Liquefaction of sugar cane bagasse with formate and water

Sugar cane bagasse is available in large quantities in Brazil. Its liquefaction with $\text{formate}\text{inert}$ gas and $\text{base}\text{CO}$ in water is studied. The $\text{formate}\text{inert}$ gas system is the most effective under certain conditions, resulting in higher conversion and better yields of heavy oils. However, the heavy oils are highly oxygenated and solidify on standing in air. As a byproduct, considerable amounts of water-soluble, unextractable carboxylic acids are formed. Systematic studies are carried out with the $\text{formate}\text{inert}$ gas system to determine the reaction conditions appropriate for a future semi-continuous bench-scale reactor. A possible mechanism for the conversion reaction with formate is discussed.     

Characterization of cellulose triacetate membranes, produced from sugarcane bagasse, using PEG 600 as additive

Cellulose Acetate (CA) produced from sugarcane bagasse cellulose was used to produce membranes, using poly(ethylene glycol) (PEG 600) as additive. Results showed that PEG 600 was washed out the membranes during the preparation step. Thermal Analysis showed that the temperature of degradation of the membranes increased in 10 °C when PEG 600 was added to the composition, but did not change as more PEG 600 was added in the composition. On the other hand, the crystalline content (%C) of the membranes increased as PEG 600 was added. The addition of PEG 600 also increased the resistance of the membranes to pressure and the pure water flux rate, but membranes produced with PEG 600 content lower than 5% did not present water flux. PEG 600 also increased the coefficient of ion diffusion of the membranes.     

Hydrolysis of sugar cane bagasse with hydrochloric acid,promoted by metallic cations

Lithium chloride, in combination with commercial grade hydrochloric acid, is very effective in the hydrolysis of prehydrolysed sugar cane bagasse. After 10 min at 50°C the holocellulosic portion is completely dissolved and after 20 min most of the sugar oligomers are hydrolysed to monomers, making the time-and energy-consuming post-hydrolysis unnecessary. With longer reaction times the sugars start to reoligomerise and decompose. Zinc chloride is a milder promoter, requiring post-hydrolysis even after reaction for 30 min at 50°C. On the other hand, it does not decompose the sugars giving the highest sugar yields after prolonged reaction time and post-hydrolysis. Ferric chloride is mostly ineffective in the hydrolysis of cellulose but is a good promoter of the hydrolysis of the sugar oligomers, under the reaction conditions.     

Diffusion of solvent from a cast cellulose acetate solution during the formation of skinned membranes

The transport of solvent out of a cast cellulose acetate (CA) solution into the coagulation bath during membrane formation is treated as a diffusion process. From the increase of solvent concentration in the bath with time (solvent leaching experiments) an overall solvent diffusion coefficient has been calculated. In size these coefficients compare well to mutual pseudo-binary solvent-non-solvent diffusion coefficients determined by means of a classical boundary broadening method applied to ternary solutions with fixed CA concentration, but with a gradient in solvent-nonsolvent composition. Since binary polymer-solvent interdiffusion coefficients are at least one order of magnitude lower, it is concluded that the diffusion of solvent into the coagulation bath is essentially a pseudo-binary solvent-non-solvent diffusion process. Combination of experimental results with model calculations for the effect of a thin dense skin on the diffusion of solvent out of the sublayer shows that the casting-leaching diffusion coefficient can be used to describe the out-diffusion of solvent from the layer under the skin provided that the relative skin resistance is not too high, or that the skin thickness is small.     

Modification of cellulose acetate: Its characterization and application as an ultrafiltration membrane

The development of cellulose acetate blend membranes using a commercial grade Mycell cellulose acetate and cellulose diacetate with suitable pore structure is discussed. These membranes were characterized in terms of resistance of the membrane, pure water flux, the molecular weight cutoff, water content, pore size, and porosity. The removal of copper metal ions by this blend membrane using polyethyleneimine as a chelating agent was studied. The effects of copper ion concentration and casting solution composition on separation are also discussed. A possible correlation between feed and permeate concentration of copper ion is evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1939–1946, 1998     

The use of the simplex method to characterize dry cellulose acetate membranes for gas separations

The normal and log-normal distributions are used to describe the pore size distribution of dry asymmetric cellulose acetate membranes for CO₂/CH₄ separations. Various optimization techniques are implemented to determine the distribution parameters R and σ as well as the constants A₁, and A₂, related to pore structure and surface transport. respectively. By using the Simplex method, a unique solution for the characterization parameters is easily obtained irrespective of the starting search point. The permeation data of helium was used to characterize the membranes and determine the flow parameters which can be used to predict the performance of those membranes in separating CO₂/CH₄ mixtures.     

Influence of quench medium on the structure and gas permeation properties of cellulose acetate membranes

Integrally skinned asymmetric cellulose acetate membranes made by the wet phase inversion for removal of CO₂ from natural gas were investigated. The membrane was cast with the membrane-forming systems of cellulose acetate–acetone and quench media, such as methanol, ethanol and isopropanol, respectively, without heat-treating and multistage exchange process. By means of evaluation on separating characteristics of the membrane for CO₂/CH₄, observation of morphologies by scanning electron photomicrographs and analysis of the phase diagrams on the membrane-forming systems, it has shown that the membrane-forming system of cellulose acetate–acetone–methanol is quite suitable to prepare integrally skinned asymmetric cellulose acetate membranes for gas separation with good selectivity CO₂/CH₄ = 30 and flux coefficient = 2.4 × 10⁻⁵ cm³/cm² − s − cm Hg. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1269–1276, 1998     

Preparation and Characterization of Cellulose Acetate/Aminated Polysulfone Blend Ultrafiltration Membranes and their Application Studies

Abstract

Ultrafiltration membranes are largely being applied for heavy metal ion separations from aqueous streams. Cellulose acetate (CA) and aminated polysulfone (APSf) based membranes are prepared in the absence and presence of the polymeric additive, polyethylene glycol, PEG 600, in various compositions. The effects of polymer blend composition and additive concentration on compaction, pure water flux, membrane hydraulic resistance, water uptake, and contact angle has been investigated to evaluate the performance of the membranes and the results are discussed. Surface and cross-sectional morphologies of membranes were also analyzed using scanning electron microscopy. Toxic heavy metal ions such as Cu²⁺, Ni²⁺, Cd²⁺, and Zn²⁺ were separated by the blend membranes using polyethyleneimine (PEI) as polymeric ligand. The rejection and permeate flux efficiencies of the blend membranes are compared with pure cellulose acetate membranes.     

Synthesis and characterization of fluorinated polyacrylate–cellulose acetate butyrate interpenetrating polymer networks

Fluorinated polyacrylates are highly hydrophobic and oleophobic. However, their poor mechanical properties prevent their development in many applications. Combination of a fluorinated polyacrylate network with a rigid cellulose acetate butyrate (CAB) network in an interpenetrating polymer network (IPN) architecture is an effective method for improving the mechanical properties of fluorinated polyacrylates. IPNs combining poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate) (polyAcRf6) with CAB were prepared according to an in situ polymerization/crosslinking synthesis. CAB was crosslinked by addition between unmodified hydroxyl groups and the isocyanate of a pluri‐isocyanate crosslinker. The fluorinated network was obtained through free‐radical copolymerization of 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate with poly(ethylene glycol dimethacrylate). The rates of formation of both networks were followed using Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) of IPNs show a single glass transition temperature and a single mechanical relaxation temperature, which are characteristic of a high degree of interpenetration between the partner networks. The mechanical properties of IPNs are greatly improved compared with those of the single fluorinated network. CAB/polyAcRf6 IPNs were prepared, and characterized using DSC and DMTA as well as contact angle measurements for their surface properties. As hoped, the mechanical properties of such materials are much improved compared with those of the fluorinated partner alone. Copyright © 2010 Society of Chemical Industry     

Studies on the composites of cellulose triacetate (prepared from sugar cane pulp) and gelatin

Sugarcane waste (bagasse) which is hitherto discarded as a waste at sugarcane parlors and jaggery units was recovered and cellulose triacetate (CTA) was prepared from the same, after isolation of cellulose. Using this CTA, CTA–gelatin composites were prepared. The materials prepared (i.e., sugarcane cellulose, CTA, CTA–gelatin composites) were characterized for their mechanical properties, water absorption capacity, infrared spectroscopy, and scanning electron microscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 847–853, 2001     

Synthesis and characterization of interpenetrating networks from polycarbonate and cellulose acetate butyrate

Polycarbonates (PC) are currently used for organic optical glass; nevertheless they show a poor impact resistance which may be increased by combination with cellulose acetate butyrate (CAB) into a PC/CAB interpenetrating polymer network (IPN), without altering the material transparency as we show here. A series of rigid IPNs based on an aliphatic polycarbonate and CAB was prepared through in situ polymerization techniques. The kinetics of the formation of two networks in the IPNs were studied by FTIR spectroscopy. Effects of the CAB cross-linking and weight proportions of the two components in the IPNs were investigated by dynamic mechanical thermal analysis.     

SEM study of the morphology of asymmetric cellulose acetate membranes produced from recycled agro-industrial residues: sugarcane bagasse and mango seeds

Cellulose, obtained both from sugarcane bagasse and mango seeds, was used for synthesizing cellulose acetate in order to produce asymmetric membranes. These were compared to membranes of commercial cellulose acetate (Rhodia). All produced membranes were asymmetric, characterized by the presence of a dense skin and a porous support. Differences regarding the morphology of the surfaces as well as of the porous support can be noticed. Scanning Electron Microscopy (SEM) showed that the morphology of the superficial layer, responsible for transport, depends on the different lignin content of the starting material and also on the viscosity average molecular weight of the cellulose acetates produced from sugarcane bagasse, mango seed, and Rhodia’s commercial cellulose acetate.     

Effect of LHW,HCl, and NaOH pretreatment on enzymatic hydrolysis of sugarcane bagasse: sugar recovery and fractal-like kinetics

Conversion of lignocellulose to sugars involves two main processes, namely pretreatment and enzymatic hydrolysis. Lignocellulose pretreatment leads to the degradation of enzymatic recalcitrance of substrate for achieving efficient saccharification. In this study, liquid hot water (LHW), hydrochloric acid (HCl), and sodium hydroxide (NaOH) were as reagents used to pretreat sugarcane bagasse (SB). Results showed that LHW, HCl, and NaOH pretreatment could solubilize 95.3%, 94.7% xylan and 88.7% lignin, respectively. Enzymatic hydrolysis of pretreated SB showed that the maximum glucose (26.0?g/L) and xylose (12.7?g/L) concentration were produced by NaOH pretreatment, and slightly more glucose and less xylose were produced after HCl pretreatment compared to LHW pretreatment. Addition of Tween 80 or xylanase could significantly improve both glucose and xylose production. At 48?h, the glucose increase for LHW, HC1 and NaOH pretreatment was 38.3%, 26.4% and 8.0%, respectively, and the xylose increase for them was 35.0%, 24.9% and 1.7%, respectively. Fractal-like kinetics showed that the value of rate constant increased after the addition of Tween 80 or xylanase, and the efficiency of enzymatic hydrolysis mainly depended on rate constant other than fractal dimension of substrate. Totally, substrate accessibility was dominated for efficient of lignocellulose to sugar compared to enzyme loading. The application of fractal-like theory on the heterogeneous enzymatic hydrolysis of lignocellulose was quite successful.     

Miscibility, free volume behavior and properties of blends from cellulose acetate and castor oil-based polyurethane

A series of blend films from cellulose acetate (CA) and castor oil-based polyurethane (PU) were prepared. Morphology, miscibility, free volume behavior and properties of such blend films were investigated by wide-angle X-ray diffraction (WXRD), infrared, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), positron annihilation lifetime spectroscopy (PALS), thermogravimetric analysis and tensile test. The results indicated that lager free volume cavities did not form at the interface of two polymers although a certain degree of phase separation was found by the studies of SEM and DSC. Strong intermolecular hydrogen bonding interactions at the interface, which was proved by Fourier transform infrared spectroscopy, favors even better molecular packing, that is, PU dispersed in CA continuous phase to form fine microphase separation domain in the CA-rich blends. Due to such special interactions in the fine microphase separation domain structure, optimized properties of tensile strength, breaking elongation and cold-resistivity were obtained in the blend film with 75 wt% CA. The toughness of all the blend films was significantly higher than that of the film CA, owing to the plasticizing of PU elastomer in the blends.     

Miscible blends of cellulose acetate hydrogen phthalate and poly(vinyl pyrollidone) characterization by viscometry,ultrasound, and DSC

Miscibility characteristics of cellulose acetate hydrogen phthalate (CAP) and poly(vinyl pyrollidone) (PVP) have been investigated by solution viscometric, ultrasonic, and differential scanning calorimetric (DSC) methods. From viscosity measurements, Krigbaum and Wall polymer–polymer interaction parameter Δb was evaluated. Ultrasonic velocity and adiabatic compressibility have been plotted versus blend composition and are found to be linear. Variation of T_g with composition follows Gordon–Taylor equation. T_g values have also been calculated from the Fox equation. The results obtained reveal that CAP forms a miscible blend with PVP in the entire composition range. Compatibility may be due to the formation of hydrogen bonding between the carbonyl group of PVP and the free‐hydroxyl group of CAP. Compatibility has also been confirmed from dielectric measurements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 859–867, 2000     

Components of the sex pheromone of the female sugar cane borer,Chilo sacchariphagus (Bojer) (Lepidoptera: Pyralidae)

The female sex pheromone of the sugar cane borer,Chilo sacchariphagus, has been shown to contain the two structurally related compounds, (Z)-13-octadecenyl acetate (I) and (Z)-13-octadecen-1-ol (II). These components were detected in female abdominal tip extracts by gas-liquid chromatography (GLC) combined with electroantennography (EAG), and were identified by their GLC behavior, microozonolysis, and interconversion, and by comparison of natural and synthetic material. Field tests in Mauritius showed that traps baited with components I and II combined in ratios from 11 to 91 caught maleC. sacchariphagus moths, and that the 71 ratio was comparable in performance with a virgin female moth. Neither component presented separately in traps caught significant numbers of moths.     

Synthesis,characterization, and anti-fouling properties of cellulose acetate/polyethylene glycol-grafted nanodiamond nanocomposite membranes for humic acid removal from contaminated water

Polyethylene glycol-grafted nanodiamond (ND-PEG) was synthesized from pristine detonation NDs and utilized to prepare novel cellulose acetate/polyethylene glycol-grafted nanodiamond(CA/ND-PEG)nanocomposite membranes. Due to unique thermal, mechanical, and antibacterial properties and very easy cleaning of fouled ND-embedded CA nanocomposite membranes, we tried to investigate the performance of CA/ND-PEG membrane for humic acid (HA) removal from contaminated water. Surface functionalization was confirmed by Fourier transform infrared spectroscopy and thermogravimetry analysis. Pristine and functionalized ND with different concentration was added in the casting solution containing CA. The prepared membranes were characterized using contact angle, mechanical strength, scanning electron microscopy (SEM), transmission electron microscopy, and permeation tests. SEM micrographs of the surface of the membranes depicted the increase in the number of pores by the addition of ND and especially ND-PEG into polymer matrix. The results indicated that the nanocomposite membrane with 0.5 wt% ND-PEG exhibited excellent hydrophilicity, mechanical properties, permeability, high rejection, high abrasion resistance, and good anti-fouling performance. The HA adsorption on the membrane surface decreased from 2.85 to 2.15 mg cm^?2 when the ND-PEG content increased from 0 to 0.5 wt%. Most importantly, the HA filtration experiments revealed that the incorporation of ND and especially ND-PEG particles reduced membrane irreversible fouling, dramatically. Meanwhile, the analysis of the fouling mechanism based on Hermia’s model revealed that cake formation is a prevailing mechanism for all membranes.     

Morphological and structural formation of the regenerated cellulose membranes recovered from its cuprammonium solution using aqueous sulfuric acid

Morphological and structural formation of the regenerated cellulose membranes from its cuprammonium hydroxide solution by acid coagulation was investigated. Scanning electron microscopic observation revealed that the morphology of the membranes changed drastically as functions of both the cellulose concentration in the original cellulose solution C_Cell and the concentration of sulfuric acid as a coagulant C_H2SO4. It was found that at a constant polymer concentration (8 wt %) the membrane prepared by using 5 wt % aqueous sulfuric acid exhibits higher water flux, far smaller swelling anisotropy parameter L_t, and larger porosity P_r with a thinner skin structure, and these parameters were proven to be associated with lower (11 0) crystal plane orientation coefficient f_{∥(11 0)} compared with those for the membranes obtained by aqueous sulfuric acid with more than 10 wt %. On the other hand, at constant coagulant concentration (10 wt %) the membrane prepared by using the polymer solution with 5 wt % shows far greater P_r with practically no distinct skin structure; hence, a higher flux. The drastic changes in the morphology and structural parameters as functions of C_Cell and C_H2SO4 were found to be well correlated with abrupt changes in material transportation (copper ion, ammonium ion, and water) from the polymer solution to aqueous coagulants as a function of C_Cell and C_H2SO4. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1669–1678, 1999     

Effect of maleic anhydride treatment on steam and water absorption of wood polymer composites prepared from wheat straw,cane bagasse,and teak wood sawdust using Novolac as matrix

Wheat straw, cane bagasse, and teak sawdust (agrowaste) were sieved up to a 425‐μm mesh size and employed for sheet preparation with and without maleic anhydride (MA) treatment using Novolac resin in a 50 : 50 (w/w) ratio. The shore D hardness of MA treated and untreated wood polymer composites (WPCs) was measured. The MA treated WPCs showed 2–3 times more hardness than that of the untreated respective WPCs. Moisture absorption had a detrimental effect on the mechanical properties of the WPCs. MA treatment restricted swelling and water and steam absorption in the agrowaste. Teak sawdust showed the best results in all respects among the three WPCs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2963–2967, 2000     

Development of new ionomer blend membranes,their characterization,and their application in the perstractive separation of alkenes from alkene–alkane mixtures. I. Polymer modification,ionomer blend membrane preparation,and characterization

In this contribution, the synthesis and characterization of novel ion‐exchange blend membranes which contain the SO₃Ag group for the application in the perstractive separation of alkene–alkane mixtures, where the Ag⁺ ion serves as facilitated transport site for the alkene via formation of a pi complex with the alkene double bond, is presented. In this part of the article, the synthesis and characterization of following blend membrane types are described: (1) acid–base blend membranes of ortho‐sulfone‐sulfonated polysulfone (PSU) with ortho‐sulfone‐diaminated PSU; (2) blend membranes of ortho‐sulfone‐sulfonated PSU with unmodified PSU; (3) blend membranes of ortho‐sulfone‐sulfonated PSU with ortho‐sulfone disilylated PSU. The differently modified PSU types were characterized via ¹H nuclear magnetic resonance (¹H‐NMR). The acid–base blend membranes were characterized via Fourier transfer infrared (FTIR) spectroscopy. It could be indirectly proved that formation of PSU–SO₃ ⁺H₃N–PSU ionic crosslinks takes place. Transmission electron microscopy (TEM) investigations of (1) and (2) yielded the results that these blends are inhomogeneous at the microscopic scale. Mechanical stabilization of these blends is accomplished by physical entanglement of the different macromolecules. The blends (3) were macroscopically inhomogeneous due to the strong difference in hydrophilicity of the blend components. Only the blend 90% PSU–SO₃H 10% PSU[Si(CH₃)₃]₂ formed a blended membrane. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 428–438, 1999