Hydrocarbon deposits formed during n-butane isomerization on sulfated zirconia

The hydrocarbon deposits formed during n-butane isomerization on sulfated zirconia are spectroscopically characterized by infrared, in situ Raman and in situ UV-VIS spectroscopy. Evidence is summarized that suggests the formation of alkenyl and cycloalkenyl ions which presumably are precursors for aromatics that lead to catalyst deactivation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Alkane isomerization over sulfated zirconia and other solid acids

Some solid acids, including sulfated zirconia and certain industrial isomerization catalysts, catalyze two types of n-butane isomerizations, avoiding primary carbenium ions or carbonium ions: (1) an internal rearrangement of the C atoms in n-butane and (2) skeletal isomerization of n-butane to iso-butane. No superacid sites are required for these reactions. The skeletal isomerization is an intermolecular reaction, involving a C₈ intermediate. Easily accessible Brønsted acid sites and small amounts of olefin are crucial. Spectroscopic examination of the acid sites on sulfated zirconia shows that they are not stronger than the acid sites in zeolites such as HY. The butane isomerization rate is suppressed by CO, even when no CO is adsorbed on Lewis sites; formation of oxocarbenium ions is likely. The decisive role of Brønsted acid sites is demonstrated by results on deuterated catalysts.     

Isomerization ofn-butane on sulfated zirconia: Evidence for the dominant role of Lewis acidity on the catalytic activity

The catalytic activity of a ZrO₂/SO₄ catalyst in the isomerization ofn-butane at 423 K is reversibly suppressed by addition of CO. IR analysis of the adsorption of CO indicates that the only -coordination of CO onto coordinatively unsaturated surface Zr⁴⁺ cations occurs in the 300–473 K interval.     

Pentane isomerization and disproportionation catalyzed by sulfated zirconia promoted with iron and manganese

Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion ofn-pentane in a flow reactor at temperatures in the range of –25 to 40C andn-pentane partial pressures in the range of 0.005 to 0.01 atm. The rates of reaction increased with time on stream during an induction period and then decreased rapidly. The predominant reaction at –25C and short times on stream was isomerization to give isopentane; no dibranched products were observed. The selectivity for isomerization decreased and that for disproportionation increased with increasing temperature, with disproportionation becoming predominant at 40C; the principal product was then isobutane. The product distribution data are consistent with acid-base catalysis and carbocation intermediates. However, there appears to be more to the reaction mechanism than acid-base chemistry, and the roles of the iron and manganese promoters are not yet explained.     

Solid superacid catalysis: kinetics of butane isomerization catalyzed by a sulfated oxide containing iron,manganese, and zirconium

Kinetics of the isomerization ofn-butane and of isobutane catalyzed by sulfated zirconium oxide containing 1.5 wt% Fe, 0.5 wt% Mn, and 4.0 wt% sulfate at 60°C are well represented by a Langmuir-Hinshelwood equation accounting for the reaction equilibrium and for adsorption of both butanes. The adsorption equilibrium constants estimated from the kinetics data are nearly the same for the two butanes. The form of the rate equation and the observation that disproportionation accompanies isomerization suggest that the reaction proceeds via a C_g intermediate.     

n-Hexane isomerization over copper oxide-promoted sulfated zirconia supported on mesoporous silica

Copper oxide-promoted sulfated zirconia (CuSZ) was supported on MCM-41 by the direct impregnation method. n-Hexane isomerization was investigated over the CuSZ/MCM-41 catalysts. 2-MP, 3-MP and 2,3-DMB are the major isomerization products, besides a small amount of 2,2-DMB. The product distribution is comparable to that reported for Pt based catalysts. The optimal CuO loading in these catalysts calcined at 700 °C is around 3.2 wt% and only leads to the formation of catalytic active metastable tetragonal ZrO₂. The improved performance of CuO-promoted SZ/MCM-41 is a trade-off between the sulfur amount and the content of tetragonal ZrO₂ phase.     

Acidity of sulfated zirconia as studied by FTIR spectroscopy of adsorbed CO and NH3 as probe molecules

The acid properties of pure and sulfated zirconias were studied by FTIR spectroscopy of adsorbed CO and NH₃ as probe molecules. Whereas pure monoclinic zirconia shows only Lewis acidity, sulfation of tetragonal and monoclinic zirconia creates new bridging OH groups. Two types of Brønsted-acidic centers and two types of Lewis-acidic centers with enhanced acid strength were identified. A communication between the different types of Lewis-acidic sites and the related adsorbed sulfate molecules could be shown. The coordination of basic molecules such as CO onto Lewis-acid sites induces a decrease of the intrinsic Brønsted-acidity of the bridging OH groups. These effects are discussed on the basis of a model of the acidic centers that was previously proposed.On leave from Department of Chemistry, Faculty of Science, Minia University, El-Minia, Egypt.     

Influence of calcination procedure on the catalytic property of sulfated zirconia

Calcination parameters, such as atmosphere, duration and catalyst bed depth have a marked influence on the catalytic and spectroscopic properties of sulfated zirconia. Sulfated zirconia calcined in nitrogen or synthetic airflow, in deep bed, exhibited comparable activity in n-butane isomerization at 373 K, which suggests that oxygen is not necessary for formation of active sites. Catalysts calcined in shallow bed are catalytically inactive. Thus, the bed depth is concluded to be crucial for the formation of active sites. The samples calcined in shallow bed possessed lower sulfate content and the S=O stretching vibration was located at lower frequency. Calcination in the presence of water vapor also led to lower catalytic activity, sulfate content, and BET area. Extended calcination reduced gradually the activity and the sulfate content, which underlines the labile property of the active sites. A new interpretation of the function of the calcination step is proposed and compared with models described in the literature.     

n-Butane conversion on sulfated zirconia: in situ 13C MAS NMR monitoring of the kinetics of the 13C-label scrambling and isomerization

The kinetics of the conversion of ¹³C-labeled n-butane adsorbed on sulfated zirconia (SZ) were monitored by in situ ¹³C MAS NMR spectroscopy. Rate constants of n- to isobutane isomerization and of the ¹³C-isotope scrambling from the primary to the secondary carbon atoms in n-butane were determined. The monomolecular scrambling of the ¹³C-label in adsorbed n-butane has an activation energy of 17 ± 3 kcal mol^–1 and occurs faster than the bimolecular process of n-butane isomerization which has an activation energy of 15.1 ± 0.2 kcal mol^–1. The transfer of the selective ¹³C-label from the primary to the secondary carbon atom in the adsorbed n-butane seems to consist of two reaction steps: (i) a hydride abstraction by SZ leading to the formation of sec-butyl cations and (ii) a label scrambling in the sec-butyl cations. This two-step process with the formation of sec-butyl cations as intermediate increases the apparent activation energy for the ¹³C-label scrambling, which is almost twice as large compared with the activation energy for carbon scrambling of sec-butyl cations in a superacidic solution.     

Characterization of palladium supported on sulfated zirconia catalysts by DRIFTS, XAS and n-butane isomerization reaction in the presence of hydrogen

Palladium supported on sulfated zirconia (PdSZ) has been characterized by the n-butane isomerization reaction in the presence of hydrogen, X-ray absorption spectroscopy (XAS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) of adsorbed carbon monoxide. Catalyst calcination at 873 K followed by hydrogen reduction at 513 K results in the formation of 30–40 Å Pd metal clusters, but the surface can only weakly adsorb CO, though stronger than Pd-free, sulfated zirconia catalysts. In the presence of hydrogen, PdSZ has a lower n-butane isomerization activity than SZ, and the Pd function cannot stabilize the reaction at low H₂/n-butane ratios.     

Simultaneous determination of lodine value and trans content of fats and oils by single-bounce horizontal attenuated total reflectance fourier transform infrared spectroscopy

A method for the simultaneous determination of iodine value (IV) and trans content from the Fourier transform infrared (FTIR) spectra of neat fats and oils recorded with the use of a heated single-bounce horizontal attenuated total reflectance (SB-HATR) sampling accessory was developed. Partial least squares (PLS) regression was employed for the development of the calibration models, and a set of nine pure triacylglycerols served as the calibration standards. Regression of the FTIR/PLS-predicted IV and trans contents for ten partially hydrogenated oil samples against reference values obtained by gas chromatography yielded slopes close to unity and SD of <1. Good agreement (SD<0.35) also was obtained between the trans predictions from the PLS calibration model and trans determinations performed by the recently adopted AOCS FTIR/SBHART method for the determination of isolated trans isomers in fats and oils.     

Development of calibration equations to predict oil content and fatty acid composition in brassicaceae germplasm by near-infrared reflectance spectroscopy

The use of nondestructive analytical methods is critical for the evaluation of very small seed samples such as those from germplasm collections. The objective of this study was to evaluate the potential of near-infrared reflectance spectroscopy (NIRS) for the simultaneous analysis of seed oil content and concentration of major fatty acids in intact-seed samples of the family Brassicaceae. A total of 495 samples from 56 genera and 128 species were analyzed by NIRS. The fatty acid composition of the seed oil was determined in all the samples by gas-liquid chromatography (GLC). The total seed oil content was determined by solvent extraction in 129 samples from 22 genera. Calibration equations for oil content (n=97) and individual fatty acids (n=410) were developed and tested through external validation with the samples not included in the calibration sets. The calibration equations for oil content (r ²=0.97 in validation) and concentrations of C_18:1 (r ²=0.93), C_18:3 (r ²=0.95), and C_22:1 (r ²=0.94) showed very good performance and provided reliable estimations of these traits in the samples of the validation set. The calibration equations for C_16:0, C_18:0, and C_18:2 content were less reliable, with r ² from 0.67 to 0.73. There was practically no response of NIRS to differences in C_20:1 (r ²=0.31). These results demonstrated that the oil content and concentrations of C_18:1, C_18:3, and C_22:1 can be estimated reliably within the family Brassicaceae by using NIRS calibration equations integrating broad taxonomic variability.     

Determination of seed oil content and fatty acid composition in sunflower through the analysis of intact seeds, husked seeds, meal and oil by near-infrared reflectance spectroscopy

A methodological study was conducted to test the potential of near-infrared reflectance spectroscopy (NIRS) to estimate the oil content and fatty acid composition of sunflower seeds. A set of 387 intact-seed samples, each from a single plant, were scanned by NIRS, and 120 of them were selected and further scanned as husked seed, meal, and oil. All samples were analyzed for oil content (nuclear magnetic resonance) and fatty acid composition (gas chromatography), and calibration equations for oil content and individual fatty acids (C_16:0, C_16:1, C_18:0, C_18:1, and C_18:2) were developed for intact seed, husked seed, meal, and oil. For intact seed, the performance of the calibration equations was evaluated through both cross- and external validation, while cross-validation was used in the rest. The results showed that NIRS is a reliable and accurate technique to estimate these traits in sunflower oil (validation r ² ranged from 0.97 to 0.99), meal (r ² from 0.92 to 0.98), and husked seeds (r ² from 0.90 to 0.97). According to these results, there is no need to grind the seeds to scan the meal; similarly accurate results are obtained by analyzing husked seeds. The analysis of intact seeds was less accurate (r ² from 0.76 to 0.85), although it is reliable enough to use for pre-screening purposes to identify variants with significantly different fatty acid compositions from standard phenotypes. Screening of intact sunflower seeds by NIRS represents a rapid, simple, and cost-effective alternative that may be of great utility for users who need to analyze a large number of samples.     

Analyzing seed weight,fatty acid composition,oil, and protein contents in <Emphasis Type="Italic">Vernonia galamensis</Emphasis> germplasm by near-infrared reflectance spectroscopy

Vernonia galamensis is a potential new industrial oilseed crop from the Asteraceae family. The interest in this species is due to the presence of a high vernolic acid content of its seed oil, which is useful in the oleochemical industry for paints and coatings. The development of a rapid, precise, robust, nondestructive, and economical method to evaluate quality components is of major interest to growers, processors, and breeders. NIR reflectance spectroscopy (NIRS) is routinely used for the prediction of quality traits in many crops. This study was conducted to establish a rapid analytical method for determining the quality of intact seeds of V. galamensis. A total of 114 Vernonia accessions were scanned to determine seed weight, FA composition, oil, and protein contents using NIRS. Conventional chemical analysis for FA composition, total oil, and protein contents were performed by GC, Soxhlet extraction, and the Dumas combustion method, respectively. Calibration equations were developed and tested through cross-validation. The coefficient of determination in cross-validation for FA ranged from 0.47 (linoleic acid) to 0.55 (vernolic acid), and for oil, protein, and seed weight from 0.71 (oil) to 0.86 (seed protein). It was concluded that NIRS calibration equations developed for seed weight and seed quality traits can be satisfactorily used as early screening methods in V. galamensis breeding programs.     

Fatty acid composition of spanish shortenings with special emphasis on <Emphasis Type="Italic">trans</Emphasis> unsaturation content as determined by fourier transform infrared spectroscopy and gas chromatography

A Fourier transform infrared spectroscopic procedure was used to analyze 34 edible fats (22 shortenings and 12 vegetable margarines) as neat fats (IR_NF) to determine their total trans fatty acid (TFA) content. The sloping baseline was corrected with a reference spectrum based on a nonprocessed olive oil. The calibration was done using seven partially hydrogenated fats with an individual TFA content previously determined by the combination of gas chromatography (GC) with argentation thin-layer chromatography. Taking into account the different absorptivities of various trans isomers, different correction factors were calculated using the calibration standards (0.83 and 1.71 for single trans bonds in both diethylene and triethylene and for trans, trans-diethylene fatty acids, respectively) and applied to calculate the total TFA of samples. Moreover, the samples were converted to their methyl esters and reanalyzed following the same procedure (IR_FAME). Differences in TFA content of fats were not found when a t-test was used to compare the results obtained by IR_NF vs. either IR_FAME or GC, suggesting that IR of neat fats could be used, thus avoiding the need to prepare sample solutions in organic solvents and to prepare fatty acid methyl esters. The mean TFA content (determined by IR_NF) of a representative group of Spanish shortenings (22 samples) that varied widely in terms of fat sources, processes, and purposes (bakery, sandwiches, ice cream, coatings, chocolate coverings) was 6.55±11.40%, although more than 54% contained <3% of TFA. Fatty acid composition of shortenings by direct GC using a 100-m polar cyanopolysiloxane capillary column indicated that the mean trans-18∶2 isomer content was 0.58%, ranging from 0.9 to 3.4%. Small amounts of trans-18∶3 isomers (<0.3%) were observed in 18 of the 22 shortenings studied; the maximal value was <2%. The mean value of the fraction saturated+TFA of shortenings was high (59.95±12.73%), including two values higher than 83%.     

Mechanistic study on Sn(Oct)<Subscript>2</Subscript>-catalyzed,ring-opening polymerization of <Emphasis Type="Italic">p</Emphasis>-dioxanone by surface-initiated polymerization and x-ray photoelectron spectroscopy

Two mechanisms on Sn(Oct)₂-catalyzed, ring-opening polymerization of p-dioxanone (PDX) were mainly proposed: activated monomer mechanism and coordination-insertion mechanism. The activated monomer mechanism assumes that alcohol complexed with Sn(Oct)₂ reacts with monomer and forms a ternary complex. The initiation and chain growth then proceeds within the complex with liberation of the intact Sn(Oct) ₂. In contrast, the coordination-insertion mechanism hypothesizes that an actual initiator is the -Sn(OR) species and the polymerization proceeds on the -Sn-O-polymer. In this paper, to investigate the presence/absence of the Sn species in the PPDX chain, we used X-ray photoelectron spectroscopy (XPS) of poly(p-dioxanone) (PPDX) grown from a gold surface using the grafting-from approach, and the XPS data supports the coordination-insertion mechanism. After the polymerization of PPDX from the surface, the peaks from Sn were observed at 153, 486, and 495 eV in XPS spectrum, and the peaks disappeared after quenching with 1N HCl.