Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction tempe...Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.展开更多
Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, ins...Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, insufficient Hg^0 oxidation activity, SO_2 oxidation, ammonia slip, and other disadvantages,modifications to traditional vanadium-titanium-based selective catalytic reduction（SCR）catalysts have been attempted by many researchers to promote their relevant performance. This article reviewed the research progress of modified vanadium-titanium-based SCR catalysts from seven aspects, namely,（1） improving low-temperature deNO_x efficiency,（2） enhancing thermal stability,（3） improving Hg^0 oxidation efficiency,（4） oxidizing slip ammonia,（5） reducing SO_2 oxidation,（6） increasing alkali resistance, and（7） others. Their catalytic performance and the influence mechanisms have been discussed in detail. These catalysts were also divided into different categories according to their modified components such as noble metals（e.g., silver, ruthenium）, transition metals（e.g., manganese, iron, copper, zirconium, etc.）, rare earth metals（e.g., cerium, praseodymium）,and other metal chlorides（e.g., calcium chloride, copper chloride） and non-metals（fluorine,sulfur, silicon, nitrogen, etc.）. The advantages and disadvantages of these catalysts were summarized.Based on previous studies and the author＇s point of view, doping the appropriate modified components is beneficial to further improve the overall performance of vanadium-titanium-based SCR catalysts. This has enormous development potential and is a promising way to realize the control of multiple pollutants on the basis of the existing flue gas treatment system.展开更多
An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio...An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.展开更多
Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth ...Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.展开更多
To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures rangi...To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures ranging from 60 to 200 ℃ was obtained by recently published critically assessed standard Gibbs energies and activity coefficients of various species. When pH2, stable regions of V3＋, VO2＋ and VO2＋ exist in the stable region of TiO2. The pH values of stable regions of vanadium and titanium decrease and redox potentials become more positive with the temperature increasing. Vanadium and titanium could be separated by one-step leaching based on thermodynamics. The experiment results of pressure acid leaching of converter slag show that leaching rates of vanadium and titanium are 96.87% and 8.76% respectively, at 140 ℃ of temperature, 0.5 MPa of oxygen partial pressure, 0.055-0.075mm of particle size, 15：1 of liquid to solid ratio, 120 min of leaching time, 500 r/min of stirring speed and 200 g/L of initial acid concentration. Vanadium and titanium could be selectively separated in the pressure acid leaching process, and the experiment result is in agreement with thermodynamic calculation result.展开更多
The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted...The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.展开更多
To achieve high efficiency utilization of high-chromium vanadium-titanium magnetite （V-Ti-Cr） fines, an investigation of V Ti42r fines was conducted using a sinter pot. The chemical composition, particle parameters,...To achieve high efficiency utilization of high-chromium vanadium-titanium magnetite （V-Ti-Cr） fines, an investigation of V Ti42r fines was conducted using a sinter pot. The chemical composition, particle parameters, and granulation of V-Ti-Cr mixtures were analyzed, and the effects of sintering parameters on the sintering behaviors were investigated. The results indicated that the optimum quicklime dosage, mixture moisture, wetting time, and granulation time for V-Ti-Cr fines are 5wt%, 7.5wt%, 10 min, and 5-8 min, respectively. Meanwhile, the vertical sintering speed, yield, tumbler strength, and productivity gains were shown to be 21.28 mm/min, 60.50wt% , 58.26wt%, and 1.36 t·m^-2·h^-1, respectively. Furthermore, the consolidation mechanism of V-Ti-Cr fines was clarified, revealing that the consolidation of a V-Ti-Cr sinter requires an approximately 14vo1% calcium ferrite liquid-state, an approximately 15vo1% silicate liq- uid-state, a solid-state reaction, and the recrystallization of magnetite. Compared to an ordinary sinter, calcium ferrite content in a V-Ti-Cr sinter is lower, while the perovskite content is higher, possibly resulting in unsatisfactory sinter outcomes.展开更多
Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range...Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range from 1 473 to 1 673 K. The scanning electron microscope （SEM） was used to characterize the microstructure of product. By analyzing reduction mechanism, it was found that the rate controlling step was gas diffusion, and the activation energy was 178.39 kJ/mol without adding any catalysts. Adding CaF2 or NaF of 3% to vanadium titano-magnetite carbon composite pellets can decrease the apparent activation energy of reduction, and the decrease extent was 14.95 and 15.79 kJ/mol, respectively. In addition, temperature was an important factor influencing on reaction rate.展开更多
The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratio...The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratios:100V/Ce=0.1,1,4,10,and 20) were prepared by an incipient-wetness impregnation method.Spectroscopic techniques(XRD,FT-IR,Raman and UV-Vis DRS) were utilized to characterize the structures of VOx/CeO2 catalysts.The results showed that the structures of CeO2-supported vanadium oxide catalysts de...展开更多
The effect of diboron trioxide(B_2O_3) on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray ...The effect of diboron trioxide(B_2O_3) on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma–atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy–energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B_2O_3 content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B_2O_3 content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B_2O_3 content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B_2O_3. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B_2O_3 content.展开更多
The process of pressure leaching the converter vanadium slag with waste titanium dioxide without roasting was studied. Mineralogy analysis indicates that the con- verter vanadium slag contains mainly three mineral pha...The process of pressure leaching the converter vanadium slag with waste titanium dioxide without roasting was studied. Mineralogy analysis indicates that the con- verter vanadium slag contains mainly three mineral phases： magnetite, titanium magnetite, and silicate phase. Vana- dium is in combination with iron, titanium, manganese, aluminum, and silicon. The impacts of leaching tempera- ture, leaching time, stirring speed, liquid-to-solid ratio, and initial leaching agent concentration were investigated on the waste titanium dioxide leaching process. The results indi- cate that under the optimal conditions, the vanadium and the iron leaching rates are 96.85 % and 93.50 %, respectively, and the content of titanium is 12.6 % in the residue. The main mineral phases for the residues under the optimal operation conditions are quartz, ilmenite, anatase, and sili- cate phase, and the residues can be reused as the extraction of titanium raw materials for titanium dioxide production technology by the sulfate method.展开更多
The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the z...The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the zeolite crystallite by V<sub>2</sub>O<sub>5</sub>.Formation of low melting pointV<sub>2</sub>O<sub>5</sub>-USY-Na<sub>2</sub>O phases accelerates the diffusion of vanadium through the catalyst.A proposedmechanism,based on accelerated dealumination,is shown in the paper.Comparative vanadiumtrapping performances have been tested for FCC catalysts and the crystalline ABO<sub>3</sub> as an effectivevanadium trap is demonstrated in laboratory tests.展开更多
(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalyt...(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].展开更多
The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis.According to the t...The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis.According to the thermodynamic results,low-melting-point regions and MgTi2O5primary phase area in the phase diagrams,the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of50%TiO2,8%-12%MgO and13%Al2O3(mass fraction)with a binary basicity of0.8-1.2.Finally,the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained.The obtained vanadium-containing molten iron contains0.681%V and0.267%Ti,and the obtained titanium slag contains52.21%TiO2(mass fraction),in which MgTi2O5is the primary phase.The titanium resource in the final titanium slag production could be used to produce TiO2pigment by acid leaching methods.展开更多
Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction deg...Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction degree.The phase compositions of the reduced materials and the leached residues were analyzed by XRD to identify the effect of reduction degree on the leaching mechanisms.The results showed that the concentrates were reduced to iron metal and titanomagnetite at 800-1000°C for 0.5 h,and the above elements of Fe and impurities were easily leached.Deeper reduction led to the formation of ilmenite and Mg-Al spinel,which hindered leaching.Mg-bearing anosovite appeared in the further reduced materials,and the leaching rates of impurities became much lower.An upgraded titanium mineral with a normalized TiO_(2) grade of 70.3%was achieved by H_(2) reduction at 850°C for 0.5 h and acid leaching,which is a satisfactory Ti resource for the preparation of titanium oxide by sulfate process.展开更多
Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of p...Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimalcondition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalyticactivity was up to 54.7% at 410℃, which was 2.2% higher than that of the Ls-8 catalyst. Only 10 minwas needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time.For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermalanalysis shifted to higher temperatures obviously, indicating that its crystal phase could melteasily. There existed an apparent endothermic peak at 283℃. SEM photographs showed a uniform sizedistribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form ofVOSO_4.展开更多
Large quantities of spent hydrodesulfurization (HDS) catalysts are available from petrochemical industry. Disposal of spent catalyst is a problem as it falls under the category of hazardous industrial waste due to its...Large quantities of spent hydrodesulfurization (HDS) catalysts are available from petrochemical industry. Disposal of spent catalyst is a problem as it falls under the category of hazardous industrial waste due to its vanadium concentration. Most of these catalysts are usually supported on alumina containing a variable percentage of elements such as nickel or molybdenum. Hence these catalysts contain environmentally critical, and economically valuable metals such as molyb denum, vanadium, and, nickel. In this paper, a spent HDS catalyst was treated with caustic soda solution. Parameters such as temperature, time, and NaOH solution concentration have been studied thoroughly, in order to settle the appropriate conditions for the maximum recovery of molybdenum and vanadium. Under the best leaching conditions (20 %w NaOH, room temperature, 2 h) about 95% recovery of Mo and V was achieved, and the recovery of nickel obtained was of 99% in the form of NiAlO4.展开更多
The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minu...The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minutes were needed to produce obvious cavitations when thecatalyst raw material was treated in the 50 W ultrasonic generator. However, only 10 minutes wouldbe needed in a 150 W ultrasonic generator. The higher the temperature of the wet material, the lesstime was needed to produce cavitations, and the optimal temperature was 60℃. The water content inthe wet material mainly affected the quantity of cavitations. Ls-8 catalyst was prepared usingultrasonic. Its activity for conversion of SO_2 reached to 52.5% at 410℃ and 4.2% at 350℃. Thedifferential thermal analyses indicate that both endothermic peaks and exothermic peaks noticeablyshifted forward compared with Ls catalyst prepared without ultrasonic, and SEM results show auniform pore size distribution for Ls-8 catalyst.展开更多
基金supported by the Program for New Century Excellent Talents in Universities(NCET-07-0142)the Program for New Century Excellent Talents in Heilongjiang Provincial Universities(NCET-06-010)+1 种基金the National Natural Science Foundation of China(No.20972025)the Science Foundation of Tianjin University of Science & Technology(No.20090420)
文摘Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.
基金supported by the Science and Technology Plan Project of Hebei Province of China(16273703D)the Fundamental Research Funds for the Central Universities(2015ZD24,2017XS123)~~
文摘Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, insufficient Hg^0 oxidation activity, SO_2 oxidation, ammonia slip, and other disadvantages,modifications to traditional vanadium-titanium-based selective catalytic reduction（SCR）catalysts have been attempted by many researchers to promote their relevant performance. This article reviewed the research progress of modified vanadium-titanium-based SCR catalysts from seven aspects, namely,（1） improving low-temperature deNO_x efficiency,（2） enhancing thermal stability,（3） improving Hg^0 oxidation efficiency,（4） oxidizing slip ammonia,（5） reducing SO_2 oxidation,（6） increasing alkali resistance, and（7） others. Their catalytic performance and the influence mechanisms have been discussed in detail. These catalysts were also divided into different categories according to their modified components such as noble metals（e.g., silver, ruthenium）, transition metals（e.g., manganese, iron, copper, zirconium, etc.）, rare earth metals（e.g., cerium, praseodymium）,and other metal chlorides（e.g., calcium chloride, copper chloride） and non-metals（fluorine,sulfur, silicon, nitrogen, etc.）. The advantages and disadvantages of these catalysts were summarized.Based on previous studies and the author＇s point of view, doping the appropriate modified components is beneficial to further improve the overall performance of vanadium-titanium-based SCR catalysts. This has enormous development potential and is a promising way to realize the control of multiple pollutants on the basis of the existing flue gas treatment system.
基金funded by the National Natural Science Foundation of China(Nos.U20A20145,51774205)the Open Project from Engineering Research Center of the Ministry of Education,Sichuan University,China.
文摘An approach for coal-based direct reduction of vanadium−titanium magnetite(VTM)raw ore was proposed.Under the optimal reduction conditions with reduction temperature of 1140℃,reduction time of 3 h,C-to-Fe molar ratio of 1.2꞉1,and pre-oxidation temperature of 900℃,the iron metallization degree is 97.8%.Ultimately,magnetic separation yields an iron concentrate with an Fe content of 76.78 wt.%and efficiency of 93.41%,while the magnetic separation slag has a Ti grade and recovery of 9.36 wt.%and 87.07%,respectively,with a titanium loss of 12.93%.This new strategy eliminates the beneficiation process of VTM raw ore,effectively reduces the Ti content in the iron concentrate,and improves the comprehensive utilization of valuable metals.
基金financially supported by the Key Basic Research Project of Shandong Province(No.ZR2019ZD49)Taishan Scholar Foundation of Shandong Province(No.tstp20230627)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences。
文摘Single-walled carbon nanotubes(SWNTs)with enriched(n,m)species are in high demand for various advanced applications.Since the SWNT structure is largely influenced by the chemistry of the active catalyst during growth process,exploiting novel catalyst with bias towards specific SWNT chiralities has been challenging.In this work,we introduce a vanadium catalyst supported by mesoporous magnesia(V-MgO)for the selective growth of SWNTs using CO chemical vapor deposition(CVD).At a reaction temperature of 650℃,the(6,5)SWNT content reaches an impressive 67.9%among all semiconducting species,exceeding the selectivity of many commercial SWNT products.Post-CVD analysis reveals that the catalyst transforms into vanadium carbide(VC),which acts as a nucleation site for SWNT growth.Molecular dynamics simulations indicate that the energy at the SWNT-VC interface and the growth kinetics of SWNTs contribute to the chirality selectivity.This research opens up possibilities for the selective synthesis of SWNTs using cost-effective early transition metals,illuminating their future applications in fields such as bioimaging.
基金Project(2007CB613504)supported by the National Key Basic Research Program of ChinaProjects(51004033,50974035,51074047)supported by the National Natural Science Foundation of ChinaProject(2008BAB34B01)supported by National Science and Technology Support Plan of China during the 11th Five-Year Plan
文摘To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures ranging from 60 to 200 ℃ was obtained by recently published critically assessed standard Gibbs energies and activity coefficients of various species. When pH2, stable regions of V3＋, VO2＋ and VO2＋ exist in the stable region of TiO2. The pH values of stable regions of vanadium and titanium decrease and redox potentials become more positive with the temperature increasing. Vanadium and titanium could be separated by one-step leaching based on thermodynamics. The experiment results of pressure acid leaching of converter slag show that leaching rates of vanadium and titanium are 96.87% and 8.76% respectively, at 140 ℃ of temperature, 0.5 MPa of oxygen partial pressure, 0.055-0.075mm of particle size, 15：1 of liquid to solid ratio, 120 min of leaching time, 500 r/min of stirring speed and 200 g/L of initial acid concentration. Vanadium and titanium could be selectively separated in the pressure acid leaching process, and the experiment result is in agreement with thermodynamic calculation result.
基金financially supported by the High-degree Talent Introduction Program of Guangdong Academy of Sciences(No.2017GDASCX-0841)the Science and Technology Program of Guangzhou(No.201607020021)+2 种基金the National Natural Science Foundation of China(No.51304055)the Innovative Platform Construction Program of Guangdong Academy of Sciences(No.2017GDASCX-0109)the Pearl River Nova Program of Guangzhou(No.201806010016)
文摘The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.
基金financially supported by the National Basic Research Program of China(Nos.2013CB632601 and 2013CB632604)the National Science Foundation for Distinguished Young Scholars of China(Nos.51125018 and 51504230)+2 种基金the Key Research Program of Chinese Academy of Sciences(No.KGZD-EW-201-2)the National Natural Science Foundation of China(Nos.51374191 and 2110616751104139)China Postdoctoral Science Foundation(Nos.2012M510552 and 2013T60175)
基金the National High Technology Research and Development Program of China (Nos. 2012AA062302 and 2012AA062304)the Program of the National Natural Science Foundation of China (Nos. 51090384 and 51174051)The International Cooperation of the Ministry of Science and Technology of China (No. 2012DFR60210)
文摘To achieve high efficiency utilization of high-chromium vanadium-titanium magnetite （V-Ti-Cr） fines, an investigation of V Ti42r fines was conducted using a sinter pot. The chemical composition, particle parameters, and granulation of V-Ti-Cr mixtures were analyzed, and the effects of sintering parameters on the sintering behaviors were investigated. The results indicated that the optimum quicklime dosage, mixture moisture, wetting time, and granulation time for V-Ti-Cr fines are 5wt%, 7.5wt%, 10 min, and 5-8 min, respectively. Meanwhile, the vertical sintering speed, yield, tumbler strength, and productivity gains were shown to be 21.28 mm/min, 60.50wt% , 58.26wt%, and 1.36 t·m^-2·h^-1, respectively. Furthermore, the consolidation mechanism of V-Ti-Cr fines was clarified, revealing that the consolidation of a V-Ti-Cr sinter requires an approximately 14vo1% calcium ferrite liquid-state, an approximately 15vo1% silicate liq- uid-state, a solid-state reaction, and the recrystallization of magnetite. Compared to an ordinary sinter, calcium ferrite content in a V-Ti-Cr sinter is lower, while the perovskite content is higher, possibly resulting in unsatisfactory sinter outcomes.
基金Item Sponsored by National Key Technology Research and Development Program of China(2008BAB32B05)
文摘Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range from 1 473 to 1 673 K. The scanning electron microscope （SEM） was used to characterize the microstructure of product. By analyzing reduction mechanism, it was found that the rate controlling step was gas diffusion, and the activation energy was 178.39 kJ/mol without adding any catalysts. Adding CaF2 or NaF of 3% to vanadium titano-magnetite carbon composite pellets can decrease the apparent activation energy of reduction, and the decrease extent was 14.95 and 15.79 kJ/mol, respectively. In addition, temperature was an important factor influencing on reaction rate.
基金supported by the National Natural Science Foundation of China (20803093,20833011,20525621)the Doctor Select Foundation for the University of State Education Ministry (200804251016)+1 种基金the Beijing Outstanding Ph.D.Thesis Foundation (YB 20091141401)the Hi-Tech Research and Development Program (863) of China (SQ2009AA06Z3488052)
文摘The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratios:100V/Ce=0.1,1,4,10,and 20) were prepared by an incipient-wetness impregnation method.Spectroscopic techniques(XRD,FT-IR,Raman and UV-Vis DRS) were utilized to characterize the structures of VOx/CeO2 catalysts.The results showed that the structures of CeO2-supported vanadium oxide catalysts de...
基金financially supported by the National Key Technology Research and Development Program of the Ministry of Science and Technology of China (No. 2015BAB19B02)the National Program on Key Basic Research Project of China (No. 2013CB632603)
文摘The effect of diboron trioxide(B_2O_3) on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma–atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy–energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B_2O_3 content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B_2O_3 content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B_2O_3 content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B_2O_3. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B_2O_3 content.
基金financially supported by the Chinese National Programs for High Technology Research and Development(Nos.2010AA03A405 and 2012AA062303)the National Natural Science Foundation of China(Nos.U1202274,51004033,51204040,and 50974035)+2 种基金the National Science and Technology Support Program(No.2012BAE01B02)the Fundamental Research Funds for the Central Universities(No.N100302005)the Doctoral Fund Project(No.20120042110011)
文摘The process of pressure leaching the converter vanadium slag with waste titanium dioxide without roasting was studied. Mineralogy analysis indicates that the con- verter vanadium slag contains mainly three mineral phases： magnetite, titanium magnetite, and silicate phase. Vana- dium is in combination with iron, titanium, manganese, aluminum, and silicon. The impacts of leaching tempera- ture, leaching time, stirring speed, liquid-to-solid ratio, and initial leaching agent concentration were investigated on the waste titanium dioxide leaching process. The results indi- cate that under the optimal conditions, the vanadium and the iron leaching rates are 96.85 % and 93.50 %, respectively, and the content of titanium is 12.6 % in the residue. The main mineral phases for the residues under the optimal operation conditions are quartz, ilmenite, anatase, and sili- cate phase, and the residues can be reused as the extraction of titanium raw materials for titanium dioxide production technology by the sulfate method.
文摘The addition of distillation residues to the FCC feedstock leads to increased vanadiumloading on catalyst and the problems in catalyst deactivation.The deactivation process is related tothe destructive attack on the zeolite crystallite by V<sub>2</sub>O<sub>5</sub>.Formation of low melting pointV<sub>2</sub>O<sub>5</sub>-USY-Na<sub>2</sub>O phases accelerates the diffusion of vanadium through the catalyst.A proposedmechanism,based on accelerated dealumination,is shown in the paper.Comparative vanadiumtrapping performances have been tested for FCC catalysts and the crystalline ABO<sub>3</sub> as an effectivevanadium trap is demonstrated in laboratory tests.
基金partly supported by Grant-in-Aid for Scientific Research on Innovative Areas ("3D Active-Site Science", No. 26105003) from The Ministry of Education, Culture, Sports, Science and Technology (MEXT), JapanGrant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (JSPS, Nos. 15H03812, 18H01982)the Tokyo Metropolitan government (Tokyo Human Resources Fund for City Diplomacy) for pre-doctoral fellowship
文摘(Imido)vanadium(V)-alkylidene complexes of type V(CHSiMe3)(NR)(OR?)(PMe3)2 [R = Ad, C6H5, 2,6-Me2C6H3, 2,6-Cl2C6H3;R?= 2,6-Me2C6H3, 2,6-i Pr2C6H3, 2,6-F2C6H3, C6F5, C6Cl5] exhibited from moderate to remarkable catalytic activities for ringopening metathesis polymerization(ROMP) of norbornene(NBE). The catalytic activities were affected by the ligand substituents, and V(CHSiMe3)(N-2,6-Cl2C6H3)(OC6X5)(PMe3)2(X = F, Cl) demonstrated the exceptionally high catalytic activities for ROMP of NBE.The complexes polymerized cycloheptene(CHPE) and cis-cyclooctene(COE), and ROMP of COE by the OC6 Cl5 analogue proceeded in a living manner even at 80℃, and the activity increased with increasing the temperature up to 120 ℃. Highly active catalysts for ROMP of cyclic olefins(NBE, cyclopentene, and CHPE) can be generated in situ by premixing isolated V(CHSiMe3)(NC6F5)(O-2,6-iPr2C6H3)(PMe3)2 with 1.0 equiv. of C6F5OH or C6Cl5OH via immediate phenoxy exchange;the activity was affected by the kind of phenol added [TOF in the ROMPs of NBE: 4.62 × 10^4 min^–1(upon addition of C6F5OH) versus 37.3 min^–1(none)].
文摘The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis.According to the thermodynamic results,low-melting-point regions and MgTi2O5primary phase area in the phase diagrams,the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of50%TiO2,8%-12%MgO and13%Al2O3(mass fraction)with a binary basicity of0.8-1.2.Finally,the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained.The obtained vanadium-containing molten iron contains0.681%V and0.267%Ti,and the obtained titanium slag contains52.21%TiO2(mass fraction),in which MgTi2O5is the primary phase.The titanium resource in the final titanium slag production could be used to produce TiO2pigment by acid leaching methods.
基金financially supported by the Beijing Natural Science Foundation, China (No. 2192056)the National Natural Science Foundation of China (No. 51771179)+1 种基金the National Key R&D Program of China (No. 2018YFC1900505)The financial supports from the Youth Innovation Promotion Association CAS and the CAS Interdisciplinary Innovation Team
文摘Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction degree.The phase compositions of the reduced materials and the leached residues were analyzed by XRD to identify the effect of reduction degree on the leaching mechanisms.The results showed that the concentrates were reduced to iron metal and titanomagnetite at 800-1000°C for 0.5 h,and the above elements of Fe and impurities were easily leached.Deeper reduction led to the formation of ilmenite and Mg-Al spinel,which hindered leaching.Mg-bearing anosovite appeared in the further reduced materials,and the leaching rates of impurities became much lower.An upgraded titanium mineral with a normalized TiO_(2) grade of 70.3%was achieved by H_(2) reduction at 850°C for 0.5 h and acid leaching,which is a satisfactory Ti resource for the preparation of titanium oxide by sulfate process.
基金The project is supported by the National Natural Science Foundation of China (No.20176065)
文摘Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimalcondition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalyticactivity was up to 54.7% at 410℃, which was 2.2% higher than that of the Ls-8 catalyst. Only 10 minwas needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time.For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermalanalysis shifted to higher temperatures obviously, indicating that its crystal phase could melteasily. There existed an apparent endothermic peak at 283℃. SEM photographs showed a uniform sizedistribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form ofVOSO_4.
文摘Large quantities of spent hydrodesulfurization (HDS) catalysts are available from petrochemical industry. Disposal of spent catalyst is a problem as it falls under the category of hazardous industrial waste due to its vanadium concentration. Most of these catalysts are usually supported on alumina containing a variable percentage of elements such as nickel or molybdenum. Hence these catalysts contain environmentally critical, and economically valuable metals such as molyb denum, vanadium, and, nickel. In this paper, a spent HDS catalyst was treated with caustic soda solution. Parameters such as temperature, time, and NaOH solution concentration have been studied thoroughly, in order to settle the appropriate conditions for the maximum recovery of molybdenum and vanadium. Under the best leaching conditions (20 %w NaOH, room temperature, 2 h) about 95% recovery of Mo and V was achieved, and the recovery of nickel obtained was of 99% in the form of NiAlO4.
基金Project(20176065)supported by the National Natural Science Foundation of China.
文摘The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minutes were needed to produce obvious cavitations when thecatalyst raw material was treated in the 50 W ultrasonic generator. However, only 10 minutes wouldbe needed in a 150 W ultrasonic generator. The higher the temperature of the wet material, the lesstime was needed to produce cavitations, and the optimal temperature was 60℃. The water content inthe wet material mainly affected the quantity of cavitations. Ls-8 catalyst was prepared usingultrasonic. Its activity for conversion of SO_2 reached to 52.5% at 410℃ and 4.2% at 350℃. Thedifferential thermal analyses indicate that both endothermic peaks and exothermic peaks noticeablyshifted forward compared with Ls catalyst prepared without ultrasonic, and SEM results show auniform pore size distribution for Ls-8 catalyst.
