Promotional Effect of Bismuth as Dopant in Bi-Doped Vanadyl Pyrophosphate Catalysts for Selective Oxidation of n-Butane to Maleic Anhydride

Bismuth-promoted （1% and 3%） vanadyl pyrophosphate catalysts were prepared by refluxing Bi（NO3）4.5H2O and VOPO4.2H2O in isobutanol. The incorporation of Bi into the catalysts lattice increased the surface area and lowered the overall V oxidation state. Profiles of temperature programmed reduction （TPR） in H2 show a significant shift of the maxima of major reduction peaks to lower temperatures for the Bi-promoted catalysts. A new peak was also observed at the low temperature region for the catalyst with 3% of Bi dopant. The addition of Bi also increased the total amount of oxygen removed from the catalysts. The reduction pattern and reactivity information provide fundamental insight into the catalytic properties of the catalysts. Bi-promoted catalysts were found to be highly active （71% and 81% conversion for 1% and 3% Bi promoted catalysts, respectively, at 703 K）, as compared to the unpromoted material （47% conversion）. The higher activity of the Bi-promoted catalysts is due to that these catalysts possess highly active and labile lattice oxygen. The better catalytic performance can also be attributed to the larger surface area.

Dehydrogenation of n-butane over vanadia catalysts supported on silica gel

VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction, FT-IR, UV-vis, Raman, and BET measurements. The effects of VOx loading and the reaction temperature on the VOx/SiO2 catalysts and their catalytic performances for the dehydrogenation of n-butane were studied. When the VOx loading was 12% g/gcat and reaction temperature was between 590 ℃ and 600℃, n-butane conversion and butenes yields reached the highest value under H2 flux of 10 ml/min and n-butane flux of 10 ml/min. Product distribution, such as the ratio of 2-butene to 1-butene and the ratio of cis-2-butene to trans-2-butene, was mainly influenced by the reaction temperature.

Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane

The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature （excluding 800 ℃）. The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.

Effect of Cr and Co Promoters Addition on Vanadium Phosphate Catalysts for Mild Oxidation of n-Butane

In this study, Cr and Co promoted, as well as unpromoted vanadium phosphate （VPO） catalysts were synthesized by the reaction of V2O5 and o-H3PO4 in organic medium followed by calcination in n-butane/air environment at 673 K. The physico-chemical properties and the catalytic behavior were affected by the addition of Cr and Co dopants. H2-TPR was used to investigate the nature of oxidants in the unpromoted and promoted catalysts. The results showed that both the Cr and Co promoters remarkably lowered the temperature of the reduction peak associated with V^5＋. The amount of oxygen species originated from the active phase, V^4＋, removed was significantly increased for Co and Cr-promoted catalysts. Both Cr and Co dopants improve strongly the n-butane conversion without sacrificing the MA selectivity. A good correlation was observed between the amount of oxygen species removed from V^4＋ phase and the activity for n-butane oxidation to maleic anhydride. This suggested that V^4＋-O was the center for the activation of n-butane.

n-Butane Oxidation over γ-Al_2O_3 Supported Vanadium Phosphate Catalysts

Four vanadium phosphate catalysts supported on γ-A1203 （20 wt%） were synthesized via wetness impregnation of VOHPO4.0.5H2O precursor and calcined for different durations （6, 10, 30 and 75 h） at 673 K in a reaction flow of n-butane/air mixture. The samples calcined for 6 and 10 h produced only a single phase of （VO）2P2O7. However, the VOPO4 phase （β-VOPO4） was detected and became more prominent with only a minor pyrophosphate peaks were found after 30 h of calcination. All these pyrophosphate peaks disappeared after 75 h of calcination. The formation of V^5＋ phase was also observed in the SEM micrographs. The redox properties and the nature of oxidants of the catalysts employed in this study were investigated by H2-TPR analysis. Selective oxidation of n-butane to maleic anhydride （MA） over these catalysts shows that the percentage of n-butane conversion decreases with the transformation of the catalysts from V^4＋ to V^5＋ phases. An appropriate ratio of V^5＋/V^4＋ can enhance the performance of the VPO catalyst. However, a higher amount of V^5＋ and its associated oxygen species are responsible to promote the MA selectivity.

Phosphate modified carbon nanotubes for oxidative dehydrogenation of n-butane

Catalytic performance of phosphate-modified carbon nanotube（PoCNT） catalysts for oxidative dehydrogenation（ODH） of n-butane has been systematically investigated. The Po CNT catalysts are characterized by SEM, TEM, XPS and TG techniques. We set the products selectivity as a function of butane conversion over various phosphate loading, and it is found that the PoCNT catalyst with the 0.8% phosphate weight loading（0.8PoCNT） exhibits the best catalytic performance. When the phosphate loading is higher than 0.8 wt%, the difference of catalytic activity among the PoCNT catalysts is neglectable. Consequently, the ODH of n-butane over the 0.8PoCNT catalyst is particularly discussed via changing the reaction conditions including reaction temperatures, residence time and n-butane/O;ratios. The interacting mechanism of phosphate with the oxygen functional groups on the CNT surface is also proposed.

Progress of vanadium phosphorous oxide catalyst for n-butane selective oxidation

The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO_(2)emission.Particularly,n-butane has gained special attention across the globe due to the abundant production of maleic anhydride(MA).Vanadium phosphorous oxide(VPO)is the most effective catalyst for selective oxidation of n-butane to MA so far.Interestingly,the VPO complex exists in more or less fifteen different structures,each one having distinct phase composition and exclusive surface morphology and physiochemical properties such as valence state,lattice oxygen,acidity etc.,which relies on precursor preparation method and the activation conditions of catalysts.The catalytic performance of VPO catalyst is improved by adding different promoters or co-catalyst such as various metals dopants,or either introducing template or structural-directing agents.Meanwhile,new preparation strategies such as electrospinning,ball milling,hydrothermal,barothermal,ultrasound,microwave irradiation,calcination,sol-gel method and solvothermal synthesis are also employed for introducing improvement in catalytic performance.Research in above-mentioned different aspects will be ascribed in current review in addition to summarizing overall catalysis activity and final yield.To analyze the performance of the catalytic precursor,the reaction mechanism and reaction kinetics both are discussed in this review to help clarify the key issues such as strong exothermic reaction,phosphorus supplement,water supplement,deactivation,and air/n-butane pretreatment etc.related to the various industrial applications of VPO.

Catalytic Performance of Bare Supporters and Supported KVO_3 Catalysts for Cracking n-Butane to Produce Light Olefins

Supported KVO3 catalysts were prepared by impregnating different kinds of supporters (α-Al2O3, γ-Al2O3 and SiO2 powders) with a KVO3 solution. The activity of the bare supporters and supported catalysts were evaluated in a continuous micro-reactivity test unit, with n-butane as a raw material. The results show that KVO3 has no catalytic activity, but it can increase the selectivity to light olefins. The supporter of α-Al2O3 has good catalytic performance for n-butane cracking when the reaction temperature is below 700℃.

The Effect of Sulfate Ion on the Isomerization of n-Butane to iso-Butane

The effect of sulfate ion （SO4^2-） loading on the properties of Pt/SO4^2-ZrO2 and on the catalytic isomerization of n-butane to/so-butane was studied. The catalyst was prepared by impregnation of Zr（OH）4 with H2SO4 and platinum solution followed by calcination at 600 ℃. Ammonia TPD and FT-IR were used to confirm the distribution of acid sites and the structure of the sulfate species. Nitrogen physisorption and X-ray diffraction were used to confirm the physical structures of Pt/SO4^2-ZrO2. XRD pattern showed that the presence of sulfate ion stabilized the metastable tetragonal phase of zirconia and hindered the transition of amorphous phase to monoclinic phase of zirconia. Ammonia TPD profiles indicated the distributions of weak and medium acid sites observed on 0.1 N and 1.0 N sulfate in the loaded catalysts. The addition of 2.0 N and 4.0 N sulfate ion generated strong acid site and decreased the weak and medium acid sites. However, the XRD results and the specific surface area of the catalysts indicated that the excessive amount of sulfate ion collapsed the structure of the catalyst. The catalysts showed high activity and stability for isomerization of n-butane to iso-butane at 200 ℃ under hydrogen atmosphere. The conversion of n-butane to iso-butane per specific surface area of the catalyst increased with the increasing amount of sulfate ion owing to the existence of the bidentate sulfate and/or polynucleic sulfate species （（ZrO）2SO2）, which acts as an active site for the isomerization.

A Novel Way to Prepareγ-A1_2O_3 Supported SO_4^(2-)/ZrO_2 Solid Superacid Catalysts for n-Butane Isomerization

Highly active solid superacid catalysts for n-butane isomerization, SZ/A1_2O_3-P, were prepared by supporting SO-(4-2)/ZrO2, (SZ) on y-A1_2O_3 carrier using a precipitation method. The activities of some catalysts were enhanced significantly j The activity of the most active sample. 60%SZ/Al_2O3-P, was even about 2 times more active than that of the SZ catalyst.

Evaluation of yields and quality parameters of oils from Cornus wilsoniana fruit extracted by subcritical n-butane extraction and conventional methods

Cornus wilsoniana fruit oil is a very important woody oil and is the main raw material of biodiesel.In this study,the oil yield,physicochemical properties,fatty acid composition,rheological properties,thermal stability,and Fourier transform infrared(FTIR)spectra of C.wilsoniana fruit oil obtained by subcritical n-butane extraction(SBE)and conventional methods such as pressing extraction(PE)and Soxhlet extraction(SE)were determined to study the influence of different extraction methods on the quality and yield of C.wilsoniana fruit oil.The oil yield of SBE(19.47%)was higher than that of PE(9.93%)but slightly lower than that of SE(21.08%).All of the extracted oils exhibited similar physicochemical properties,and the SBE oil was richer in polyunsaturated fatty acids(PUFA)than that of the PE oil,with an approximate 1:2 ratio of total saturated fatty acids against unsaturated fatty acids.The results of rheological behavior and thermal stability showed that all extracted oils had Newtonian flow characteristics,wherein the SBE oil exhibited lower viscosity and higher thermal stability.Furthermore,scanning electron microscopy(SEM)images of the surface topography indicated that different oil extraction methods will affect the residual oil content of the C.wilsoniana fruit powder.Compared with PE,the pores on the surface of the C.wilsoniana fruit powder after oil extraction were clearly visible,indicating that the driving force of SBE for oil extraction is stronger than that of PE.Based on the above results,it is implied that SBE is the best of the three methods for extracting C.wilsoniana fruit oil and can be potentially applied to extract other edible oils.

Development of the ignition delay prediction model of n-butane/hydrogen mixtures based on artificial neural network

Based on the experimental ignition delay results of n-butane/hydrogen mixtures in a rapid compression machine,a Genetic Algorithm(GA)optimized Back Propagation(BP)neural network model is originally developed for ignition delay prediction.In the BP model,the activation function,learning rate and the neurons number in the hidden layer are optimized,respectively.The prediction ability of the BP model is validated in wide operating ranges,i.e.,compression pressures from 20 to 25 bar,compression temperatures from 722 to 987 K,equivalence ratios from 0.5 to 1.5 and molar ratios of hydrogen(X_(H2))from 0 to 75%.Compared with the BP model,the GA optimized BP model could increase the average correlation coefficient from 0.9745 to 0.9890,in the opposite,the average Mean Square Error(MSE)decreased from 2.21 to 1.06.On the other hand,to assess the BP-GA model prediction ability in the never-seen-before cases,a limited BP-GA model is fostered in the𝑋X_(H2) range from 0 to 50%to predict the ignition delays at the cases of𝑋X_(H2)=75%.It is found that the predicted ignition delays are underestimated due to the training dataset lacking of“acceleration feature”that happened at𝑋X_(H2)=75%.However,three possible options are reported to improve the prediction accuracy in such never-seen-before cases.

Application of butane geochemistry of natural gas in hydrocarbon exploration

In order to distinguish the source and migration direction of natural gas by geochemical characteristics of butane,the components and carbon isotopes of natural gas from major hydrocarbonbearing basins in China were analyzed.The results showed that：（1） Oil-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -28‰,δ 13 C i-butane -27‰,δ 13 C n-butane -28.5‰,whereas coal-type gas has i-C 4 /n-C 4 0.8,δ 13 C butane -25.5‰,δ 13 C i-butane -24‰,δ 13 C n-butane -26‰.（2） When δ 13 C i-butane-δ 13 C n-butane is greater than 0,the maturity of oil-type gas is generally more than 2.4% and that of coal-type gas is greater than 1.4%,whereas when the difference is less than 0,the maturity of oil-type gas is generally less than 1.1% and that of coal-type gas is less than 0.8%.（3） When natural gas migrates through dense cap rocks,the value of i-C 4 /n-C 4 increases,whereas when it migrates laterally along a reservoir,the value of i-C 4 /n-C 4 decreases.（4） Sapropelic transition zone gas with composition and carbon isotopic signatures similar to those of oil-type gas in the low thermal evolution stage is found to have a relatively high butane content.（5） The values of i-C 4 /n-C 4 and δ 13 C n-butane δ 13 C i-butane of gas which has suffered biological degradation are significantly higher than those obtained from thermogenic and bio-thermocatalytic transition zone gas.Thus,natural gas of different genetic types can be recognized through component analysis and carbon isotopic signatures of butane,the natural gas maturity can be estimated from the difference in carbon isotopic content between isobutane and n-butane,and the migration direction of natural gas can be determined from i-C 4 /n-C 4 ratios and transport conditions,which can also be used to thermogenic and bio-thermocatalytic transition zone gas.

Effect of Rare Earth Additives on the Catalytic Property ofVanadium－Phosphorus Catalyst

Phase composition and surface characterization of vanadium-phosphorus catalysts containing rare earth elements were investigated by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), NH3-temperature programmed desorption (NH3-TPD) and so on. The catalysts were used for the selective oxidation of n-butane to maleic anhydride. Catalytic performance has been carried out in a fixed-bed reactor. Experimental results showed that yield of maleic anhydride was enhanced by 4%～15% over vanadium-phosphorus catalysts by the addition of rare earth elements. Rare earth elements as promotors played the role of increasing surface acidity of the catalysts.

^(31)P solid-state NMR spectroscopy of VPO catalysts

VPO are well-known catalysts for the oxidation of n-butane to maleic anhydride. The catalytic behavior is influenced by several factors, such as the phase composition and the vanadium oxidation state of VPO catalysts. These catalysts have been characterized by means of XRD and XPS, but it is difficult to detect the presence of low concentrations of VOPO4 phases