Oxidative Dehydrogenation Of Butane Research Articles

Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene Over Metal Ferrite Catalysts

The oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene was studied over a series of AFe2O4 catalysts, where A = Zn, Mn, Ni, Cu, Mg and Fe. The catalysts were characterised by XPS, EPR spectroscopy, BET surface area analysis, Raman spectroscopy and XRD. All the ferrites were active for ODH and gave an order of activity after 80 h on-stream of ZnFe2O4 > NiFe2O4 > MnFe2O4 > MgFe2O4 > CuFe2O4 > FeFe2O4. All catalysts lost significant surface area (up to ~ 80%) under reaction conditions of 0.75:1:15 oxygen:1-butene:steam with an overall GHSV of 10,050 h−1 at 693 K. Fe3O4 was unstable under reaction conditions and was converted to Fe2O3, which showed very low activity. Nickel ferrite was the only material that gave carbon dioxide as a significant product, all others were selective to 1,3-butadiene. Zinc ferrite gave a steady-state yield of 1,3-butadiene of ~ 80%. Inversion parameters were determined for the ferrites from XPS and a correlation was obtained between 1,3-butadiene yield and inversion parameter, indicating that Fe3+ in an octahedral hole is a key species in the mechanism of oxidative dehydrogenation. Butene isomerisation and ODH were shown to occur on different sites.

Cooling effects of different molten salts and tube diameters on the performance of chemical reactors using butadiene synthesis as a case study

Many industrial applications adopt solar salt as the go-to heat transfer fluid for both cooling and thermal storage systems. However, the high melting temperature of this salt makes it economically unattractive. Hence, in this study, the investigation of 12 different molten salts was carried out to provide the right decision basis for selecting suitable salts for both cooling and thermal storage applications. In light of this, we developed a computational fluid dynamics (CFD) model to simulate butadiene synthesis via the oxidative dehydrogenation of butene in a single tube reactor equipped with a cooling jacket. The CFD model was validated against experimental results with an average error of 3.5%. Parametric studies involving the different salts indicated that low melting point salts resulted in high heat removal efficiencies but reduced the overall conversion, yield, and selectivity of the reactor due to the lower reaction temperatures. Thermophysical properties such as specific heat capacities were found to have no significant impact on the cooling efficiency of the reactor. An economic evaluation of the salts based on their heating costs indicated that salts of LiNaKCsCaNO3 and NaKCaNO3 are most suitable, especially for thermal storage systems where only latent heat of fusion is required. However, in cases where further heating of the salt is needed, higher melting point salts (such as solar salt) proved to be much more economical. Investigation of the effect of different tube diameters on the cooling performance of the reactor indicated that reactors having a diameter to length ratio between 32 and 58 provide sufficient cooling and high conversion.

3-D Multi-Tubular Reactor Model Development for the Oxidative Dehydrogenation of Butene to 1,3-Butadiene

The oxidative dehydrogenation (ODH) of butene has been recently developed as a viable alternative for the synthesis of 1,3-butadiene due to its advantages over other conventional methods. Various catalytic reactors for this process have been previously studied, albeit with a focus on lab-scale design. In this study, a multi-tubular reactor model for the butadiene synthesis via ODH of butene was developed using computational fluid dynamics (CFD). For this, the 3D multi-tubular model, which combines complex reaction kinetics with a shell-side coolant fluid over a series of individual reactor tubes, was generated using OpenFOAM®. Then, the developed model was validated and analyzed with the experimental results, which gave a maximum error of 7.5%. Finally, parametric studies were conducted to evaluate the effect of thermodynamic conditions (isothermal, non-isothermal and adiabatic), feed temperature, and gas velocity on reactor performance. The results showed the formation of a hotspot at the reactor exit, which necessitates an efficient temperature control at that section of the reactor. It was also found that as the temperature increased, the conversion and yield increased whilst the selectivity decreased. The converse was found for increasing velocities.

Oxygen exchange in Bi2MoO6 nanosheets with different thicknesses during oxidative dehydrogenation of 1-butene

A series of Bi2MoO6 nanosheet catalysts with different thicknesses were synthesized for oxidative dehydrogenation (ODH) of 1-butene and the oxygen exchange process during ODH was clarified.

Closing the balance by the CLOBAL procedure: Towards more accurate concentration, conversion and selectivity values

In continuous flow reactor analyses, the experimentally obtained molar flow rates of unreacted reactants and formed products are called useful if the corresponding atom balances are closed, i.e., within 90–110%. This manuscript (1) shows that even for the validity condition of a balance between 95% and 105%, deviations for conversion and selectivity can be very pronounced and (2) offers, likewise, a very simple a posteriori calculation procedure to address these deviations. To validate the proposed procedure, called ‘CLOBAL’ – after ‘closing the balances’, an example from butane oxidative dehydrogenation (ODH) is taken and it is clearly shown that the CLOBAL method gives values for conversion and selectivity, closest to the ‘real’ values, compared to the conventional methods, i.e., without correction.As an example of batch reactor operation, the aldol condensation towards jasmine aldehyde is taken to show that the application of the presented CLOBAL procedure gives corrected concentrations values which result in more accurate kinetic parameter estimates with a lower residual sum of squares.

Effect of Excess Iron on Oxidative Dehydrogenation of 1-Butene over a Series of Zinc Ferrite Catalysts

The influence of excess Fe3+ in ZnFe2O4 for the catalytic oxidative dehydrogenation of 1-butene to 1, 3-butadiene was investigated to try to clarify inconsistencies in the existing literature. A series of nanoscale zinc ferrite powders were produced with increasing Fe: Zn ratios. The materials were characterized by a range of techniques, which showed the presence of α-Fe2O3 as a distinct phase with an increasing excess of Fe3+ and SEM highlighted the increased presence of surface structures on the ferrites at higher Fe: Zn ratios. Reaction testing showed α-Fe2O3to be virtually inactive for the oxidative dehydrogenation of 1-butene. Results for the ferrite catalysts showed a significant decrease in both conversion and yield with an increasing excess of Fe3+. Therefore an excess of Fe3+ has a negative effect on catalytic activity and selectivity of zinc ferrite for the oxidative dehydrogenation of 1-butene, but acts as a promoter for competing hydrogenation and combustion side reactions.

Preparation of Foam Structured Catalyst ZnFe2O4-α-Fe2O3/SiC and its Performance in Oxidative Dehydrogenation of Butene

Preparation of Foam Structured Catalyst ZnFe2O4-α-Fe2O3/SiC and its Performance in Oxidative Dehydrogenation of Butene

Bimetallic Bi‐Ni oxides over carbide supports for oxidative dehydrogenation of n‐butane: Experimental and kinetic modelling

Abstractn‐butane oxidative dehydrogenation was studied over Bi‐Ni/TiC, Bi‐Ni/SiC, Bi‐Ni/Silicalite‐1, and unsupported Bi‐Ni catalyst. The co‐impregnation technique was followed, with fixed 0.30 and 0.20 g/g for Bi and Ni respectively. The physico‐chemical properties were measured by means of BET, XRD, CO2/NH3‐TPD, and H2‐TPR techniques. The catalytic test results revealed that bimetallic Bi‐Ni/TiC catalyst exhibited the highest n‐butane conversion of 16.6 % with dehydrogenation selectivity of 83.7 % (1,3‐butadiene and butenes selectivity of 50.7 % and 33 % respectively). As regards Bi‐Ni/TiC catalyst, the main operating parameters including O2/n‐C4H10 feed ratio, space velocity, and reaction temperature were varied. The Bi‐Ni/TiC catalyst showed adequate stability for a 10 h time on stream test. The high performance of Bi‐Ni‐O/TiC catalyst is attributed to the synergistic role of reducibility, presence of strong basic sites and weak acidic sites, and an increased metal species dispersion over the TiC support. A kinetic study of n‐butane oxidative dehydrogenation was carried out. The apparent activation energy for formation of butadiene was estimated to be the lowest (15 kJ/mol), while the highest activation energy (105 kJ/mol) is required for the undesirable cracking reaction.

Catalytic oxidative dehydrogenation of 1-butene to 1,3-butadiene with CO2 over Fe2O3/γ-Al2O3 catalysts: the effect of acid or alkali modification

Fe2O3/γ-Al2O3 catalysts were modified by acid and alkali (H2SO4, LiOH, NaOH and KOH) and were investigated for 1,3-butadiene (BD) synthesis through the oxidative dehydrogenation of 1-butene with CO2. Nitrogen sorption and XRD results revealed that physical and original crystalline structure of Fe2O3/γ-Al2O3 catalysts remained intact after the modification. The acidity and alkalinity of the catalysts were determined quantitatively and qualitatively by NH3-TPD and CO2-TPD, respectively. The sequence of catalyst activity for these five catalysts was: Li–Fe2O3/γ-Al2O3 > S–Fe2O3/γ-Al2O3 > Fe2O3/γ-Al2O3 > K–Fe2O3/γ-Al2O3 > Na–Fe2O3/γ-Al2O3. The catalytic activity (BD rate) of Fe2O3/γ-Al2O3 catalysts was improved ~41% after the modification of LiOH. Results indicated that too little amount of acid sites as well as the strong basic sites over catalyst surface were not facilitate to the formation of BD. TG characterization results illustrated that the coke resistant ability of the catalysts was enhanced with the catalyst alkalinity.

Effect of oxygen adsorption on the electrical conductivity of semiconducting nickel–iron oxide catalyst with spinel structure

Nickel–iron oxide catalyst semiconductor with spinel structure is synthesized from oxalates. Oxygen adsorption and its effect on the catalyst’s electrical conductivity in the temperature range of 353–693 K and the ferromagnetic state are studied. The presence of durable and reversible form of adsorbed oxygen is detected. It is established that the resistivity of samples and their activation energy depend on the type of adsorption and the temperature. Strongly adsorbed atomic oxygen is charged negatively and can participate in the reaction of oxidative dehydrogenation of butene-1.

Production of butene and butadiene by oxidative dehydrogenation of butane over carbon nanomaterial catalysts

C4 alkenes are generally used to produce synthetic rubbers, plastics, and other important chemicals. Transition metal oxides are traditionally used as catalysts to produce C4 alkenes from n-butane by oxidative dehydrogenation (ODH). On the other hand, metal-free carbon nanomaterials are receiving much attention as catalysts for ODH due to their environmental benignity, corrosion resistance, and unique surface properties. In this work, a systematic methodology was designed to measure conversion of the reactants, selectivity to main products, and other catalytic performances of a set of carbon catalysts, including graphite and activated carbon. The experiments were carried out under a wide range of reaction conditions, and the reaction mechanism and kinetics were developed based on Marsvan Krevelen interpretation of the experimental results.

Europium oxide containing catalysts for oxidative dehydrogenation of alkanes

A method is developed to incorporate europium into Mg–Al hydrotalcites, which are precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes; samples of oxide catalysts are prepared, where europium oxide and gallium, magnesium, aluminum, chromium, vanadium, molybdenum, and niobium oxides are contained in various combinations. The catalytic properties of these catalysts in the reactions of ethane, propane, and butane ODH are studied. The incorporation of europium into some of our studied multicomponent catalysts enhances the reaction selectivity and increases yields of desired products.

Oxidative dehydrogenation of butenes over Bi‐Mo and Mo‐V based catalysts in a two‐zone fluidized bed reactor

The oxidative dehydrogenation of a 1‐butene/trans‐butene (1:1) mixture to 1,3‐butadiene was carried out in a two‐zone fluidized bed reactor using a Mo‐V‐MgO and a γ‐Bi2MoO6 catalyst. The significant operating conditions temperature, oxygen/butene molar ratio, butene inlet height, and flow velocity were varied to gain high 1,3‐butadiene selectivity and yield. Furthermore, axial concentration profiles were measured inside the fluidized bed to gain insight into the reaction network in the two zones. For optimized conditions and with a suitable catalyst, the two‐zone fluidized bed reactor makes catalyst regeneration and catalytic reaction possible in a single vessel. In the lower part of the fluidized bed, the oxidation of coke deposits on the catalyst as well as the filling of oxygen vacancies in the lattice can occur. The oxidative dehydrogenation reaction takes place in the upper zone. Thorough particle mixing inside fluidized beds causes permanent particle exchange between both zones. © 2016 American Institute of Chemical Engineers AIChE J, 63: 43–50, 2017

Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts.

銅フェライト触媒を用いる1-ブテンの酸化的脱水素反応－アンモニア処理の影響－

銅フェライト触媒を用いる1-ブテンの酸化的脱水素反応－アンモニア処理の影響－

V-Mg複合酸化物触媒を用いる1-ブテンの酸化的脱水素反応－鉄の添加効果－

V-Mg複合酸化物触媒を用いる1-ブテンの酸化的脱水素反応－鉄の添加効果－

Magnesium oxide as a heterogeneous catalyst support

AbstractResearchers normally consider MgO as a promising high-surface-area heterogeneous catalyst support, additive, and promoter for many kinds of chemical reactions due to its certain properties, including stoichiometry and composition, cation valence, redox properties, acid-base character, and crystal and electronic structure. The presence of MgO as a support catalyst also modifies the electronic state of the overall catalytic performance by electron transfer between the native catalyst and MgO as support. The influence is clarified by alteration of acid-base properties of the catalyst-supported MgO. Meanwhile, the method, chemical composition, and condition in the preparation of MgO are the important factors affecting its surface and catalytic properties. Therefore, MgO with a high surface area and nanocrystalline structure has encouraging applications for some reactions, including as dry reforming, dehydrohalogenation, oxidative dehydrogenation of butane, nonoxidative dehydrogenation of ethylbenzene, decomposition of CCl

Influence of the catalyst composition in the oxidative dehydrogenation of 1-butene over BiVxMo1−x oxide catalysts

BiVxMo1−x oxide catalysts with varying compositions were investigated in the oxidative dehydrogenation (ODH) of 1-butene to 1,3-butadiene (BD). Notably, incorporation of vanadium in the Bi-Mo oxide significantly enhanced the catalytic performance in the ODH of 1-butene. Among the tested catalysts, the BiV0.6Mo0.4 oxide catalyst exhibited superior oxygen mobility in temperature-programmed re-oxidation experiments, revealed the facile desorption of adsorbed BD species in the temperature-programmed desorption of 1-butene, and displayed the highest performance (72.2% conversion of 1-butene and 64.0% yield in BD) in the ODH of 1-butene. Moreover, the performance of the tested catalysts decreased in the following order BiV0.6Mo0.4>BiV0.4Mo0.6>BiV0.8Mo0.2>BiV0.2Mo0.8>BiMo>BiV. In addition, the BiV0.6Mo0.4 oxide catalyst displayed stable performance over 85h and its excellent catalytic ability makes it economically viable.

Oxidative dehydrogenation of 1-butene over vanadium modified bismuth molybdate catalyst: an insight into mechanism

The effect of vanadium addition on the performance of bismuth molybdate catalysts has been discussed. The mechanism of oxygen mobility on the prepared catalysts is proposed.

Co-V系複合酸化物の格子酸素を用いる1-ブテンの酸化的脱水素反応

Co-V系複合酸化物の格子酸素を用いる1-ブテンの酸化的脱水素反応