Selective conversion of light gasoline into aromatic hydrocarbons over shape selective zeolites, I. Catalytic activity of various zeolites for aromatization of light gasoline, heavy gasoline and coker naphtha

Studies about the development of a new effective aromatization process for converting gasoline rich in light saturated hydrocarbons, using modified molecular shapeselective zeolites, have been carried out. Naphthas with olefins and naphthenes are potential feedstocks. The yield of aromatic hydrocarbons increases with decreasing hydrogen content of the feed. Zn-SABO and Zn-ZSM type zeolites have been shown to be excellent catalysts for the process.     

Thermal and FTIR spectroscopic analysis of the interactions of aniline adsorbed on to MCM-41 mesoporous material

The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline.     

THE EFFECT OF ACIDS ON THE INFRARED SPECTRA OF SCHIFF BASES—II. IMINES CONTAINING THE C=C-C=N AND C=C-C=C-C=N UNITS

Abstract— The Fourier-transform infrared spectra of chloroform-d solutions of conjugated imines CH₃CH=CHCH=NCH(CH₃)₂ and CH₃CH₂CH=CHCH=CHCH=NCH(CH₃)₂ and the related protonated species with HCl, HBr, HI, trichloro, dichloro, monobromo and monochloroacetic acids or propionic acid are presented. The effects of conjugation and protonation are examined. The results show that conjugation slightly increases the basicity of the Schiff bases. HCl, HBr and HI protonate the Schiff bases completely. The carboxylic acids protonate partially depending on their p K _a, values. When the Schiff base contains two (or more) C=C bonds conjugated with C=N, the main C=C stretching band undergoes a strong intensification showing that sizeable dipole moment variations occur along the conjugated chain.     

n-Pentane conversion to aromatic hydrocarbons over Zn-ZSM-11 zeolite

The transformation of n-pentane into aromatic hydrocarbons over Zn-exchanged ZSM-11 zeolite (Zn-ZSM-11) has been studied. The catalyst exhibited a high activity and BTX selectivity for n-C5 conversion at about 538°C, 1 h^–1 and 1 atm. Zn-species are effective for the activation of the n-pentane and the transformation of intermediate products into aromatic compounds.

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- ZSM-11, (Zn-ZSM-11). - 538°C, 1^–1 1 . Zn - .

     

Studies on the conversion of isopentane over shape selective zeolites II., H-Zn-ZSM-11 zeolites

Studies on the conversion ofi-pentane over Zn containing zeolites have been carried out under different reaction conditions. The incorporation of Zn²⁺ as counter-ion into ZSM-11 zeolite modified the activation mode of the alkane, generating highly reactive intermediates and enhanced the aromatic yields.     

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.     

Aromatization of natural propane using modified molecular-shape selective zeolites

The conversion of propane into aromatic hydrocarbons has been studied at 400–540°C, using H-ZSM-11, Zn-ZSM-11, H-ZSM-5 and Zn-ZSM-5 zeolites. The zinc-exchanged forms of ZSM-11 and ZSM-5 were more active and gave better aromatic selectivity. The aromatics yield increased with the temperature and BTX selectivity increased with space velocity.

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400–540°C H-ZSM-11, Zn-ZSM-11, H-ZSM-5 Zn-ZSM-5. , . .

     

Synthesis and characterization of SBA-3, SBA-15, and SBA-1 nanostructured catalytic materials

A highly ordered large pore mesoporous silica molecular sieve SBA-3, SBA-15, Al-SBA-15, and SBA-1, were developed and characterized by XRD, BET, FTIR, SEM, and NMR-MAS. The catalytic materials were synthesized using different raw materials and operation conditions. These materials contain a regular arrangement of uniform channels with diameters between 1.8 and 10 nm, high specific surface area and high specific pore volume. The designed methods were effective for the synthesis, presenting each mesostructured materials, patterns of XRD and other characteristics corresponding to the reported ones in literature. The new route employed to synthesize Al-SBA-15, generates a catalyst with only aluminum in tetrahedral form, according to the data of (27)Al NMR-MAS. However, several reports indicated that the coordination of the Al atoms changes below the Si/Al ratio of 45, presenting peaks corresponding to penta and hexa-coordinated aluminum, which are absent in our samples (Si/Al = 50 and 33).     

Selective transformation of light olefins into aromatic hydrocarbons over pentasil zeolites

1-Pentene and 1-hexene transformation into aromatic hydrocarbons over H-ZSM-5, H-ZBS-11 and H-ZSM-11 modified with Zn(II), Ga(III), Mn(II) and Fe(III) has been studied. Aluminosilicate zeolites exhibited higher activity than borosilicate zeolites. Zn-species are effective in dehydrogenation, generating allylic intermediates from olefins used as feed.     

Selective conversion of light gasoline into aromatic hydrocarbons over shape selective zeolites, II. Effect of the reaction condition and time on stream

Zn-exchanged ZSM zeolite exhibits high activity and aromatic selectivity. The results, in concordance with Mole et al. [1], suggest that the zinc loading of ZSM zeolite changes the activation mode of light paraffins and greatly improves the effective aromatization of the intermediates.