Joseph R. Samaniuk

The effect of high intensity mixing on the enzymatic hydrolysis of concentrated cellulose fiber suspensions.

Enzymatic hydrolysis of lignocellulosic biomass in a high shear environment was examined. The conversion of cellulose to glucose in samples mixed in a torque rheometer producing shear flows similar to those found in twin screw extruders was greater than that of unmixed samples. In addition, there is a synergistic effect of mixing and enzymatic hydrolysis; mixing increases the rate of cellulose conversion while the increased conversion facilitates mixing. The synergy appears to result in part from particle size reduction, which is more significant when hydrolysis occurs during intense mixing.

Sorption and Interfacial Rheology Study of Model Asphaltene Compounds

The sorption and rheological properties of an acidic polyaromatic compound (C5PeC11), which can be used to further our understanding of the behavior of asphaltenes, are determined experimentally. The results show that C5PeC11 exhibits the type of pH-dependent surface activity and interfacial shear rheology observed in C6-asphaltenes with a decrease in the interfacial tension concomitant with the elastic modulus when the pH increases. Surface pressure-area (Π-A) isotherms show evidence of aggregation behavior and π-π stacking at both the air/water and oil/water interfaces. Similarly, interactions between adsorbed C5PeC11 compounds are evidenced through desorption experiments at the oil/water interface. Contrary to indigenous asphaltenes, adsorption is reversible, but desorption is slower than for noninteracting species. The reversibility enables us to create layers reproducibly, whereas the presence of interactions between the compounds enables us to mimic the key aspects of interfacial activity in asphaltenes. Shear and dilatational rheology show that C5PeC11 forms a predominantly elastic film both at the liquid/air and the liquid/liquid interfaces. Furthermore, a soft glassy rheology model (SGR) fits the data obtained at the liquid/liquid interface. However, it is shown that the effective noise temperature determined from the SGR model for C5PeC11 is higher than for indigenous asphaltenes measured under similar conditions. Finally, from a colloidal and rheological standpoint, the results highlight the importance of adequately addressing the distinction between the material functions and true elasticity extracted from a shear measurement and the apparent elasticity measured in dilatational-pendant drop setups.

Rheological modification of corn stover biomass at high solids concentrations

Additives were tested for their ability to modify the rheology of lignocellulosic biomass. Additive types included water-soluble polymers (WSPs), surfactants, and fine particles. WSPs were the most effective rheological modifiers, reducing yield stresses of concentrated biomass by 60–80% for additive concentrations of 1–2 wt. % (based on mass of dry biomass solids). Yield stress and plastic viscosity of rheologically modified biomass depended on WSP molecular weight and degree of substitution. The apparent shear stress-shear rate data are represented with the Bingham model. In the absence of WSP, the biomass exhibited a positive yield stress and a negative plastic viscosity, which suggests a nonmonotonic dependence of shear stress on shear rate. When WSP was added, the yield stress decreased and the plastic viscosity increased, becoming positive for sufficiently large WSP concentrations.

Soft-Glassy Rheology of Asphaltenes at Liquid Interfaces

The presence of asphaltenes in oil and water emulsions promotes emulsion stability, a major concern in the recovery of oil reserves. A number of mechanisms for this stabilizing effect have been proposed recently, including those that implicate the interfacial rheology of asphaltenes as a primary factor. We present interfacial shear rheological data for asphaltenes at liquid–liquid interfaces and show conclusively that asphaltenes at an oil–water interface exhibit a soft-glassy rheological behavior in agreement with the soft-glassy rheology (SGR) model. This characteristic allows the stabilization of emulsions via mechanical resistance to coalescence. GRAPHICAL ABSTRACT

Effects of process variables on the yield stress of rheologically modified biomass

Additives that alter the rheology of lignocellulosic biomass suspensions were tested under conditions of variable pH, temperature, and solid concentration. The effects of certain ions, biomass type, and time after the addition of rheological modifier were also examined. Torque and vane rheometry were used to measure the yield stress of samples. It was found that the effectiveness of rheological modifiers depends on pH over a range of 1.5 to 6, biomass type, concentration of certain ions, and time after addition. The time-dependent properties of rheologically modified biomass are sensitive to the type of rheological modifier, and also to mixtures of these additives, which can result in unexpected behavior. We show that time-dependent rheology is not correlated with time-dependent changes of the water-soluble polymer (WSP) in the aqueous environment, such as slow polymer hydration, suggesting that time-dependent changes in the polymer-fiber interaction may play a more significant role.

Pressure-driven flow of lignocellulosic biomass: A compressible Bingham fluid

Experimental data for the pressure-driven flow of concentrated lignocellulosic biomass (corn stover) in a circular pipe are presented. A positive curvature was observed in the pressure profile at steady state, both when the biomass was flowing, and for several minutes after the flow had stopped. After the flow into the pipe was stopped, biomass continued to be expelled for at least five minutes, suggesting that the material is compressible. Occasionally, the pressure and outlet flow rate exhibited rapid, transient fluctuations. The fluctuations would cease when dryer-than-average heterogeneities exited the pipe. A mathematical model is developed to treat the biomass as a compressible Bingham fluid with a density-dependent yield stress. This model quantitatively reproduces steady-state pressure profiles for both flowing and nonflowing states, and captures the transition between the two states after the inlet flow rate is set to zero. Our model cannot predict the rapid pressure fluctuations that appear to be associated with heterogeneities in composition.Experimental data for the pressure-driven flow of concentrated lignocellulosic biomass (corn stover) in a circular pipe are presented. A positive curvature was observed in the pressure profile at steady state, both when the biomass was flowing, and for several minutes after the flow had stopped. After the flow into the pipe was stopped, biomass continued to be expelled for at least five minutes, suggesting that the material is compressible. Occasionally, the pressure and outlet flow rate exhibited rapid, transient fluctuations. The fluctuations would cease when dryer-than-average heterogeneities exited the pipe. A mathematical model is developed to treat the biomass as a compressible Bingham fluid with a density-dependent yield stress. This model quantitatively reproduces steady-state pressure profiles for both flowing and nonflowing states, and captures the transition between the two states after the inlet flow rate is set to zero. Our model cannot predict the rapid pressure fluctuations that appear to b...