿物质组成的影响, 揭示了Na2O影响煤灰熔融特性的本质.通过FactSage计算了高温下矿物质反应的ΔG, 探讨了Na2O影响煤灰中矿物质组成的机理.结果表明, Na2O对煤灰矿物质组成的影响与原煤灰的硅铝含量密切相关.硅铝总含量82.89%的煤灰, Na2O含量为5%-20%时, 钠长石和霞石的生成是煤灰熔融温度降低的主要原因; 当Na2O含量大于20%时, 导致煤灰熔融温度降低的原因是霞石的生成.硅铝总含量47.85%的煤灰, Na2O含量小于10%时, 没有含钠矿物质生成; 当Na2O含量大于10%时, 主要生成菱硅钙钠石、青金石和含钠的硅铝酸盐矿物, 导致煤灰熔融温度降低.FactSage计算表明生成含Na矿物质反应的ΔG较小, 其在高温下更容易发生.
High resolution TEM image analysis of coals with different metamorphic degrees
LI Xia, ZENG Fan-gui, SI Jia-kang, WANG Wei, DONG Kui, CHENG Li-yuan
2016, 44(3): 279-286.  
[Abstract](290) [FullText HTML](244) [PDF 12189KB](23)
利用高分辨率透射电子显微镜(HRTEM) 分析了三种不同变质程度煤样的结构特征.基于傅里叶-反傅里叶变换方法, 并结合Matlab、Arcgis和AutoCAD软件, 通过图像分析技术, 获得了HRTEM照片的晶格条纹参数.结果表明, 三种煤样的晶格条纹呈现不同特征, 按条纹长度分别归属于1×1-8×8共计八个类型.以3×3为临界点, 在1×1和2×2中, ML-8中芳香层片的比例高于DP-4和XM-3;在3×3-8×8中, ML-8中芳香层片的比例低于DP-4和XM-3.对比HRTEM和XRD参数d002发现, 随着镜质组反射率的增加d002都呈现递减趋势.
Research progress in the direct conversion of syngas to lower olefins
YU Fei, LI Zheng-jia, AN Yun-lei, GAO Peng, ZHONG Liang-shu, SUN Yu-han
2016, 44(7): 801-814.  
[Abstract](663) [FullText HTML](418) [PDF 8665KB](68)
合成气直接催化转化制备低碳烯烃是C1化学与化工领域中一个极具挑战性的研究课题, 具有流程短、能耗低等优势, 已成为非石油路径生产烯烃的新途径。直接转化方式主要包括经由OX-ZEO双功能催化剂直接制低碳烯烃的双功能催化路线以及经由费托反应直接制备低碳烯烃的FTO路线。综述简述了近年来在合成气直接制备低碳烯烃方面的研究进展, 重点讨论了低碳烯烃的形成机理、新型催化剂的研发及助剂对其催化性能的影响, 并对合成气直接制烯烃的未来进行了展望。
Relationship between coal ash fusibility and ash composition in terms of mineral changes
WANG Yang, LI Hui, WANG Dong-xu, DONG Chang-qing, LU Qiang, LI Wen-yan
2016, 44(9): 1034-1042.  
[Abstract](314) [FullText HTML](187) [PDF 809KB](34)
通过在一种真实煤灰中添加不同的氧化物或直接用氧化物配制合成灰,探究了不同灰成分对灰熔融特性的影响规律。利用FactSage 7.0对不同灰分的熔融过程进行了热力学模拟,通过熔融过程中的矿物质变化为各种灰成分对熔融特性的影响规律提供理论依据。结果表明,氧化钠对灰熔点的降低作用源于钠长石和霞石对钙长石的取代;氧化镁含量的增加对灰熔点起先降低后升高的作用,当氧化镁含量超过一定时,产生的镁橄榄石能够升高灰熔点;硫对灰熔点的升高作用源于镁橄榄石和硫酸钙对透辉石的取代;氧化钙含量的增加对灰熔点起到先降低后升高的作用,当氧化钙含量超过一定时,硅从熔点较低的矿物质迁移到熔点较高的矿物质中,升高了灰熔点。在与硅氧单元体结合的过程中,氧化钠优先于氧化钙;与氧化钙和硅氧单元体结合的氧化物的优先级为:氧化铝>氧化镁>氧化铁。
Effect of rare-earth element modification on the performance of Cu/ZnAl catalysts derived from hydrotalcite precursor in methanol steam reforming
YANG Shu-qian, HE Jian-ping, ZHANG Na, SUI Xiao-wei, ZHANG Lei, YANG Zhan-xu
2018, 46(2): 179-188.  
[Abstract](220) [FullText HTML](119) [PDF 7028KB](21)
采用原位合成法在γ-Al2O3表面合成了锌铝水滑石,再通过顺次浸渍法制备了一系列掺杂稀土改性的MM=Y、La、Ce、Sm、Gd)/Cu/ZnAl催化材料,并将其应用于甲醇水蒸气重整制氢反应。探讨了稀土掺杂改性对Cu/ZnAl催化剂催化性能的影响,并采用XRD、SEM-EDS、BET、H2-TPR、XPS和N2O滴定等手段对催化剂进行了表征。结果表明,催化剂的活性与Cu比表面积和催化剂的还原性质密切相关,Cu比表面积越大,还原温度越低,催化活性越高。稀土Ce、Sm、Gd的引入能改善活性组分Cu的分散度、Cu比表面积以及催化剂的还原性质,进而提高催化剂的催化活性。其中,Ce/Cu/ZnAl催化剂表现出最佳的催化活性,在反应温度为250 ℃时,甲醇转化率达到100%,CO含量为0.39%,相比Cu/ZnAl催化剂,甲醇转化率提高了近40%。
Performance of Mn-Ce catalysts supported on different zeolites in the NH3-SCR of NOx
HUANG Zeng-bin, LI Cui-qing, WANG Zhen, XU Sheng-mei, FENG Ling-bo, WANG Hong, SONG Yong-ji, ZHANG Wei
2016, 44(11): 1388-1393.  
[Abstract](292) [FullText HTML](206) [PDF 780KB](25)
Effects of NH3 and SO3 on the generation of ammonium bisulfate and ammonium sulfate
YANG Jian-guo, YANG Wei-ying, ZHENG Fang-dong, ZHAO Hong
2018, 46(1): 92-98.  
[Abstract](185) [FullText HTML](102) [PDF 865KB](23)
Effects of acid-alkali treatment on properties and reactivity of ZSM-5 catalyst
LV Jiang-jiang, HUANG Xing-liang, ZHAO Lei-lei, SUN Ren-shan, HU Long-wang, GONG Yan
2016, 44(6): 732-737.  
[Abstract](273) [FullText HTML](209) [PDF 2776KB](29)
考察了碱处理、先碱后两步酸处理对HZSM-5分子筛物化性质以及苯与甲醇烷基化反应性能的影响。结果表明, 碱处理在脱除分子筛中非骨架硅的同时, 提高了晶孔的利用率, 也中和了分子筛的强酸中心, 使催化剂活化甲醇的能力减弱, 苯与甲醇反应活性降低; 先碱后两步酸处理既脱除了分子筛中的非骨架铝, 也恢复了一部分强酸中心, 提高了苯与甲醇的反应活性。进一步考察了先碱后两步酸处理中不同碱浓度的影响, 结果表明, 适宜浓度的碱处理后再两步酸处理, 一方面, 能脱除分子筛的非骨架硅铝物种, 使分子筛的颗粒粒径更加均匀; 另一方面, 分子筛的强酸中心有所减少, 降低了催化剂的积炭失活速率, 苯转化率提高15%以上。
Preparation of core-shell catalysts for one-step synthesis of dimethyl ether from syngas
WANG Wen-li, WANG Yan, CHEN Yue-xian, ZHAO Wen-chao, LI Rui-feng
2013, 41(08): 1003-1009.  
[Abstract](2232) [PDF 13334KB](41)
A core-shell catalyst CuO-ZnO-Al2O3@Al2O3 for one-step synthesis of dimethyl ether from synthesis gas was prepared using glucose, sucrose or starch as template, and characterized by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS). The thickness of the Al2O3 shell in the catalyst was altered by controlling the synthesis condition, such as temperature and time. The catalytic performance of dimethyl ether (DME) synthesized from CO hydrogenation on the catalysts were investigated. The conversion of CO and the selectivity of DME on CuO-ZnO-Al2O3@Al2O3 achieved 35.2% and 61.1% at 260 ℃, 5.0 MPa and 1 500 mL/(h·gcat), respectively.
Effect of wastewater treatment processes on thermal treatment properties of sewage sludge
JIE Li-Beng, Zheng-Shi-Mei, LI Chao
2009, 37(04): 501-505.  
[Abstract](1631) [PDF 1335KB](37)
The properties of pyrolysis and combustion for five different sewage sludges are studied by thermal gravimetric analysis at a heating rate of 10℃/min in the atomosphere of nitrogen and oxygen, respectively. The results show that both of the “anaerobic” wastewater treatment and the sludge anaerobic digestion make the organic compounds in sludge so complicated that the organic compounds decomposition and release temperature becomes higher during pyrolyzing, and the “aerobic + anaerobic” process makes the organic compounds in sludge more complicated than the “anaerobic +aerobic” process. There is no influence on the combustion process and the burnout point, but can make the combustion temperature of sludge higher. The thermal reaction mechanisms have been studied with šatava-šesták equation. It shows that the pyrolysis mechanism of these sludges is a process of volatile diffusion at first and then the chemical reaction function, while the combustion mechanism of them is a process of chemical reaction and diffusion function.