Hydrolysis of pentosans in bagasse pith

Work has been conducted on the hydrolysis of pentosans in bagasse pith as the first part of a study of the chemistry of bagasse processing aimed at establishing an integrated industry. Bagasse pith is the fine part screened out and discarded as waste during the preparation of raw material for bagasse pulping plant. By using dilute sulphuric acid at a concentration less than 2% by weight and at a temperature lower than 165°C, pith is hydrolysed to pentoses in a yield of 80–90% based on potential pentoses in pith. Hydrolysis of pentosans in pith, within the scope of experiment, seems to be a first order reaction. However, the semi-logarithmic time plot for the hydrolysis of potential pentoses in the residue consists of two straight lines of different slope. This may be explained on the assumption that bagasse pith contains two major fractions of pentosans that are hydrolysed at different rates. Saeman's equation for hydrolysis of wood with sulphuric acid may be adapted to represent dependence of rate constant K on acid concentration C and reaction temperature T in hydrolysis of the two major parts of pentosans in bagasse pith. K₁ = 6.4 × 10⁵C^1.02 exp (?6378/T) K₂ = 10.7C^0.363 exp (- 2826/T)     

Hydrolysis of aromatic sulphonic acids in industrial effluents. I. Hydrolysis of 7-hydroxy-2-naphthalenesulphonic acid

The protodesulphonation of 7-hydroxy-2-naphthalenesulphonic acid (F-acid) was investigated in dilute aqueous sulphuric acid at temperatures of 522–553 K. The hydrolysis of the sulpho group is irreversible and F-acid can be completely converted into 2-naphthol in a short time. The hydrolysis rate depends strongly on the temperature and on the sulphuric acid concentration; a rate equation was derived from the experimental data.     

Evaluation of acids and cellulase enzyme for the effective hydrolysis of agricultural lignocellulosic residues

This paper reports the results of experimentation carried out to compare the ability of mineral acids (HCl and H₂SO₄) and cellulase enzyme (from Trichoderma reesei QM 9414) in the saccharification of corn-cob, groundnut shell, sugarcane bagasse and wheat straw. With the exception of corn-cobs, acids proved to be better saccharifying agents than the cellulase complex, but the former gave a poor substrate for alcoholic fermentation since the saccharified mashes contained large amounts of pentoses which are not metabolized by most strains of yeast. In addition, both acids and enzymes have been found to be substrate specific. Maximal saccharification of groundnut shell, sugarcane bagasse and wheat straw were obtained with sulphuric acid at 15.0, 5.0 and 5.0% (v/v) under 15, 15 and 15 psi pressure for 15, 30 and 30 min, respectively; whereas hydrochloric acid at 7.5% (v/v) with. autoclaving for 30 min at 10 psi resulted in maximum saccharification of corn-cob. However, the order of susceptibility of substrates to enzymatic attack was corn-cob > wheat straw > sugarcane bagasse > groundnut shell. Increase in enzyme concentration (1–4 IU ml^?1) and treatment duration (12–72 h) improved saccharification, but increases in substrate concentration (>5.0%, w/v) had an inhibitory effect on the hydrolytic ability of the cellulase enzyme complex. Of the various substrate-acid ratios tested, a ratio of 1:8 was found to be optimal for the eflcient hydrolysis of the substrates under study.     

Acid and enzymatic saccharification of agricultural mixed polymers for alcohol production

The paper reports the evaluation of potentials of acid (HCl and H₂SO₄) and enzymatically (cellulase) saccharified corncob, groundnut shell, sugarcane bagasse and wheat straw biopolymers for ethanol production. Of the three yeast isolates tested, Saccharomyces cerevisiae var. ellipsoideus was found to be most efficient, closely followed by Kluyveromyces marxianus NCYC 179 in its ability to ferment enzymatically hydrolysed mash of all the substrates tested to ethanol. However, S. cerevisiae NCYC 240 and acid hydrolysed agricultural polymers were found to be a poor organism and poor substrates, respectively, for ethanol fermentation. The order of ethanol production on substrate basis was corncob > wheat straw > sugarcane bagasse > groundnut shell biomass biopolymer. An incubation period of 24 h was found optimum for the optimal production of ethanol by S. cerevisiae var. ellipsoideus in both acid and enzymatically hydrolysed agricultural residues.     

Studies on determination of molecular weight for ultrahigh molecular weight partially hydrolyzed polyacrylamide

The molecular weight characterization of partially hydrolyzed polyacrylamide (HPAM) for enhanced oil recovery use is rather difficult because of its ultrahigh molecular weight copolymer and polyelectrolyte behaviors in solution. In this work the effects of aqueous NaCl solution concentration and degree of hydrolysis of polymer on molecular dimension were studied. A simple and precise method for determining molecular weight of HPAM is presented. The molecular weight of HPAM with any degree of hydrolysis can be calculated from the [η]−M_w equation of unhydrolyzed PAM in an H₂O system by measuring , of HPAM obtained in aqueous NaCl solutions by extrapolating salt concentration to infinity. Because the values of of HPAM of different degrees of hydrolysis are all equal to the corresponding [η] value of the unhydrolyzed PAM of the same degree of polymerization, the molecular weight of HPAM of any degree of hydrolysis can thus be calculated from the [η] − M_w equation for PAM homopolymer. © 1996 John Wiley & Sons, Inc.     

Hydrolysis of 1,4-cyclohexanedimethanol-based copolyester

The solid state hydrolysis of a copolyester based on a mixture of 1,4-cyclohexanedimethanol and ethylene glycol condensed with terephthalic acid was studied at 100°C and 57 to 96 kPa water vapor partial pressure (55% to 95% relative humidity). The equilibrium water sorption in weight percent (C_∞) was found to be where P is the water vapor partial pressure in kPa. For specimens 0.32-cm thick, it took about 24 h to reach 0.9C_∞. The intrinsic viscosity (IV) was measured and used to calculate the relative change in molecular weight (M?_w) from the relationship IV ∝? (M?_w)^0.7. The decrease in molecular weight was linear with time, and the rate of decrease was found to be proportional to C_∞; the empirical correlation is where the rate constant, k, is in day^?1. A decrease of 50% in M?_w was observed after 22 days at 95% relative humidity.     

Saccharification of bagasse pith

Work is reported here on a process for the saccharification of bagasse pith, as the second part of a study of bagasse processing aimed at establishing an integrated industry. A method for pentose preparation from bagasse pith is designed on the basis of the conclusions reached in the first part of the study. It is preferable to Scholler's process in recovery of sugar and in concentration of the sugar solution. A process for glucose production from pentose-exhausted cellulosic residue is also developed to avoid the difficulties encountered in the Udic-Rheinau process. It seems to be a promising continuous process capable of giving a higher yield of glucose with less acid at a higher speed and affording favourable conditions for crystallising the dissolved glucose.     

Synthesis and studies of egyptian bagasse pith phenol formaldehyde cationic exchangers

The article is concerned with a simple method for preparing cationic resins from polycondensation of Egyptian bagasse pith (as a source of cheap and renewable material) with phenol and paraformaldehyde as a cross-linking agent. Optimum principal reaction conditions of the preparation and properties are determined and compared with resin without bagasse pith content. The Synthesized resins are stable in water, organic solvents, thermal treatment, and mineral acids (1M). The sample having a cation exchange capacity up to 3.92 meq g^?1 of dry resins are being introduced as new cationic exchangers. The synthesized resins are used in the study of the possible separation of univalent cations. The rational thermodynamic equilibrium constants (In K) are calculated for Li⁺ ?Na⁺ exchanges on the resins having a various amount of bagasse pith. The thermodynamic parameters are computed and suitable explanations are described. © 1994 John Wiley & Sons, Inc.     

Nitrogen containing additives in soda pulping of bagasse pith

Unbleached soda pulp was prepared from Egyptian bagasse pith by varying the alkali concentration and the time of heating at the boiling point of the liquor under atmospheric pressure. A linear relationship was observed between the dissolved pith and the dissolved lignin. Pulping with alkali concentration higher than 10% but not exceeding 16% was more effective, since more delignification took place with lower dissolved pith percentage. p- And m-nitrobenzoic acids and also hydroxylamine hydrochloride had a slight or no effect on the yield of the pulps. The alkali solubility percentage of the pulps prepared in the presence of any of the additives was lower than the control pulp. The delignification was enhanced more on the addition of hydroxylamine hydrochloride than p-nitrobenzoic acid, while m-nitrobenzoic acid seemed to have no effect. The yield of the pulps thus prepared, as determined by weighing, showed lower values than those determined by a chemical method. The soda delignification rate was shown to be proportional to the amount of unremoved lignin and the concentration of alkali in the liquor. The delignification reaction was found to follow approximately first-order kinetics.     

Thermal decomposition of potassium persulfate in aqueous solution at 50°C in an inert atmosphere of nitrogen in the presence of acrylonitrile monomer

The rate of thermal decomposition of persulfate in aqueous solution in the presence of acrylonitrile (AN) monomer (M) and of nitrogen, may be written as: in the concentration range of persulfate (1.8 to 18.0) ×10^-3, and of monomer (M), 0.30 to 1.20, mol dm^-3. It was observed that the pH of the solution containing persulfate and monomer did not alter during polymerization if the monomer concentrations were close to its solubility under the experimental conditions. Conductance of the aqueous solutions of persulfate and monomer was found to decrease during the reactions. In an unbuffered aqueous solution containing only persulfate, however, the pH was found to decrease continuously at 50°C with time, while the conductance of the solution was found to increase. The monomer (AN) had no effect on the glass electrodes of the pH meter in aqueous solutions, and also on the electrodes of the conductivity cell. It has been suggested that the secondary or induced decompositions of persulfate were due to the following elementary reactions: where (M_j^· radicals (j = 1 to 10) are water-soluble oligomeric or polymeric free radicals. k_x and k_y at 50°C have been estimated as 1.70 X 10^-5 and 5.08 × 10³ dm³ mol^-1 s^-1, respectively. By measuring pH of freshly prepared persulfate solutions at 25°C, it is suggested that 0.05–0.30% of persulfate reacts molecularly with water (i.e., hydrolysis), as soon as it (10^-3 to 10^-2 mol dm^-3) is added to distilled water (pH 7.0). This hydrolysis was found to be stopped in dilute sulfuric acid solution (pH 3–4).     

Stability of hydrolase enzymes in ionic liquids

In this work we attempted to evaluate the stability of penicillin G acylase (PGA) from Escherichia coli in their native form and free Candida antarctica lipase B (CaLB) in ionic liquids (ILs) at low water content. The hydrolysis of penicillin G to 6‐aminopenicillanic acid (6‐APA), and phenyl acetic acid (PAA) catalysed by PGA and the synthesis of butyl butyrate from vinyl butyrate and 1‐butanol catalysed by CaLB were chosen as activity tests. The influence of these new solvents on enzyme stability was studied by incubating the enzyme (PGA or CaLB) in ILs based on dialkylimidazolium cations associated with perfluorinated and dicyanamide anions at a given temperature. Stability studies indicate that CaLB and PGA exhibited greater stability in water‐immiscible ILs than in water‐miscible ILs. Specifically, native PGA shows greater stability in IL media than in organic solvents. For example, a half‐life time of 23 h was obtained in 1‐ethyl‐3‐methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, , which was about 2000‐fold higher than that in 2‐propanol. The higher half‐life time of CaLB was observed in (t_1/2 = 84 h).     

Determination of carboxyl endgroups and comonomers in poly(ethylene terephthalate) with hydrazine

On complete hydrazinolysis of poly(ethylene terephthalate), terephthalomonohydrazide is formed from carboxyl-end terephthaloyl residues in a quantity equivalent to the content of carboxyl endgroups in the polymer. The compound is separated from the reaction mixture by ion exchange and determined photometrically [epsiv;₂₄₀ in 0.1 N HCl = 16,700 (1000 cm²/mole)]. A COOH determination carried out in this way is endgroup specific and, unlike titration, is not subject to interference by ionogenic fiber additives. Aromatic comonomers with acidic substituents (e.g., 5-sulfoisophthalic acid) in chemically modified, cationically dyeable poly(ethylene terephthalate) are determined simultaneously with the carboxyl endgroups by the same analytical method. In this case, the terephthalamonohydrazide and 5-sulfoisophthalodihydrazide are separated by ion exchange, and the difference in their spectral behavior is used for quantitative determination with the aid of a two-component analysis: where c₁c₂ = concentration of terephthalomonohydrazide and 5-sulfoisophthalodihydrazide, respectively; and D₂₄₀ D₂₁₂ = optical density at 240 and 212 nm, respectively. The content of carboxyl endgroups in polyether esters poly(p-(2-ethyleneoxy)-benzoate), is determined on the basis of the p-(β-hydroxyethoxy)benzoic acid [epsiv;₂₅₈ in 0.1 N HCl = 16,100 (1000 cm²/mole)] liberated from carboxyl-end monomer units by hydrazinolysis. For copolyether esters with p-(β-hydroxyethoxy)benzoic acid as a comonomer, the contents of carboxyl-end terephthalic acid and p-(β-hydroxyethoxy)benzoic acid are determined simultaneously with the acid of a spectrophotometric twocomponent analysis: where c₂, c₂ = concentration of terephthalomonohydrazide and p-(β-hydroxyethoxy)-benzoic acid, respectively; and D₂₄₀, D₂₅₈ = optical density at 240 and 258 nm, respectively.     

A one-point intrinsic viscosity method for polyethylene and polypropylene

A statistical analysis of dilute solution viscosity data for a wide range of polyethylene and polypropylene samples in Decalin at 135°C has shown that the Martin equation fits the experimental data better than the Huggins equation at higher values of [η]c. A grand average k of 0.139 is applicable to both polymers. Based upon this, tables have been calculated permitting the ready determination of [η] from a single relative viscosity measurement at a known concentration. The Martin equation has been put into a universal form, permitting [η] to be calculated from a measured η_sp if k and c are known. Graphs relating η_sp to [η] are included for use of the Martin equation over wide ranges of both k and c. It was found that the Solomon and Ciuta equation fits the experimental polyethylene and polypropylene data, and the reasons for this are discussed.     

The kinetics and mechanism of the chloride-chlorate reaction

The kinetics of the reaction have been studied at 25°C. in strong acid solution; the effects of acidity, chloride, chlorate and chlorine are reported. A mechanism is postulated to interpret the peculiar features of this reaction as well as the stoichiometry and some of the kinetics of the parallel reaction The mechanism involves HClO₂ and HOCl as intermediates General rate expressions are derived for the formation of chlorine dioxide and chlorine, and the individual rate constants are calculated. An expression is obtained for the relationship between the ratio of chlorine dioxide to chlorine produced and the ratio of chlorate to chloride.     

Analysis of pressure fluctuations in fluidized beds. II. Reconstruction of the data by the Fokker–Planck and Langevin equations

In this part of the sequel we develop a continuum representation of the pressure fluctuation time series p(t) for a fluidized bed (FB), analyzed in part I, by using stochastic methods based on the Markov processes. It is shown that the data may be represented by Markov series with a Markov time scale t_M that is estimated based on the data. Using the relation between the Markov processes and the Kramers–Moyal (KM) expansion that is a continuum equation that involves, in principle, an infinite number of coefficients, we represent the pressure fluctuation time series by a KM expansion. However, since the third and higher-order coefficients of the expansion are very small, the KM expansion reduces to a Fokker–Planck (FP) equation that represents p(t) in terms of a drift and a diffusion coefficients that are computed based on the data. The FP equation is, in turn, equivalent to a Langevin equation, which is used to reconstruct the data, i.e. generate the time series that mimic, in a statistical sense, the original data. Thus, the Langevin equation may also be used to make probabilistic predictions for the future values of the pressure over time scales that are of the order of the Markov time scale t_M. The accuracy of the reconstructed series and, hence, their continuum representation, is demonstrated. We also compute the frequency of level-crossing at a given level α, i.e. the relative frequency (probability) of occurrence of the event defined, for two times t_i−1 and t_i, by, , where P(x) is the probability of the event. Thus, yields the frequency that a given pressure fluctuation level may be expected. The average time that one should wait in order to observe the pressure at a given level again is also computed. The two quantities may be particularly important for modeling of the FBs. A relation is presented between the drift and diffusion coefficients of the FP equation and the Hurst exponent that has previously been used to describe the pressure fluctuation time series in terms of self-affine stochastic distributions.     

KINETICS OF ACID HYDROLYSIS OF PHASE-TRANSFERRED TETRAALKYLAMMONIUM THIOCYANATES

Solutions of tetraalkylammonium thiocyanates in dichloro-methane are hydrolysed by concentrated sulphuric acid in two stages; the first is transfer of thiocyanate ion to the aqueous layer independently of the pairing ion and the second is a homogeneous hydrolysis: the process is important for the regeneration of phase transfer extractants.     

Diffusion of electrolytes across inhomogeneous permselective membranes

Permeability of sulphuric acid through cation-exchange membranes of different inhomogeneity has been investigated. It has been found that the diffusion coefficient of the acid within the membrane D _i is related to that in the aqueous solution D_0,i by the equation: where V is the membrane volume fraction inaccessible for diffusion. This volume was calculated as the sum of the polymer volume fraction V_p and the volume fraction of the internal solution V_G with the local concentration of the ionogenic groups equal or higher than the concentration of the external electrolyte. Introducing the volume V into the equations by Meares, Prager and Yasuda it is possible to find a high correlation between D _i and f(V), which is related to the membrane structure and their inhomogeneity. The best results have been obtained with the equation of Prager; the calculated diffusion coefficients D_0,i for different membranes are then close to the coefficient of H₂SO₄ in a free aqueous solution.     

New catalysts for urea formation reactions. II. Catalytic activity of carboxylic acids

Carboxylic acids with weak acidities showed large catalytic activity. For instance, for chlorine-substituted acetic acid the activity increased with decreasing chlorine content. For benzoic acid derivatives, electron acceptor substituents, such as NO₂, CI, and OH, lowered the catalytic activity, while electron donor substituents such as alkyl and alkoxy groups increased it. Detailed study on the cure rate of polyureaurethane, with 2-methyl benzoic acid as a catalyst, showed that pot life (PL) and the minimum demolding time (DT) had a correlation with the catalyst amount [X] represented by the following equation: where A and B are constants. Further, use of appropriate amounts of the catalyst enhanced tensile strength at break for polyureaurethane.