Yonghao Ni

Synthesis and characterization of cationically modified nanocrystalline cellulose

In this study, nanocrystalline cellulose (NCC) resulting from sulfuric acid hydrolysis of wood cellulose fiber, was rendered cationic by grafting with glycidyltrimethylammonium chloride (GTMAC). An optimization of the reaction parameters, such as water content, reactant mole ratio, and reaction media was performed. The presence of cationic GTMAC on the surface of NCC was confirmed by Fourier Transform Infrared Spectroscopy (FTIR). The cationically modified NCC was characterized by surface charge density, degree of substitution, ζ potential, and particle size. It was found that the cationic surface charge density of NCC can be increased by controlling the water content of the reaction system. Surface cationization of NCC led to an increase in the surface charge density over the un-modified NCC. The cationically modified NCC was well dispersed and stable in aqueous media due to enhanced cationic surface charge density. Transmission electron microscopy (TEM) images showed the improvement in state of dispersion of cationically modified NCC over the un-modified NCC. The optimum water content was found to be 36 wt% for aqueous based media and 0.5 water to DMSO volume ratio for aqueous-organic solvent reaction media. The increased surface charge density of NCC also delayed the onset of gelation in aqueous system.

Hemicellulose Removal from Hardwood Chips in the Pre-Hydrolysis Step of the Kraft-Based Dissolving Pulp Production Process

Abstract A pre-hydrolysis step to remove hemicelluloses from mixed hardwood chips consisting of maple, aspen, and birch with a ratio of 7:2:1 has been carried out. The effects of parameters on the pre-hydrolysis such as time, temperature, acetic acid addition, and raw material species, were determined. Different sugars, acetic acid, and furfural formation in the pre-hydrolysis liquor were quantified. The results showed that the pre-hydrolysis is a dynamic process, in which the removal of hemicelluloses increased with time while the conversion of extracted hemicelluloses to monosaccharides due to acid hydrolysis increased and part of the xylose was converted to furfural. The maximum temperature was the most critical parameter for hemicelluloses extraction and conversion, and a temperature of 170°C was the optimum for hemicelluloses extraction with relatively low conversion of xylose to furfural. About 11% of the xylan (in both monomeric and oligomeric forms) was removed at 170°C. Due to the presence of a high amount of xylan, birch produced the highest amount of xylose, followed by maple, and then aspen.

Evaluations of cellulose accessibilities of lignocelluloses by solute exclusion and protein adsorption techniques

Cellulose accessibilities of a set of hornified lignocellulosic substrates derived by drying the never dried pretreated sample and a set of differently pretreated lodgepople pine substrates, were evaluated using solute exclusion and protein adsorption methods. Direct measurements of cellulase adsorption onto cellulose surface of the set of pretreated substrates were also carried out using an in situ UV–Vis spectrophotometric technique. The cellulose accessibilities measured by the solute exclusion and a cellulose‐binding module (CBM)‐containing green fluorescent protein (TGC) adsorption methods correlate well for both sets of samples. The substrate enzymatic digestibilities (SEDs) of the hornified substrates are proportional to the measured cellulose accessibilities. Approximately over 90% of the SED was contributed by the accessible pore surfaces of the hornified substrates, suggesting that the substrate external surface plays a minor role contributing to cellulose accessibility and SED. The cellulose accessibilities of the pretreated substrates correlated well with the amounts of cellulase adsorbed. The SEDs of these substrates directly correlated with the amounts of adsorbed cellulase. Biotechnol. Bioeng. 2012; 109:381–389.

Separation of lignocellulosic materials by combined processes of pre-hydrolysis and ethanol extraction.

In this paper, we proposed a new modification for an ethanol-based pulping process, which would consist of the pre-hydrolysis (pre-extraction) of wood chips for removing hemicelluloses; the ethanol extraction of pre-hydrolyzed wood chips for removing lignin; and the post purification of cellulose, leading to the production of pure cellulose. We also experimentally evaluated the separation of hemicelluloses from the pre-hydrolysis liquor (PHL) obtained from a pulp mill. To remove lignin from the PHL, it was acidified to a pH of 2, which resulted in 47% lignin precipitation. The lignin separation from the acidified PHL was further improved via adding polyethylene oxide and poly aluminum chloride or adding ethyl acetate. To recover the hemicelluloses from the acidified PHL, ethanol was added to the acidified PHL with a volumetric ratio of 4 to 1. The isolated lignin and hemicelluloses were characterized by a Fourier transform infrared spectroscopy (FTIR) and a gas permeation chromatography (GPC).

A combined acidification/PEO flocculation process to improve the lignin removal from the pre-hydrolysis liquor of kraft-based dissolving pulp production process

The presence of lignin impairs the utilization of the hemicelluloses dissolved in the pre-hydrolysis liquor (PHL) of the kraft-based dissolving pulp production process. In this paper, a novel process was developed by combining the acidification and poly ethylene oxide (PEO) flocculation concepts to improve the lignin removal. The results showed that the lignin removal was improved by the addition of PEO to the acidified PHL, particularly at a low pH of 1.5. The main mechanisms involved are the lignin/PEO complex formation and the bridging of the formed complexes. This hypothesis was supported by the turbidity, FTIR and particle size measurements. Interestingly, the hemicelluloses removal from the acidification/PEO flocculation was marginal, which would be beneficial for the down-stream ethanol production from the PHL. Additionally, a process flow diagram was proposed that incorporates this new concept into the existing configuration of kraft-based dissolving pulp production process.

Hydrophilic modification of polyester fabric by applying nanocrystalline cellulose containing surface finish

In this study, polyethylene terephthalate (PET) fabric was modified by applying a hydrophilic surface finishing agent that contains nanocrystalline cellulose (NCC). To impart superior hydrophilicity, NCC was further cationically modified through quaternization by grafting glycidyl tri-methyl ammonium chloride (GTMAC). A textile binder, PrintRite595(®), was added to the finishing system. The surface finish was applied on the fabric using a rolling-drying-curing process. The modified fabric was characterized in terms of coating durability, moisture regain, and wettability. The durability of the surface finish was tested by six repeated washing steps. The surface properties of the fabric changed from hydrophobic to hydrophilic after heat treatment with the NCC-containing surface finishing agent. The results from the washing fastness, SEM, FTIR, and EDX analyses confirmed that the cationic NCC-containing textile surface finish showed superior adhesion onto the cationic dyeable (anionic) PET surface over the un-modified NCC. Furthermore, the cationic textile surface finish was capable of withstanding multiple washing cycles.

A combined process of activated carbon adsorption, ion exchange resin treatment and membrane concentration for recovery of dissolved organics in pre-hydrolysis liquor of the kraft-based dissolving pulp production process.

To recover dissolved organics in pre-hydrolysis liquor (PHL) of the kraft-based dissolving pulp production process, a new combined process concept of sequential steps of activated carbon adsorption, ion exchange resin treatment, and membrane concentration, was proposed. The removal of lignin in the PHL was achieved in the activated carbon adsorption step, which also facilitates the subsequent operations, such as the membrane filtration and ion exchange resin treatment. The ion exchange resin treatment resulted in the removal/concentration of acetic acid, which opens the door for acetic acid recovery. The membrane filtration is to recover/concentrate the dissolved sugars. The combined process resulted in the production of PHL-based concentrate with relatively high concentration of hemicellulosic sugars, i.e., 22.13%.

Furfural formation from the pre-hydrolysis liquor of a hardwood kraft-based dissolving pulp production process

This study aimed to produce furfural from the PHL. Results showed best furfural yield of 32.8% and the furfural selectivity of 37.7% in the monophase system (170 °C, 100 min), while they were 60.1% and 69.8%, respectively in the biphase system. The lower furfural selectivity in the monophase system was explained by more side reactions, such as fragmentation, condensation reactions, resinification and others. Model compounds such as: xylose, furfural, syringaldehyde, were used to confirm/identify these side reactions. The addition of dilute sulfuric acid/acetic acid in the system under the same conditions decreased the recovery of furfural. The addition of syringaldehyde into the PHL also led to a decrease in the furfural yield, supporting the conclusion that lignin structures in the PHL may also be involved in the side reactions, thus decreasing the furfural yield.

Removal of inhibitors from pre-hydrolysis liquor of kraft-based dissolving pulp production process using adsorption and flocculation processes.

A process for removing inhibitors from pre-hydrolysis liquor (PHL) of a kraft-based dissolving pulp production process by adsorption and flocculation, and the characteristics of this process were studied. In this process, industrially produced PHL was treated with unmodified and oxidized activated carbon as an absorbent and polydiallyldimethylammonium chloride (PDADMAC) as a flocculant. The overall removal of lignin and furfural in the developed process was 83.3% and 100%, respectively, while that of hemicelluloses was 32.7%. These results confirmed that the developed process can remove inhibitors from PHL prior to producing value-added products, e.g. ethanol and xylitol via fermentation.

Recovery of lignocelluloses from pre-hydrolysis liquor in the lime kiln of kraft-based dissolving pulp production process by adsorption to lime mud

Dissolved lignocelluloses from the pre-hydrolysis liquor (PHL) of kraft-based dissolving pulp production process were recovered by adsorption to lime mud produced in the causticizing plant of the kraft process. The adsorption of lignocelluloses was a fast process, and could be completed within one hour. The addition of polydiallyldimethylammonium chloride (PDADMAC) significantly increased the amounts of adsorbed lignin and hemicelluloses, which more than doubled at the PDADMAC dosage of 0.1% (based on the weight of PHL). The measured heating values of the adsorbed lignocelluloses indicate that adsorption of lignocelluloses to lime mud may result in the energy saving of the lime kiln. The process proposed in this study could also be adapted to decrease inhibitor concentrations (lignin and acetic acid) if the dissolved hemicelluloses in the PHL were used to produce value-added products, e.g., ethanol, xylitol, based on the fermentation process.