Enhancement of distillate selectivity in Fischer-Tropsch synthesis by using iron and cobalt catalysts in a novel dual-bed reactor ?

Summary An integrated process for producing liquid fuels from synthesis gas via a two-stage Fischer-Tropsch (FT) reaction is disclosed. An iron catalyst was used in the first bed of a fixed-bed reactor followed by a ruthenium promoted cobalt catalyst in the second bed. The activity and selectivity of the dual-bed system were assessed and compared with those using catalysts in a single bed system, separately. The methane selectivity in the dual-bed reactor was about 11% less compared to that of the single-bed system. The C₅⁺ selectivity for the dual-bed reactor was 19.7% higher than that of the single-bed system.     

Pyrrole studies part 41. Reactivity of 3,4-diformyl-2,5-dimethylpyrrole with diaminoalkanes. An unusual formation of 2-azafulvenes

3,4-Diformyl-2,5-dimethylpyrrole (1) reacts with ,ω-diamino-alkanes, NH₂(CH₂)_nNH₂t' to form either the potentially tautomeric 2:2 macrocyclic adduct (7a) (8), when N = 2, or the potentially tautomeric 1:1 bicyclic adduct (18) (19), when N = 4, 5, 6, and 12. ¹H and ¹³C N.m.r. spectral data indicate that the 2-azafulvene structures predominate for both types of cycloadducts. Only polymeric material was obtained when N = 3.     

Organosilicon compounds : LI. Further studies of the base-catalysed solvolysis of N-(triorganosilyl)anilines

Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC₆H₄NHSiEt₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO₂, 18; p-CN, ca. 43; p-NO₂, ca. 120. (ii) For PhNHSi(C₆H₄Y)₃ compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR₃ compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R₃ =) Et₃, 1.0; Et₂Me, 18 (at 30°); Me₂-i-Pr, 8 (at 30°);Me₂-t-Bu, 0.012 (at 50°);i-Pr₃, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ^?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed.     

The use of Nafion-H® as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions

Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions.     

Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of iron in alloys and biological samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by third derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate on naphthalene (ATPB-naphthalene) provides a simple, rapid, economical and selective technique for preconcentrating iron from approximately 500 ml of aqueous solution of standard alloys and biological samples. Iron reacts with 2-(5-bromo-2-pryidlazo)-5-diethylaminophenol (5-Br-PADAP) to form a water-soluble cationic complex. When the aqueous solution of this cationic species in the pH range 3.2-8.5 is passed over the adsorbent ATPB-naphthalene at a flow rate of 1 ml min(-1), it is quantitatively retained on naphthalene as an uncharged ion-associated complex. The solid mass from the column was dissolved out with 5 ml of dimethylformamide (DMF) and iron is determined by third derivative spectrophotometry by measuring the signal d(3)A/ dlambda(3) between lambda(2)(773 nm) and lambda(3)(737 nm). The calibration curve is linear over the concentration range 0.10-25.0 mug of iron in 5 ml of DMF solution. Eight replicate determinations of 5 mug of iron gave a mean intensity (peak-to-peak signal between lambda(2) and lambda(3)) of 1.534 with a relative standard deviation of 0.90%. The sensitivity of the method is 0.307 (d(3)A/dnm(3) )/mug found from the slope of the calibration curve. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of iron in various standard alloys and biological samples.     

A study of the formation of silica-supported mixed magnesium-manganese spinel oxides from multicomponent gels

The effects of thermal treatment on composite materials prepared by the gelation of sols comprising large concentrations of metal oxide precursor salts have been investigated, in order to determine the compositional and thermal requirements for forming spinel magnesium manganates in such systems. The preparative technique has been found to give rise to derived gel materials in which the metal oxide phase, in the form of regular spherical particles, is dispersed throughout a continuous silica matrix. Silica-supported mixed magnesium and manganese spinel oxide phases were obtained for systems comprising at least 30 wt% metal nitrate after heating to temperatures between 700 and 850°C, but not without concomitant formation of Mn₂O₃ and modification of the silica network by magnesium.     

Synthesis, characterization, and electrochemical and electrochromic properties of sandwich dilutetium tetraphthalocyanine

A new sandwich-tpype dilutetium tetraphthalocyanine 4 has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine 3 with two equiv. of dilithium octakishexylthiophthalocyanine in amyl alcohol. Compound 3 was prepared from 4',5',4",5"-tetraiminoisoindoline(1,4,7,10-tetrathia-12-crown-4) 1, 4,5-bis(hexylthio)-1,2-diiminoisoindoline and lutetium acetate in amyl alcohol. Compounds 3 and 4 were characterized by elemental analysis, UV/visible, IR, (1)H NMR and ESR spectroscopy. The electrochemical and electrochromic properties of 3 and 4 have been examined by cyclic voltammetry. Both 3 and 4 displayed well-defined electrochromic behavior.     

PHTHALOCYANINE-INDUCED PHOTOHEMOLYSIS: STRUCTURE-ACTIVITY RELATIONSHIP AND THE EFFECT OF FLUORIDE

Abstract— Phthalocyanine (Pc) containing AI, Ga or Zn as central metal ligand and substituted with a varying number of sulfonic acid residues as well as additional benzene rings were synthesized and their photodynamic activity was assayed using photohemolysis of human erythrocytes as an endpoint. The Pc derivatives vaned > 300-fold in their photodynamic activity. Activity corrclated with binding of the dye to the cell, with the exception of some of the amphiphilic dyes where cell uptake was an order of magnitude higher than expected from the observed activity. Fluoride was shown to inhibit AIPcS_n-induccd photohemolysis. This effect occurred also with other AlPc and GaPc derivatives, but the concentration of F required to slow photohemolysis by a factor of two (K_i) varied between 4 μ M and 10 mM. Fluorescence spectral studies indicated complex formation between F⁻ and the dye, which was stronger for AlPc than GaPc derivatives. Ultrastructural studies using scanning electron microscopy showed that the photosensitized cells were converted to spherocytes and that F⁻ prevented this to a large extent.     

Thermal synthesis and characterisation of N,N'-di(chlorobenzyl) ureas

The thermal stability of the Schiff base ethylacetoacetate-o-chlorobenzylamine (bdII), N-o-chlorobenzyl-C-benzoyl acetamide (bdIII), and N-p-chlorobenzyl-C-benzoyl acetamide (bdIV) were studied by thermogravimetric analysis. II Gave N,N'-di(o-chlorobenzyl) urea (bdIa) at 60° C, whereas the thermogravimetric curves of III and IV indicate that reactions other than formation of I may occur. The urea derivatives (I) have also been prepared from benzylamines and the corresponding β-ketoester and identified.     

Nitroxide mediated living radical polymerization of styrene onto poly (vinyl chloride)

Nitroxide‐mediated ‘living’ free radical polymerisation (LREP) was employed for the first time to prepare graft copolymer by having arylated poly (vinyl chloride) (PVC‐Ph) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PVC carrying 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, the arylated PVC was prepared in the mild conditions and these reaction conditions could overcome the problem of gelation and crosslinking in polymers. Then, 1‐hydroxy TEMPO was synthesized by the reduction of TEMPO with sodium ascorbate. This functional nitroxyl compound was coupled with brominated arylated PVC (PVC‐Ph‐Br). The resulting macro‐initiator (PVC‐Ph‐TEMPO) for ‘living’ free radical polymerization was then heated in the presence of styrene to form graft copolymer. DSC, GPC, ¹HNMR, and FT‐IR spectroscopy were employed to investigate the structure of the polymers. Copyright © 2007 John Wiley & Sons, Ltd.