Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the t...Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.展开更多
It has been introduced several ways for rising fuel burning rate. Using catalyzers is a common way to rising fuel burning rate. Cu-Chromite catalyzer used in solid fuels, as burning rate catalyzer in thermal decomposi...It has been introduced several ways for rising fuel burning rate. Using catalyzers is a common way to rising fuel burning rate. Cu-Chromite catalyzer used in solid fuels, as burning rate catalyzer in thermal decomposition of Ammonium Perchlorate and results were satisfying. This catalyzer is produced by several methods such as: ceramic, coprecipitating, sol-gel, vacuum depositioning, but this paper explains producing catalyzer by Citrate sol-gel. Thermal analysis is used for studying process also SEM, XRD, TEM, FTIR tests used for determination of particle sizes.展开更多
With the implementation of more strict national environmental protection laws,energy conservation,emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techni...With the implementation of more strict national environmental protection laws,energy conservation,emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techniques and catalyzers.As for Claus tail gas,conventional hydrogenation catalyzers are gradually being replaced by low-temperature hydrogenation catalyzers.This paper concentrates on the development of technologies for low-temperature hydrogenation hydrolysis catalyzers,preparation of such catalyzers and their industrial application.In view of the specific features of SO2 hydrogenation and organic sulfur hydrolysis during low-temperature hydrogenation,a new technical process involving joint application of hydrogenation catalyzers and hydrolysis catalyzers was proposed.In addition,low-temperature hydrogenation catalyzers and low-temperature hydrolysis catalyzers suitable for low-temperature conditions were developed.Joint application of these two kinds of catalyzers may reduce the inlet temperatures in the conventional hydrogenation reactors from 280℃ to 220℃,at the same time,hydrogenation conversion rates of SO2 can be enhanced to over 99%.To further accelerate the hydrolysis rate of organic sulfur,the catalyzers for hydrolysis of low-temperature organic sulfur were developed.In lab tests,the volume ratio of the total sulfur content in tail gas can be as low as 131×10^(-6) when these two kinds of catalyzers were used in a proportion of 5:5 in volumes.Industrial application of these catalyzers was implemented in 17 sulfur recovery tail gas processing facilities of 15 companies.As a result,Sinopec Jinling Petrochemical Company had outstanding application performances with a tail gas discharging rate lower than 77.9 mg/m^(3) and a total sulfur recovery of 99.97%.展开更多
The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen...The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.展开更多
The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemica...The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemical composition of Fe_(3)O_(4) crystals was achieved under the microwave shock method with the same effect as that of calcination treatment.Fe_(3)O_(4) catalyst for the removal of the dye Rhodamine B (Rh B) from polluted wastewater under microwave (MW),H_(2)O_(2) system.The results showed that Fe_(3)O_(4) nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W,0.4 mol/L H_(2)O_(2) and10 mg/L Rh B,and the removal rate of Rh B reached 98.5%after 10 min.The Fe_(3)O_(4) catalysts also exhibited good stability and degradation efficiency.Electron paramagnetic resonance experiments confirmed that·OH plays a major role in the rapid degradation of Rh B.Under microwave action,the catalyst produces electron-hole pairs,in which the holes react with OH-produced by water ionisation to form·OH,and the microwave-treated Fe_(3)O_(4) produces more active species.Fe^(3+)and Fe^(2+)serve as microwave catalytic activity centers and Fenton catalytic activity centers,respectively.This research demonstrates that optimizing the Fe^(2+)/Fe^(3+) ratio significantly enhances the degradation efficiency of Rh B.This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.展开更多
The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace K...The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.展开更多
Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were...Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.展开更多
The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,...The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,particularly in the efficient construction of complex molecular architectures.However,most existing C-H activation systems rely on expensive noble metal catalysts,including palladium,rhodium,ruthenium,and iridium.These metals not only come at a high cost but are also often associated with significant toxicity,which further limits their viability and sustainability in industrial applications.展开更多
The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and N...The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and Nb exhibit superior hydrogen absorption energies as compared to Mg.By integrating two-dimensional Nb_(n)C_(n-1)T_(x)-MXene(with a large specific surface area and strong hydrogen absorption capacity provided by Nb)with Ni clusters,we developed an effective catalyst for hydrogen adsorption in MgH_(2).This study focused on the synthesis of an efficient MXene-Nb_(2)CT_(x)composite containing nano Ni cluster to enhance the hydrogenation and dehydrogenation processes of the Mg/MgH_(2)system.The Txend groups(-F,-O)were found to interact with Ni to create Ni-F or Ni-O bonds,which subsequently engage with adjacent Ni atoms to form Ni-Ni bonds.This interaction facilitates the loading of Ni clusters onto Nb_(2)CT_(x)and mitigates the inhibitory effects of-F or-O on hydrogen adsorption and desorption in the Mg-based system.Consequently,Nb_(2)C and Ni operate synergistic ally to enhance hydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds enhancehydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds facilitate hydrogen molecule dissociation on the Nb_(2)C/Ni composite.Hydrogen storage performance assesments demonstrated that the Nb_(2)C/Ni catalyst efficiently catalyzed hydrogen absorption and desorption;specifically,the hydrogenation/dehydrogenation capacity of Nb_(2)C/Ni@MgH_(2)reachedca.5.0 wt%at 100℃,while at 200℃,the capacities for hydrogenation and dehydrogenation reached 7.0 wt%and6.0 wt%,respectively,within 6 min.展开更多
The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassi...The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassium permanganate, phenol, 1,2 dihydroxybenzene and their combination on the oxidation of sodium thioantimonite were investigated. A pilot test was carried out. The results show that the respective use of sodium tartrate, cupric sulfate, potassium permanganate, phenol and 1,2 dihydroxybenzene have little catalytic effect on the oxidation of sodium thioantimonite. However there exists obvious catalytic oxidation by the combination of 0.25 g/L 1,2 dihydroxybenzene, 0.5 g/L potassium permanganate and 1.0 g/L phenol. Moreover, high blast intensity, the increase of temperature and NaOH concentration favor the oxidation of antimony. The oxidation process of antimony has such advantages as quick reaction and low operation costs. The results of the pilot test are consistent with those of laboratory experiments.展开更多
The secondary reinforcement,crbon whiskers,may grow on the surface of parent rein- forcement,carbon fibres,by chemical vapour growth from acetylene using Fe salt as catalyzer.The optimal growing temperature is about 1...The secondary reinforcement,crbon whiskers,may grow on the surface of parent rein- forcement,carbon fibres,by chemical vapour growth from acetylene using Fe salt as catalyzer.The optimal growing temperature is about 1000℃,and while the concentra- tion of catalytic solution is appropriate,the carbon whiskers may deposite uniformly and link each other on the parent carbon fibre surface.If the temperature or concentration is too high,the coarse clusters of carbon may deposite on the fibre surface.The mechanism of carbon whisker growth is believed that the carbon atoms in vapour phase dissolve in the Fe salt drops over fibres,then the solid carbon grains precipitate on the fibre surface.展开更多
Effects of the KCI additions （1%, 3%, 5% and 7% of the phenolic resin mass ） on phase composition and microstructure of the resin carbon and the growth mechanism of carbon fibers were investigated by using commercia...Effects of the KCI additions （1%, 3%, 5% and 7% of the phenolic resin mass ） on phase composition and microstructure of the resin carbon and the growth mechanism of carbon fibers were investigated by using commercial liquid phenolic resin as carbon source and micron-scaled KCl us catalyzer, mixing, hexamethylene- tetramine solidification treating, carbon-embedded firing at 1 000 ℃ for 3 h in order to accelerate the graphitization of phenolic resin during carbonization. The results show that the graphitization degree of resin carbon is im- proved by catalysis of KCl, numerous carbon fibers with 30 - 200 nm in diameter and 10 - 20 μm in length and sheet-like carbon in situ grow in resin carbon. The opti- mal addition of KCl is 5% when lots of carbon fibers can be found in resin carbon, and doo2 diffraction peak of graphite appears obviously in the XRD pattern. The growth mechanism of carbon fiber is that the molten KCl at high temperatures absorbs carbonaceous gas from the decomposition of phenolic resin, accelerating the diffu- sion of solid C atoms in liquid KCl ; after the dissolution of C saturates, carbon atoms separate continuously in lo- cal parts to form carbon fibers or flakes ; meanwhile, the concentration gradient formed by local carbon atoms in the melt offers growth drive for the separation of carbon fibers or flakes on KCl surface.展开更多
Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process...Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.展开更多
The synthesis of solar-driven chemical value-added products and the degradation of pollutants is a promising approach for sustainable development. However, achieving these works via photocatalysts with efficient charg...The synthesis of solar-driven chemical value-added products and the degradation of pollutants is a promising approach for sustainable development. However, achieving these works via photocatalysts with efficient charge-separation, photo-absorption is challenging. A yolk-shell CuCo_(2)S_(4)@Cu_(2)O Z-scheme nanoreactor (YS-CuCo_(2)S_(4)@Cu_(2) O-NR) with octahedron Cu_(2)O as the core and tubular CuCo2 S4 as the shell, has been synthesized by regulating composition and morphology. YS-CuCo_(2)S_(4)@Cu_(2)O-NR shows superior photocatalytic activities for producing H_(2) O_(2) collaborates by selective oxidation of benzyl alcohol (BA) to high value-added benzaldehyde (BAD)/utilized Fenton-like reaction to degrade multi-pollutants through space-confinement effect, reaching 80% conversion and 99% selectivity of BA, a yield of 12 mM g^(−1) for H_(2)O_(2) and above 90% degradation efficiency for multi-pollutants. A photocatalysis nanoconfinement reactor system is proposed and demonstrated by using yolk-shell to enhance the performance of the chemical reaction. Mechanism studies show that the yolk-shell provides confined space to accelerate redox reaction kinetics;while the inner void promotes light harvesting and keeps yolk Cu_(2) O from deactivation;combined with the Z-scheme charge transfer, engineering Cu^(+) /Cu^(2+) active composition, they are favorable for enhancing the H_(2) O_(2) generation and Fenton-like activity. These findings provide new opportunities for application of yolk-shell Z-scheme metal-oxide-based photocatalysts.展开更多
The single-walled carbon nanotube（SWNT） bundles and ropes have been prepared by using the anode are discharge plasma to evaporate the graphite rods which contain Fe, Co and Ni powders as catalyst in He atmosphere. M...The single-walled carbon nanotube（SWNT） bundles and ropes have been prepared by using the anode are discharge plasma to evaporate the graphite rods which contain Fe, Co and Ni powders as catalyst in He atmosphere. Many purifying methods are used for the products. It indicates that the synthesis of SWNTs has been greatly affected by the preparation parameters of catalyzer, the buffer gas and its pressure, the arc current intensity, etc. The optimal condition for preparing SWNTs in our case has been proposed. The forming mechanism of the SWNTs bundles and ropes is also studied qualitatively. The evaporated single graphite sheet tends to reduce its active energy.展开更多
This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by t...This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.展开更多
Securing new sources of energy has become a major concern, because fossil fuels are expected to be depleted within several decades. In some of the major wars of the 20th century, control of oil was either a proximate ...Securing new sources of energy has become a major concern, because fossil fuels are expected to be depleted within several decades. In some of the major wars of the 20th century, control of oil was either a proximate cause or a decisive factor in the outcome. Especially in Japan and Germany, a great deal of research was devoted to making liquid fuels from coal. In one such experiment, a large amount of excess heat was observed. The present study was devoted to replicating and controlling that excess heat effect. The reactant is phenanthrene, a heavy oil fraction, which is subjected to high pressure and high heat in the presence of a metal catalyst. This results in the production of excess heat and strong penetrating electromagnetic radiation. After the reaction, an analysis of residual gas reveals a variety of hydrocarbons, but it seems unlikely that these products can explain the excess heat. Most of them form endothermically, and furthermore heat production reached 60 W. Overall heat production exceeded any conceivable chemical reaction by two orders of magnitude.展开更多
Neutral isotopes and ions of H, He and Li define the chemistry of the early universe by collisional and radiative process, where under low temperature and radiation regime, only neutral species were essential in the c...Neutral isotopes and ions of H, He and Li define the chemistry of the early universe by collisional and radiative process, where under low temperature and radiation regime, only neutral species were essential in the cooling mass that gave origin to the first proto star structures. Nevertheless, up to now, in every kinetic model Li is permanently discarded from fundamental reactions due to its extremely low density. Contrarily to these previous models we have developed a novel kinetic model based on two consecutive reactions of Li and LiH with H, in order to generate a recursive process that fit well H2 production to temperatures as low as 200 K, according to the cosmological time at the end of the dark epoch. Our results show how Li and LiH merge as first catalyzers of the H to H2 chemical reaction and permit us to explain the expected abundance of H2 as the main coolant in the early universe as well as in cold regions of the cosmos.展开更多
The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇...The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇ iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders＇ iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10：1 （w/w） were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders＇ iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders＇ iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode （Cu） and anode （Fe） compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.展开更多
This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（C...This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.展开更多
基金Supported by the National Natural Science Foundation of China （No.60574047） and the Doctorate Foundation of the State Education Ministry of China （No.20050335018）.
文摘Abstract Data-driven tools, such as principal component analysis （PCA） and independent component analysis （ICA） have been applied to different benchmarks as process monitoring methods. The difference between the two methods is that the components of PCA are still dependent while ICA has no orthogonality constraint and its latentvariables are independent. Process monitoring with PCA often supposes that process data or principal components is Gaussian distribution. However, this kind of constraint cannot be satisfied by several practical processes. To ex-tend the use of PCA, a nonparametric method is added to PCA to overcome the difficulty, and kernel density estimation （KDE） is rather a good choice. Though ICA is based on non-Gaussian distribution intormation, .KDE can help in the close monitoring of the data. Methods, such as PCA, ICA, PCA.with .KDE（KPCA）, and ICA with KDE,（KICA）, are demonstrated and. compared by applying them to a practical industnal Spheripol craft polypropylene catalyzer reactor instead of a laboratory emulator.
文摘It has been introduced several ways for rising fuel burning rate. Using catalyzers is a common way to rising fuel burning rate. Cu-Chromite catalyzer used in solid fuels, as burning rate catalyzer in thermal decomposition of Ammonium Perchlorate and results were satisfying. This catalyzer is produced by several methods such as: ceramic, coprecipitating, sol-gel, vacuum depositioning, but this paper explains producing catalyzer by Citrate sol-gel. Thermal analysis is used for studying process also SEM, XRD, TEM, FTIR tests used for determination of particle sizes.
文摘With the implementation of more strict national environmental protection laws,energy conservation,emission reduction and clean production will present higher requirements for sulfur recovery tail gas processing techniques and catalyzers.As for Claus tail gas,conventional hydrogenation catalyzers are gradually being replaced by low-temperature hydrogenation catalyzers.This paper concentrates on the development of technologies for low-temperature hydrogenation hydrolysis catalyzers,preparation of such catalyzers and their industrial application.In view of the specific features of SO2 hydrogenation and organic sulfur hydrolysis during low-temperature hydrogenation,a new technical process involving joint application of hydrogenation catalyzers and hydrolysis catalyzers was proposed.In addition,low-temperature hydrogenation catalyzers and low-temperature hydrolysis catalyzers suitable for low-temperature conditions were developed.Joint application of these two kinds of catalyzers may reduce the inlet temperatures in the conventional hydrogenation reactors from 280℃ to 220℃,at the same time,hydrogenation conversion rates of SO2 can be enhanced to over 99%.To further accelerate the hydrolysis rate of organic sulfur,the catalyzers for hydrolysis of low-temperature organic sulfur were developed.In lab tests,the volume ratio of the total sulfur content in tail gas can be as low as 131×10^(-6) when these two kinds of catalyzers were used in a proportion of 5:5 in volumes.Industrial application of these catalyzers was implemented in 17 sulfur recovery tail gas processing facilities of 15 companies.As a result,Sinopec Jinling Petrochemical Company had outstanding application performances with a tail gas discharging rate lower than 77.9 mg/m^(3) and a total sulfur recovery of 99.97%.
文摘The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.
基金supported by Beijing Natural Science Foundation(No.2232062)the Fundamental Research Funds for the Central Universities (No.2652022006)。
文摘The Fenton method is an effective technology for the removal of organic materials from wastewater.In this work,an induced catalyst Fe_(3)O_(4) was synthesized by a hydrothermal method,and the modulation of the chemical composition of Fe_(3)O_(4) crystals was achieved under the microwave shock method with the same effect as that of calcination treatment.Fe_(3)O_(4) catalyst for the removal of the dye Rhodamine B (Rh B) from polluted wastewater under microwave (MW),H_(2)O_(2) system.The results showed that Fe_(3)O_(4) nanomicrospheres prepared by microwave shock exhibited superior catalytic activity under the conditions of 500 W,0.4 mol/L H_(2)O_(2) and10 mg/L Rh B,and the removal rate of Rh B reached 98.5%after 10 min.The Fe_(3)O_(4) catalysts also exhibited good stability and degradation efficiency.Electron paramagnetic resonance experiments confirmed that·OH plays a major role in the rapid degradation of Rh B.Under microwave action,the catalyst produces electron-hole pairs,in which the holes react with OH-produced by water ionisation to form·OH,and the microwave-treated Fe_(3)O_(4) produces more active species.Fe^(3+)and Fe^(2+)serve as microwave catalytic activity centers and Fenton catalytic activity centers,respectively.This research demonstrates that optimizing the Fe^(2+)/Fe^(3+) ratio significantly enhances the degradation efficiency of Rh B.This study presents novel views regarding the mechanism of microwave synergistic catalyst-induced Fenton.
基金supported by the National Natural Science Foundation of China(52376103,542B2081).
文摘The technology for green and macro-conversion of solid waste biomass to prepare high-quality activated carbon demands urgent development.This study proposes a technique for synthesizing carbon adsorbents using trace KOH-catalyzed CO_(2) activation.Comprehensive investigations were conducted on three aspects:physicochemical structure evolution of biochar,mechanistic understanding of trace KOH-facilitated CO_(2) activation processes,and application characteristics for CO_(2) adsorption.Results demonstrate that biochar activated by trace KOH(<10%)and CO_(2) achieves comparable specific surface area(1244.09 m^(2)/g)to that obtained with 100%KOH activation(1425.10 m^(2)/g).The pore structure characteristics(specific surface area and pore volume)are governed by CO and CH4 generated through K-salt catalyzed reactions between CO_(2) and biochar.The optimal CO_(2) adsorption capacities of KBC adsorbent reached 4.70 mmol/g(0℃)and 7.25 mmol/g(25℃),representing the maximum values among comparable carbon adsorbents.The 5%KBC-CO_(2) sample exhibited CO_(2) adsorption capacities of 3.19 and 5.01 mmol/g under respective conditions,attaining current average performance levels.Notably,CO_(2)/N_(2) selectivity(85∶15,volume ratio)reached 64.71 at 0.02 bar with robust cycling stability.Molecular dynamics simulations revealed that oxygen-containing functional groups accelerate CO_(2) adsorption kinetics and enhance micropore storage capacity.This technical route offers simplicity,environmental compatibility,and scalability,providing critical references for large-scale preparation of high-quality carbon materials.
文摘Gold,unlike other transition metals such as Pd,Ni,and Cu,offers unique reactivity profiles and has emerged as an attractive area of research in organic chemistry over the last two decades.Initially,gold catalysts were widely used for theπ-activation of unsaturated carbon−carbon bonds,particularly alkynes.Moreover,they exhibit favorable functional-group compatibility,good biocompatibility,and,generally,gold-catalyzed reactions are not sensitive to air or water.
文摘The activation of carbon-hydrogen(C-H)bonds is of great scientific importance and offers broad applications in modern organic chemistry[1].In recent years,strategies for C-H bond activation have made notable advances,particularly in the efficient construction of complex molecular architectures.However,most existing C-H activation systems rely on expensive noble metal catalysts,including palladium,rhodium,ruthenium,and iridium.These metals not only come at a high cost but are also often associated with significant toxicity,which further limits their viability and sustainability in industrial applications.
基金financially supported by the Natural Science Foundation of Jiangsu Province of China(No.BK20210079)Xuzhou Science and Technology Project(No.KC23011)
文摘The robust Mg-H bonds present in magnesium hydride(MgH_(2))hinder the dissociation of hydrogen molecules on MgH_(2),leading to suboptimal thermo dynamic and kinetic properties.Transition metals such as nickel(Ni)and Nb exhibit superior hydrogen absorption energies as compared to Mg.By integrating two-dimensional Nb_(n)C_(n-1)T_(x)-MXene(with a large specific surface area and strong hydrogen absorption capacity provided by Nb)with Ni clusters,we developed an effective catalyst for hydrogen adsorption in MgH_(2).This study focused on the synthesis of an efficient MXene-Nb_(2)CT_(x)composite containing nano Ni cluster to enhance the hydrogenation and dehydrogenation processes of the Mg/MgH_(2)system.The Txend groups(-F,-O)were found to interact with Ni to create Ni-F or Ni-O bonds,which subsequently engage with adjacent Ni atoms to form Ni-Ni bonds.This interaction facilitates the loading of Ni clusters onto Nb_(2)CT_(x)and mitigates the inhibitory effects of-F or-O on hydrogen adsorption and desorption in the Mg-based system.Consequently,Nb_(2)C and Ni operate synergistic ally to enhance hydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds enhancehydrogen dissociation and weaken Mg-H bonds.Theoretical simulations revealed that the inclusion of the Nb_(2)C/Ni catalyst in an elongation of Mg-H bonds facilitate hydrogen molecule dissociation on the Nb_(2)C/Ni composite.Hydrogen storage performance assesments demonstrated that the Nb_(2)C/Ni catalyst efficiently catalyzed hydrogen absorption and desorption;specifically,the hydrogenation/dehydrogenation capacity of Nb_(2)C/Ni@MgH_(2)reachedca.5.0 wt%at 100℃,while at 200℃,the capacities for hydrogenation and dehydrogenation reached 7.0 wt%and6.0 wt%,respectively,within 6 min.
文摘The behavior of antimony oxidation in the solution of sodium thioantimonite was studied in the presence of catalytic agents. The catalytic effects of the respective addition of cupric sulfate, sodium tartrate, potassium permanganate, phenol, 1,2 dihydroxybenzene and their combination on the oxidation of sodium thioantimonite were investigated. A pilot test was carried out. The results show that the respective use of sodium tartrate, cupric sulfate, potassium permanganate, phenol and 1,2 dihydroxybenzene have little catalytic effect on the oxidation of sodium thioantimonite. However there exists obvious catalytic oxidation by the combination of 0.25 g/L 1,2 dihydroxybenzene, 0.5 g/L potassium permanganate and 1.0 g/L phenol. Moreover, high blast intensity, the increase of temperature and NaOH concentration favor the oxidation of antimony. The oxidation process of antimony has such advantages as quick reaction and low operation costs. The results of the pilot test are consistent with those of laboratory experiments.
文摘The secondary reinforcement,crbon whiskers,may grow on the surface of parent rein- forcement,carbon fibres,by chemical vapour growth from acetylene using Fe salt as catalyzer.The optimal growing temperature is about 1000℃,and while the concentra- tion of catalytic solution is appropriate,the carbon whiskers may deposite uniformly and link each other on the parent carbon fibre surface.If the temperature or concentration is too high,the coarse clusters of carbon may deposite on the fibre surface.The mechanism of carbon whisker growth is believed that the carbon atoms in vapour phase dissolve in the Fe salt drops over fibres,then the solid carbon grains precipitate on the fibre surface.
文摘Effects of the KCI additions （1%, 3%, 5% and 7% of the phenolic resin mass ） on phase composition and microstructure of the resin carbon and the growth mechanism of carbon fibers were investigated by using commercial liquid phenolic resin as carbon source and micron-scaled KCl us catalyzer, mixing, hexamethylene- tetramine solidification treating, carbon-embedded firing at 1 000 ℃ for 3 h in order to accelerate the graphitization of phenolic resin during carbonization. The results show that the graphitization degree of resin carbon is im- proved by catalysis of KCl, numerous carbon fibers with 30 - 200 nm in diameter and 10 - 20 μm in length and sheet-like carbon in situ grow in resin carbon. The opti- mal addition of KCl is 5% when lots of carbon fibers can be found in resin carbon, and doo2 diffraction peak of graphite appears obviously in the XRD pattern. The growth mechanism of carbon fiber is that the molten KCl at high temperatures absorbs carbonaceous gas from the decomposition of phenolic resin, accelerating the diffu- sion of solid C atoms in liquid KCl ; after the dissolution of C saturates, carbon atoms separate continuously in lo- cal parts to form carbon fibers or flakes ; meanwhile, the concentration gradient formed by local carbon atoms in the melt offers growth drive for the separation of carbon fibers or flakes on KCl surface.
文摘Conjugated linoleic acid (CLA) is a fatty acid with physiological activities and potential application prospect. This paper focuses on the method of synthesis of conjugated linoleic acid of high purity and the process line and conditions for its purification that can be used in large scale production. CLA of more than 95% purity was prepared by means of urea adduct purification and conjugation using safflower oil as material. The total recovery of the product adds up to more than 48%. The reactive kinetics about linoleic acid from sunflower oil converted into CLA was investigated, and its apparent kinetic model was also established, which can be used as a base for industrial designs.
基金supported by the National Nature Science Foundation of China(Nos.NSFC52072164 and NSFC 32102086)Liaoning Province Science and Technology Planning Project(No.20180551203).
文摘The synthesis of solar-driven chemical value-added products and the degradation of pollutants is a promising approach for sustainable development. However, achieving these works via photocatalysts with efficient charge-separation, photo-absorption is challenging. A yolk-shell CuCo_(2)S_(4)@Cu_(2)O Z-scheme nanoreactor (YS-CuCo_(2)S_(4)@Cu_(2) O-NR) with octahedron Cu_(2)O as the core and tubular CuCo2 S4 as the shell, has been synthesized by regulating composition and morphology. YS-CuCo_(2)S_(4)@Cu_(2)O-NR shows superior photocatalytic activities for producing H_(2) O_(2) collaborates by selective oxidation of benzyl alcohol (BA) to high value-added benzaldehyde (BAD)/utilized Fenton-like reaction to degrade multi-pollutants through space-confinement effect, reaching 80% conversion and 99% selectivity of BA, a yield of 12 mM g^(−1) for H_(2)O_(2) and above 90% degradation efficiency for multi-pollutants. A photocatalysis nanoconfinement reactor system is proposed and demonstrated by using yolk-shell to enhance the performance of the chemical reaction. Mechanism studies show that the yolk-shell provides confined space to accelerate redox reaction kinetics;while the inner void promotes light harvesting and keeps yolk Cu_(2) O from deactivation;combined with the Z-scheme charge transfer, engineering Cu^(+) /Cu^(2+) active composition, they are favorable for enhancing the H_(2) O_(2) generation and Fenton-like activity. These findings provide new opportunities for application of yolk-shell Z-scheme metal-oxide-based photocatalysts.
文摘The single-walled carbon nanotube（SWNT） bundles and ropes have been prepared by using the anode are discharge plasma to evaporate the graphite rods which contain Fe, Co and Ni powders as catalyst in He atmosphere. Many purifying methods are used for the products. It indicates that the synthesis of SWNTs has been greatly affected by the preparation parameters of catalyzer, the buffer gas and its pressure, the arc current intensity, etc. The optimal condition for preparing SWNTs in our case has been proposed. The forming mechanism of the SWNTs bundles and ropes is also studied qualitatively. The evaporated single graphite sheet tends to reduce its active energy.
基金supported by the Petrochemical Joint Funds of NSFC-CNPC (U1362202)the Postgraduate Innovation Project of China University of Petroleum (East China) (YCXJ2016030)~~
文摘This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.
文摘Securing new sources of energy has become a major concern, because fossil fuels are expected to be depleted within several decades. In some of the major wars of the 20th century, control of oil was either a proximate cause or a decisive factor in the outcome. Especially in Japan and Germany, a great deal of research was devoted to making liquid fuels from coal. In one such experiment, a large amount of excess heat was observed. The present study was devoted to replicating and controlling that excess heat effect. The reactant is phenanthrene, a heavy oil fraction, which is subjected to high pressure and high heat in the presence of a metal catalyst. This results in the production of excess heat and strong penetrating electromagnetic radiation. After the reaction, an analysis of residual gas reveals a variety of hydrocarbons, but it seems unlikely that these products can explain the excess heat. Most of them form endothermically, and furthermore heat production reached 60 W. Overall heat production exceeded any conceivable chemical reaction by two orders of magnitude.
文摘Neutral isotopes and ions of H, He and Li define the chemistry of the early universe by collisional and radiative process, where under low temperature and radiation regime, only neutral species were essential in the cooling mass that gave origin to the first proto star structures. Nevertheless, up to now, in every kinetic model Li is permanently discarded from fundamental reactions due to its extremely low density. Contrarily to these previous models we have developed a novel kinetic model based on two consecutive reactions of Li and LiH with H, in order to generate a recursive process that fit well H2 production to temperatures as low as 200 K, according to the cosmological time at the end of the dark epoch. Our results show how Li and LiH merge as first catalyzers of the H to H2 chemical reaction and permit us to explain the expected abundance of H2 as the main coolant in the early universe as well as in cold regions of the cosmos.
基金Project supported by the Hi-Tech Research and Development Program(863) of China (No. 2002AA601270)
文摘The dectrochemical reduction characteristics of carbon tetrachlofide （CT） were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders＇ iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders＇ iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10：1 （w/w） were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders＇ iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders＇ iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode （Cu） and anode （Fe） compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.
基金supported by the National High Technology Research and Development Program of China(863)(No.2013AA065304)
文摘This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.
