Modeling of Isobutane/Butene Alkylation Using Solid Acid Catalysts in a Fixed Bed Reactor

A dynamic mass transfer model of isobutane/butene alkylation over solid acid catalysts in a fixed bed reactor was established. In the model, a modified equation for the relationship between point activity and effective diffusion coefficient was proposed. It is found that the simulation results fit the experimental data well and the breakthrough time of the bed layer is predicted accurately. By modeling the alkylation process, the time-space distribution of butene and point activity profiles of catalysts can be obtained. Furthermore, the reasons for the deactivation of solid acid catalysts were investigated. It indicates that the main reason for the deactivation of catalysts is the site coverage near the inlet of the reactor, while it is ascribed to the steric effect in the region far away from the inlet.

Research progress in ionic liquids catalyzed isobutane/butene alkylation

The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought to be new potential acid catalysts for C_4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Br?nsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C_4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.

Coke precursor as an intermediate during the alkylation of isobutane/butene over a solid superacid

Alkylation of isobutene/butene was conducted on a Brфnsted-Lewis conjugated solid superacid.It is found that some hydrocarbons accumulated on the catalyst surface.These hydrocarbons,as called coke precursor,played an intermediate role at the initial stage of the al-kylation before they lead the catalyst to lose its activity.The presence of the intermediate is beneficial to the alkylation between isobutene and butene,while increase the TMP content and TMP/DMH ratio in the products.

MCM-36 zeolites tailored with acidic ionic liquid to regulate adsorption properties of isobutane and 1-butene

Adsorption properties of an adsorbent or a catalyst towards adsorbates are crucial in the process of adsorption separation or catalytic reaction. Surface morphology and structure of adsorbents have a significant impact on the adsorption properties. In this study, a novel acidic ionic liquid, 1-butyl-3-(triethoxysilylpropyl)imidazolium hydrogen sulfate(i.e., [BTPIm][HSO_4]), was synthesized and subsequently grafted onto the MCM-36 zeolite for the regulation of its adsorption properties towards isobutane and 1-butene. The resultant [BTPIm][HSO_4]-immobilized MCM-36(i.e., MCM-36-IL) was characterized by FT-IR, XPS, XRD, SEM, TG/DTG and N_2 adsorption–desorption measurement. It was found that the specific surface area, micropore volume and mesopore volume of the MCM-36 support underwent a reduction upon the immobilization of ionic liquid,while the surface density of acid increased from 0.0014 to 0.0035 mmol·m^(-2). The adsorption capacity of isobutane and 1-butene on the MCM-36-IL was determined by a static volumetric method. Results demonstrated that the interaction between isobutane and MCM-36-IL was enhanced and the interaction between 1-butene and MCM-36-IL was reduced. As a result, a tunable adsorption ratio of isobutane/1-butene on MCM-36 was achieved.With the increase in surface density of acid and the tunable adsorption ratio of isobutane and 1-butene on the functionalized MCM-36, the acidic ionic liquid-immobilized zeolites are beneficial to obtain an improved reaction yield and a prolonged catalyst life in the reactions catalyzed by solid acid.

Alkylation of Isobutane and Butene on BrФnsted-Lewis Conjugated Solid Superacids

A BrΦnsted-Lewis (B-L) conjugated solid superacid HPW-SbF5/SiO2 was synthesized by a two-step method. This B-L acid shows high acid strength, high activity, good selectivity and moderate stability in alkylation of isobutane/butene due to strong interaction between the BrΦnsted acid and the Lewis acid, as confirmed by the results of IR, NMR and XPS. Under a mild reaction condition (30℃, 15-35x105 Pa), the conversion of butene was maintained at 100% for 1 10 hours on stream and the main products were C8 and TMP. The results of alkylation conducted under various operating conditions indicated that the activity was improved by increasing the loading content of HPW and SbF5. The selectivity of TMP in the products was enhanced when the isobutane/butene ratio in the feedstock was increased. The existence of some intermediates was also reported.

Dehydrogenation of isobutane to isobutene over a Pt-Cu bimetallic catalyst in the presence of LaAlO_(3) perovskite

In this study,isobutane dehydrogenation to isobutene reaction was carried out in a series of PtCu bimetallic catalysts prepared by coimpregnation method.The catalysts were characterized by means of several techniques,including XRD,N_(2) adsorptiondesorption,TEM,XPS,H2TPR and TG.The results show that the existence of LaAlO_(3) perovskite can enhance the dispersion and sintering resistance of metal nanoparticles and facilitate the transfer of carbon deposits from active sites to the support.Interestingly,the perovskite nanoparticles can also inhibit the reduction of CuOx and the formation of PtCu alloys,resulting in the suitable interaction between Pt and Cu.The PtCu/LaAlO_(3)/SiO_(2)catalyst exhibits the optimal dehydrogenation performance with an isobutane conversion of 47%and isobutene selectivity of 92%after 310 min reaction,which was ascribed to the unique role of LaAlO_(3) perovskite as well as the appropriate PtCu interaction.

Comparative catalytic study on butene/isobutane alkylation over LaX and CeX zeolites: The influence of calcination atmosphere

Lanthanum-containing(LaX)and cerium-containing X zeolites(CeX)were prepared by a doubleexchange,double-calcination method.By changing the calcination atmospheres between nitrogen and air,the Ce^(IV) contents in CeX zeolites were adjusted and their impacts on physicochemical properties and catalytic performance in isobutane alkylation were established.The crystallinity of CeX zeolite was found to be negatively correlated with the Ce^(IV) content.This i s believed to be due to the water formed during the oxidation of Ce^(III),which facilitates the framework dealumination.As a consequence,calcining in air resulted in a great elimination of strong Brønsted acid sites while under nitrogen protection,this phenomenon was mostly hindered and the sample’s acidity was preserved.When tested in a continuously flowed slurry reactor,the catalyst lifetime for isobutane alkylation was found to be linearly related to the strong Brønsted acid concentration.In addition,Ce^(3+)was found more benefit for the hydride transfer compared with La^(3+),which is ascribed to the stronger polarization effect on the CH bond of isobutane.Moreover,the decline of hydride transfer activity can be slowed down by the catalytic cracking of the bulky molecules.Based on the product distribution,a new catalytic cycle of dimethylhexanes(DMHs)involving a direct formation of isobutene rather than tert-butyl carbocation was proposed in isobutane alkylation.

Regulation of isobutane/1-butene adsorption behaviors on the acidic ionic liquids-functionalized MCM-22 zeolite

The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C_4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid(i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22(i.e., MCM-22-IL)was characterized by FTIR, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to 1-butene(I/O) were investigated to correlate with surface features of MCM-22-IL. Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene(I/O) was significantly improved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length of ILs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.

Synergistic effect between Sn and K promoters on supported platinum catalyst for isobutane dehydrogenation

Catalytic dehydrogenation of isobutane has recently received considerable attention because of the increasing demand for isobutene.In this study,the synergistic effect between Sn and K on PtSnK/γ-Al2O3 catalysts has been investigated by changing the content of Sn.It was found that with the presence of potassium,suitable addition of Sn could not only increase the metal dispersion,but also reduce the catalyst acidity.In these cases,the synergistic effect could also strengthen the interactions between the metal and support,which resulted in an increase in both catalytic activity and stability.In our experiments,Pt-0.6SnK/Al catalyst exhibited the lowest deactivation rate （12.4%） and showed a selectivity to isobutene higher than 94% at the isobutane conversion of about 45.3% after running the reaction for 6 h.However,with the excessive loading of Sn,surface property of active sites and the interactions between metal and support were changed.As a result,the initial optimal ratio between the metallic function and acid function would be destroyed,which was disadvantageous to the reaction.

Investigation of the characteristics and deactivation of catalytic active center of Cr-Al_2O_3 catalysts for isobutane dehydrogenation

Deactivation mechanism of Cr-Al2O3catalyst and the interaction of Cr-A1 in the dehydrogenation of isobutane, as well as the nature of the catalytic active center, were studied using XRD, SEM, XPS, H2-TPR, isobutane-TPR and TPO techniques. The results revealed that the deactivation of Cr-Al2O3 catalyst was mainly caused by carbon deposition on its surface. The Cr3＋ ion could not be reduced by hydrogen but could be reduced to Cr2＋ by hydrocarbons and monoxide carbon. The active center for isobutane dehydrogenation could be Cr2＋/Cr3＋ produced from Cr6＋ by the on line reduction of hydrocarbon and carbon monoxide. The binding energy of Al3＋ was strongly affected by the state of chromium cations in the catalysts.

Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA–AlCl3 based ionic liquid analog

Isobutane alkylation with 2-butene to produce high-quality gasoline was catalyzed by Nmethylacetamide(NMA)-AlCl3 based ionic liquid(IL) analog with a NMA/AlCl3 molar ratio of 0.75 and CuCl modification,which was marked as CuCl-modified 0.75 NMA-1.0 AlCl3.The long-term experiment was carried out in the autoclave operated in continuous mode to investigate the distribution of alkylate under different experimental nodes.The result indicated that the long-term alkylation was divided into three stages:rising,stable,and descending regions.C8 selectivity and molar ratio of trimethylpentanes(TMPs) to dimethylhexanes(DMHs) reached the highest level in the stable region,and research octane number(RON) of alkylate was as high as 97.Anionic Al species([AlbCl7]^-,[A1 CuC15]^-) and cationic Al species([AlCl2 L]^+) from IL analog as two active Lewis acidic species played a catalytic role in the long-term alkylation,whereas the neutral Al species did not participate into the alkylation.Moreover,the structure of CuCl-modified 0.75 NMA-1.0 AlCl3 was destroyed after the deactivation,and CuCl was enriched in the CD2 Cl2-insoluble substance,resulting in a decreasing TMP/DMH ratio.The catalytic lifetime of IL analog was similar with CuCl-modified 0.55 Et3 NHCl-1.0 AlCl3 IL,but IL analog had a lower cost.

Isobutane dehydrogenation over chromia alumina catalysts prepared from MIL-101: Insight into chromium species on activity and selectivity

Various mesoporous chromia alumina catalysts were prepared by five different methods based on a metal-organic framework MIL-101 and their catalytic performances over isobutane dehydrogenation were investigated. The highly dispersed chromium species were produced on catalyst KCrAI-I1 with largest specific surface area of 198 m2-g-1 prepared with aluminium isopropoxide （Al（i-OC3HT）3） by ultrasonic im- pregnation method. However, the catalyst KCrAI-I2 synthesized by stirring impregnation possessed crystalline a-Cr203 phase, which was poorly dispersed. Two types of Cr-rich and Al-rich CrzA12_zO3 solid solutions, designated as CrAI-I and CrAI-II phase, were formed over the catalysts KCrAI-I3 （prepared by Al（i-OC3HT）3 with nitric acid regulation）, KCrA1-C4 （prepared by aluminium chloride hexahydrate） and KCrA1-N5 （prepared by aluminium nitrate nonahydrate）. Catalytic evaluation results revealed that KCrAI-I1 exhibited the high isobutane con- version due to its highly dispersed chromium species. However, KCrAI-I3, KCrA1-C4 and KCrA1-N5 showed the higher isobutene selectivity （95.2%-96.4%） on account of the formation of chromia alumina solid solutions in the catalysts. Moreover, the solid solution over the chromia alumina catalysts could greatly suppress the coke formation.

Partial amination of cationic exchange resins and its application in the hydration of butene

In this work, the amination of sulfonated polystyrene resin with alkyl secondary amine is investigated. The catalytic activities of the modified resins are determined through the hydration of l-butene. The optimum chain length and the best range of amination rate are determined. It is found that the single-pass conversion of 1 -butene was raised 2% on average, and the relative activity was increased over 30% after modification. A hypothesis about the enhancement of catalytic activities by the inclusion of alkyl chain to wrap up the butene molecule is proposed.

Metathesis of 1-butene and 2-butene to propene over Re_2O_7 supported on macro-mesoporous γ-alumina prepared via a dual template method

Macro-mesoporous γ-alumina support（MMA） was prepared by a sol-gel route in aqueous medium using pseudo-boehmite as aluminum source and polystyrene microspheres and Pluronic P123 as hard and soft dual templates,respectively.MMA had a BET specific surface area of about 259 m2 g-1,total pore volume of about 1.61 cm3 g-1,macropore diameter of about 102 nm,and mesopore diameter of about 14 nm.Re2O7/MMA and conventional Re2O7/Al2O3 were prepared by a incipient-wetness impregnation method,and their catalytic performances in the metathesis of 1-butene and 2-butene were tested in a fixed-bed tubular reactor.The result showed that Re2O7/MMA possessed higher activity and far longer working life-span than conventional Re2O7/Al2O3.

Novel Pt-Ni Bimetallic Catalysts Pt(Ni)-LaFeO_3/SiO_2 via Lattice Atomic-Confined Reduction for Highly Efficient Isobutane Dehydrogenation

In this study, a series of novel Pt-Ni bimetallic catalysts supported on LaFeO_3/SiO_2 with different amounts of Ni were prepared by the lattice atomic-confined reduction of LaFe_(1-x)(Ni, Pt)_xO_3/SiO_2 perovskite precursors and applied in isobutane dehydrogenation to isobutene reaction. The catalysts were characterized by X-ray diffraction, H_2-temperature-programmed reduction, Brunauer-Emmett-Teller analysis, transmission electron microscopy, energy dispersive X-ray, CO chemisorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The as-synthesized Pt-Ni bimetallic catalysts possessed smaller most probable particle size with tunable Pt-Ni interaction, depending on the Ni content. The catalyst with Ni content of 3.0 wt% showed excellent activity and stability(the isobutane conversion and isobutene selectivity remained at about 38% and 92%, respectively, after 310 min) for the isobutane dehydrogenation reaction. It also provided approximately six times turnover frequency of the catalyst without Ni. The excellent activity and stability of the 3.0 wt% Ni-containing catalyst can be attributed to its small metal nanoparticles with high dispersion and suitable Pt-Ni interaction. Moreover, the Pt(Ni)-LaFeO_3/SiO_2 catalyst with Ni content of 3.0 wt% had been run for more than 35 h without obvious loss of activity,indicating its long-term stability, and the decrease in the Pt-Ni interaction that accompanied the formation of the FeNi alloy phase was thought to be responsible for the slight decrease in activity.

Effects of Cs-substitution and partial reduction on catalytic performance of Keggin-type phosphomolybdic polyoxometalates for selective oxidation of isobutane

The catalytic performance of Cs-substituted phosphomolybdic salts was studied for selective oxidation of isobutane. The results of activity tests revealed that 360 °C was the optimal reaction temperature. It was demonstrated that oxidizing sites not only took dominating part in the activation of isobutane, but also influenced the product distribution. Besides, appropriate Cs addition led to moderate acidity of catalysts, favoring the selectivity to desired products. Furthermore, to obtain partially reduced catalysts, different calcination atmospheres were investigated and certain proportion of Mo^（5＋） produced during calcination was crucial for the redox reaction. The catalyst calcined in N2 showed the highest yield of MAA（7.0%）. Fe-substitution enhanced the activity of catalysts by rapid reoxidation of Mo^（5＋）.

Simple Preparation of Spherical Activated Carbon with Mesoporous Structure from Phenolic Resol and Associated Catalytic Performance in Isobutane Dehydrogenation

This study provides a detailed report on the synthesis of spherical activated carbon with mesoporous structure using a soluble low molecular weight phenolic resol precursor through an ammonium alginate assisted sol–gel method. The effects of calcinating temperature and the addition of CaCO_3 as a pore-enlarging agent on texture structure and catalytic performance in isobutane dehydrogenation to isobutene were investigated. Characterization of N_2 sorption,mechanical strength tests,and optical photographs confirmed that the obtained carbon materials had high mechanical strength,a good degree of sphericity,and a large surface area. Introducing CaCO_3 as a pore-enlarging agent during the preparation process promoted the formation of a mesoporous structure of carbon spheres and evidently increased the surface area and oxygen content,which can improve isobutane conversion and isobutene selectivity of these carbon spheres. The conversion of isobutane reached up to 28% for this spherical activated carbon,and the selectivity of isobutene reached up to 96%. Isobutane conversion increased with an increase in calcination temperature due to an increase in the oxygen content,whereas the selectivity of isobutene decreased due to the slight decrease in the specific surface area.

Preparation of mesoporous alumina with large pore size and their supported rhenium oxide catalysts in metathesis of 1-butene and 2-butene to propene

Mesoporous γ-aluminas with large pore size （up to 19 nm, denoted as MAI9） are prepared from dispersed pseudo-boehmite using pluronic P123 as template. It is found that these mesoporous alumina supported rhenium oxide catalysts were more active and have far longer working life-span in gas-phase metathesis of 1-butene and 2-butene to propene than rhenium oxide on conventional alumina with small pore size （5 nm）. At 60 ℃ and atmospheric pressure with WHSV = 1 h^-1, the similar stable conversions of butene （ca. 55%） for all the 13 wt% Re207/alumina catalysts were obtained near the chemical equilibrium, and the stable working life-spans of Re2OT/MA19 were far longer than that of Re2O7/A1203, being about 70 h and 20 h, respectively.