THE DESIGN OF VANADIUM TRAPPING SYSTEM FOR FCC CATALYSTS

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 V2O5.Formation of low melting pointV2O5-USY-Na2O 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 ABO3 as an effectivevanadium trap is demonstrated in laboratory tests.

Review on the latest developments in modified vanadium-titanium-based SCR catalysts

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.

Calcified roasting-acid leaching process of vanadium from low-grade vanadium-containing stone coal

The low-grade vanadium-containing stone coal used in this experiment was collected from Wuxi Country, Chongqing City, China. The experiment focused on the vanadium recovery from roasted residue through optimizing the process conditions of an effective and environmentally-friendly technology, named calcified roasting-sulfuric acid leaching technology. By single-factor experiments and orthogonal experiments, the effects of roasting temperature, roasting time, sulfuric acid concentration and leaching time on the leaching ratio of vanadium were analyzed. The results showed that the leaching ratio of vanadium reached 85.5% under the proper technological conditions of roasting temperature=950℃, roasting time=4 h, 40% concentration of sulfuric acid and leaching time=6 h.

Activity Enhancement of Vanadium Catalysts with Ultrasonic Preparation Process for the Oxidation of Sulfur Dioxide

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.

Amine-functionalized boehmite nanoparticle-supported molybdenum and vanadium complexes:Efficient catalysts for epoxidation of alkenes

Boehmite nanoparticles with a high surface area and a high degree of surface hydroxyl groups were covalently functionalized by 3‐（trimethoxysilyl）‐propylamine to support vanadium‐oxo‐sulfate and molybdenum hexacarbonyl complexes. These supported catalysts were then characterized by Fou‐rier‐transform infrared spectroscopy, powder X‐ray diffraction, thermogravimetry and differential thermal analysis, X‐ray‐photoelectron spectroscopy, elemental analysis, inductively coupled plasma, and transmission electron microscopy techniques. The catalysts were subsequently used for the epoxidation of cis‐cyclooctene, and the experimental procedures were optimized. The progress of the reactions was investigated by gas‐liquid chromatography. Recycling experiments revealed that these nanocatalysts could be repeatedly used several times for a nearly complete epoxidation of cis‐cyclooctene. The optimized experimental conditions were also used successfully for the epoxida‐tion of some other substituted alkenes.

Effect of cooling rate on morphology and type of vanadium-containing phases in Al-10V master alloy

Effects of cooling rates on the morphology, sizes and species of primary vanadium-containing phases in Al-10V master alloys were investigated. The results show that the primary vanadium-containing phases with different morphologies and compositions present in Al-10V master alloys at different cooling rates with the pouring temperature of 1,170 °C. When the Al-10V master alloy is solidified in the refractory mold at a cooling rate of 2 °C·s-1, the vanadium-containing phases are mainly plate-like Al10V phases, with the average size of 100.0 μm in the center and 93.2 μm at the edge of the ingot. When the master alloy is solidified in the graphite mold at a cooling rate of 24.3 °C·s-1, the primary vanadium-containing phases are dendritic Al3V phases, with the average length of 297.0 μm for the first dendrite in the center and 275.0 μm at the edge of the ingot. The secondary dendrite arm spacing (SDAS) is 9.5 μm in the center and 9.3 μm at the edge of the ingot, respectively. When the solidification is carried out in the copper mould at a cooling rate of 45.7 °C·s-1, the primary vanadium-containing phases are also Al3V phases but with smaller size, compared with that prepared at the cooling rate of 24.3 °C·s-1. As a result, the average length is 190.0 μm for the first dendrite in the center and 150.0 μm at the edge of the ingot. The SDAS is 9.8 μm in the center and 4.4 μm at the edge of the ingot, respectively.

Influence of Coke Content on Sintering Process of Chromium-containing Vanadium-titanium Magnetite

The sintering of chromium-containing vanadium-titanium magnetite using different coke contents was studied through the sintering pot tests, X-ray diffraction analysis and mineralogical phase analysis. Results showed that, as the coke content increased from 3.2% to 4.4%, the liquid phase and combustion zone thickness increased while the vertical sintering rate and ratio of sintered product decreased. In addition, the combustion ratio of exhaust gas also increased with increasing the coke content, indicating that combustion zone temperature also increased, and the excessive the coke content in the sintering process of vanadiumtitanium magnetite is harmful. As the coke content increased, the magnetite, silicates, and perovskite contents of the sintered ore increased while the contents of hematite and calcium ferrite of sintered ore decreased; drum strength decreased, and reduction degradation properties increased while reduction ability decreased. We found that the appropriate coke content for the sintering process is 3.6 wt%.

Reduction of Sulphur-containing Aromatic Nitro Compounds with Hydrazine Hydrate over Iron(III) Oxide-MgO Catalyst

Sulphur-containing aromatic amines were prepared efficiently in good to excellent yields by reduction of the corresponding sulphur-containing aromatic nitro compounds with hydrazine hydrate in the presence of iron（Ⅲ） oxide-MgO catalyst. The catalyst exhibited high activity and stability for the reduction of sulphur-containing aromatic nitro compounds. The yields of sulphur-containing aromatic amines were up to 91-99 % at 355 K after reduction for 1-4 h over this catalyst.

Preparation of Sulphur-containing Aromatic Amines by Reduction of the Corresponding Aromatic Nitro Compounds with Hydrazine Hydrate over Iron Oxide Hydroxide Catalyst

Sulphur-containing aromatic nitro compounds were rapidly reduced to the corresponding amines in high yields by employing hydrazine hydrate as a hydrogen donor in the presence of iron oxide hydroxide catalyst. It was worth noting that the catalyst exhibited extremely high activity. The reduction could be completed within 20-50 min and the yields were up to 97-99 %.

HYDROXYLATION OF BENZENE BY HETEROPOLY ACIDS(SALTS)CONTAINING VANADIUM

Direct hydroxylation of benzene catalyzed by vanadium-con- taining heteropoly compounds with Keggin or Dawson structure has been investigated.The effects of several factors upon the hydroxylation reaction have also been examined.It is indicated that the highest yield of phenol reached 76%(based on H_2O_(?))with 99.4～100% selectivity.

Recovery of vanadium and molybdenum from spent petrochemical catalyst by microwave-assisted leaching

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.

Promoted catalytic performances of highly dispersed V-doped SBA-16 catalysts for oxidative dehydrogenation of ethane to ethylene

V-doped SBA-16 catalysts (V-SBA-16) with 3D nanocage mesopores have been successfully synthesized by a modified one-pot method under weak acid condition. The obtained materials were characterized by means of small angle XRD, N2adsorption–desorption, TEM, UV–Vis and UV-Raman spectroscopy. These characterization results indicated that well-order mesoporous structures were maintained even at higher vanadium loadings and high concentration of VOxspecies were incorporated into the framework of SBA-16 support. The catalytic performances of V-SBA-16, V/SBA-16 and V/SiO2catalysts were comparatively investigated for the oxidative dehydrogenation of ethane to ethylene. The highest selectivity to ethylene of 63.3% and ethylene yield of 25.6% were obtained over 1.0V-SBA-16 catalyst. The superior catalytic performance of V-SBA-16 catalysts could be attributed to the presence of isolated framework VOxspecies, the unique structure of SBA-16 support and weak acidity. Moreover, V/SiO2catalyst exhibited relatively poor catalytic activity duo to the formation of V2O5nanoparticles on the surface of SiO2support and the low dispersion of VOxspecies. These results indicated that the catalytic performances of the studied catalysts were strongly dependent on the vanadium loading, the nature and neighboring environment of VOxspecies and the structure of support. © 2016

Enhancement in Activity of a Vanadium Catalyst for the Oxidation of Sulfur Dioxide by Radio Frequency Plasma During the Preparation Process

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.

Chemical Treatment to Recover Molybdenum and Vanadium from Spent Heavy Gasoil Hydrodesulfurization Catalyst

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.

SUPPORTED ZIEGLER-NATTA CATALYSTS FOR ETHYLENE SLURRY POLYMERIZATION AND CONTROL OF MOLECULAR WEIGHT DISTRIBUTION OF POLYETHYLENE

The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-supported catalyst affect of MWD of PE produced in broad range:Vanadium-magnesium catalyst(VMC)produce PE with broad and bimodal MWD(M_w/M_n=14-21).MWD of PE,produced over titanium-magnesium catalyst(TMC)is narrow or medium depending on Ti content in the catalyst(M_w/M_n=3.1-4.8).The oxidation ...

Mass Spectrometric Studies of Selective Oxidation of n-Butane over a Vanadium Phosphorus Oxide Catalyst

The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.

Effects of Vanadium Oxidation Number on Light Olefins Selectivity of FCC Catalyst

Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.

Influence of TiO2 on the melting property and viscosity of Cr-containing high-Ti melting slag

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag(CaO–SiO2–MgO–Al2O3–TiO2–Cr2O3) with TiO2 contents ranging from 38.63 wt% to 42.63 wt% was conducted. The melting properties were investigated with a meltingpoint apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy(SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO2 content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO2 content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO2 content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO2.

Effect of Sr loading on oxydehydrogenation of propane to propylene over Al_2O_3-supported V-Mo catalysts

Incorporation of strontium into V-Mo alumina-supported catalyst enhanced its performance (increased conversion and selectivity,decreased reducibility and improved stability) in propane oxydehydrogenation to propylene.12.5% Sr loading was shown to be the optimum content to the V-Mo catalyst.The results were supported by various characterization techniques,namely,BET,XRD,SEM,FTIR and TPD.

Purified oxygenand nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen and nitrogen-functionalized carbon nanotubes （OCNTs and NCNTs） were applied as metal-free catalysts in selective olefin hydro- genation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 ℃ led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.