Comparison of batchstirred and electrospray reactors for biodesulfurization of dibenzothiophene in crude oil and hydrocarbon feedstocks

Biological removal of organic sulfur from petroleum feedstocks offers an attractive alternative to conventional thermochemical treatment, because of the mild operating conditions afforded by the biocatalyst. In order for biodesulfurization to realize commercial success, reactors must be designed that allow for sufficient liquid-liquid and gas-liquid mass transfer, while simultaneously reducing operating costs. Electro-spray bioreactors were investigated for use as desulfurization reactors because of their reported operational cost savings relative to mechanically agitated reactors. Unlike batch-stirred reactors, which mix the biocatalystcontaining aqueous phase with the organic feedstock by imparting momentum to the entire bulk solution, electro-spray reactors have the potential for tremendous cost savings, creating an emulsion <5 (μm in diameter, at a cost of only 3 W/L. Power law relationships indicate that mechanically stirred reactors would require 100-1000-fold more energy to create such a fine emulsion, but these relationships generally do not account for the effect of endogenously produced surfactant in the system. Here, the rates dibenzothiophene (DBT) oxidation to 2-hydroxybiphenyl (2-HBP) in hexadecane, byRhodococcus sp IGTS8 are compared in the two reactor systems. Desulfurization rates ranged from 1.0 to 5.0 mg 2-HBP/(dry g cells · h), independent of the reactor employed. The batch-stirred reactor was capable of forming a very fine emulsion in the presence of the biocatalyst IGTS8, similar to that formed in the emulsion phase contactor (EP^TM), presumably because the biocatalyst produces its own surfactant. Although EPC did not prove to be advantageous for the IGTS8 desulfurization system, it may prove advantageous for systems that do not produce surface-active bioagents, in addition to being mass-transport limited.     

A variable projection method for solving separable nonlinear least squares problems

Consider the separable nonlinear least squares problem of findinga εR ⁿ and α εR ^k which, for given data (y _i ,t _i ),i=1,2,...m, and functions ? _j (α,t),j=1,2,...,n(m>n), minimize the functional $$r(a,\alpha ) = \left\| {y - \Phi (\alpha )a} \right\|_2^2$$ where θ(α) _ij =? _j (α,t _i ). Golub and Pereyra have shown that this problem can be reduced to a nonlinear least squares problem involvingα only, and a linear least squares problem involvinga only. In this paper we propose a new method for determining the optimalα which computationally has proved more efficient than the Golub-Pereyra scheme.     

Ab initio calculations of the ground-state potential energy surface for the C?F bond decomposition in n-fluoropropane within the method for approximation of the frozen molecular fragment

The recently proposed ab initio method for calculation on many-electron molecular systems with the approximation of the inactive part of a molecule by a frozen molecular fragment was tested further in a case of the dissociation reaction of the C? F bond in n-fluoropropane. Results from the Hartree–Fock, multiple reference double-excitation configuration–interaction and second-order Møller–Plesset methods are presented. The reproduction of potential energy surfaces as well as the reproduction of electron density distribution are in excellent agreement with extended basis-set calculations. Different choices of fragments to be frozen have been examined.     

Ab initio MRD–CI calculations on cubane (neutral,carbocation, carboanion) and dissociation of nitrocubanes based on localized orbitals

Ab initio MRD –CI calculations based on localized orbitals were carried out for cubane (neutral, carbocation, carboanion) both in our customary MODPOT basis set and in an all-electron 4–31G basis set. The calculated MRD –CI charge distributions on C1 (the skeletal atom from which the H^? or H⁺ was removed) (ab initio MODPOT neutral 4.221, carbocation 3.796, carboanion 4.282; all-electron 4–31G neutral 6.171, carbocation 5.717, carboanion 6.078) indicate that the + or - charge does not remain localized on C1 but redistributes itself. This has significant implications for preparative reactions of energetically substituted cubanes. The MRD –CI population analyses differ somewhat from the SCF population analyses, especially in the calculated total overlap populations. To investigate this effect on electrostatic molecular potential contour (EMPC ) maps generated from SCF or MRD –CI wave functions, we wrote additional routines to calculate EMPC maps from MRD –CI wave functions. The EMPC maps generated from SCF or MRD –CI wave functions are different if the molecule needs an MRD –CI multideterminant wave function to describe it adequately. The EMPC map is a one-electron property. One-electron properties are derived from the 1-matrix. The 1-matrix is different for SCF or MRD –CI wave functions. Thus, all the one-electron properties (EMPC maps, population analyses, bond deviation indices, etc.) are different when calculated from SCF or MRD –CI wave functions if MRD –CI wave functions are necessary to describe a system properly. We calculate these one-electron properties from the 1-matrix from the final natural orbitals. Our preliminary calculations for the dissociation pathway indicate it takes more energy to dissociate a bond in 1-nitrocubane than in octanitrocubane. Even in their ground electronic states at equilibrium geometry, both 1-nitrocubane and octanitrocubane require MRD –CI wave functions to describe them properly. The c² of the single determinant SCF wave function is only 0.8401 for 1-nitrocubane and 0.8300 for octanitrocubane. There are contributions from skeletal excitations as there are for cubane itself as well as excitations involving the nitrogroup. As the bond in nitrocubane is dissociated to 8.00 bohrs, the c² of the SCF contribution drops to only 0.4606 (1-nitrocubane) and 0.4445 (octanitrocubane). At this C₁? N₁ intermolecular distance, the largest excitations are in the C₁? N₁ bond: (C₁? N₁)² → (C₁? N₁*)², (C₁? N₁) → (C₁? N₁*). We also calculated the first electronically excited state for the dissociation pathway for selected points for both 1-nitrocubane and octanitrocubane.     

Benzodifurans. I. The synthesis of benzo[1,2-b:5,4-b]difuran and some methyl analogs

The first parent benzodifuran (XVI) and three di- and trimethylated derivatives have been synthesized and screened for erythemal activity (negative response). Two benzodifurans were prepared from resorcinol and 2-methylresorcinol by acetylation, Fries rearrangement, alkylation of the resulting 4,6-diacetylresorcinols with ethyl bromoacetate, saponification, and then cyclization of the (4,6-diacetyl-1,3-phenylenedioxy)diacetic acids. Another was prepared from the Claisen rearrangement product of 1,3-bis(allyloxy)-2-methylbenzene by acetylation, bromina-tion, and cyclization. Ozonolysis of the Claisen rearrangement product gave additional support to the formulation of o-hydroxyphenylaeetaldehydes as cyclic hemiacetals. The parent benzodifuran was synthesized from 5-formyI-6-hydroxybenzofuran, which was prepared in two steps from 5-bromo-6-methoxybenzofuran. Alkylation of the former with ethyl bromoacetate, saponification, and cyclization furnished benzo[1,2-b.5,4-b ]difuran. The ultraviolet and nuclear magnetic resonance spectra of the four benzodifurans are compared.     

Graph theoretical characterization and computer generation of certain carcinogenic benzenoid hydrocarbons and identification of bay regions

An algorithm is developed for generating and characterizing carcinogenic catacondensed benzenoid hydrocarbons. The bay regions in these structures are identified by a technique that we developed at Johns Hopkins. Using the three-digit code proposed by Balaban, and the concept of ring adjacency matrix expounded here, we generate catacondensed benzenoid hydrocarbons in the computer and identify the number of potentially carcinogenic bay regions in each of them. The results of computer generation agree with the combinatorial enumeration of Harary and Read. All structures containing up to five rings and some with six rings and the number of bay regions in these are presented. Computer results for the structures and bay regions of all seven-, eight-, and nine-membered unbranched catacondensed benzenoid hydrocarbons and the number of bays are available from the authors.