过氧化氢-乙酸联合预处理对甘蔗渣酶解和发酵的影响

采用过氧化氢-乙酸(HPAC)对甘蔗渣(SCB)进行了联合预处理。以预处理后的甘蔗渣为原料, 先进行酶水解, 然后将水解液进行乙醇发酵, 探讨预处理对甘蔗渣酶解和发酵的影响。实验结果表明: 20 g甘蔗渣, 加入150 mL过氧化氢水溶液(75 mL过氧化氢(30%)和75 mL水)和150 mL乙酸(99%), 硫酸用量为过氧化氢-乙酸溶液体积的0.5%, 在70 ℃反应2 h时, HPAC预处理脱除了88.85%的木质素, 并使90.10%的纤维素保留在底物中。底物(HPAC/70-SCB-0.5)的酶可及度是80.30 mg/g, 与相同条件下单独过氧化氢预处理(HP/70-SCB)和单独乙酸预处理(AC/70-SCB)相比, 分别增加了38.26%和31.08%, 甘蔗渣木质素的表面覆盖率从原料的0.66降低至0.22。酶解上清液在酶用量为5 FPIU/g(以底物计)条件下水解后, 葡萄糖得率是87.63%, 分别是HP/70-SCB和AC/70-SCB的6.89和20.62倍, 发酵产乙醇质量浓度是7.57 g/L, 分别是HP/70-SCB和AC/70-SCB的7.65和22.94倍。     

Dissolving grade eco-clean cellulose pulps by integrated fractionation of cardoon (Cynara cardunculus L.) stalk biomass

A biorefinery scheme with separate processing of the two main carbohydrate streams (cellulose and hemicellulose-derived) was employed to the energy crop cardoon (Cynara cardunculus L.) to fractionate the whole stalk material. A high quality xylose-enriched substrate was obtained after selective one-step dilute sulfuric acid hydrolysis of hemicelluloses, yielding 18.1 g of xylose per 100 g of dry biomass. The xylan-free solid residue was delignified by sulfur-free organosolv pulping to produce dissolving grade pulps having 93.8% of α-cellulose (33.1 g per 100 g dry initial biomass) and 79.5% degree of crystallinity. About 76% of crop lignin (13.8 g per 100 g dry initial biomass) was recovered from the spent pulping liquor as a high purity reactive precipitated organosolv lignin. Response surface methodology was used for statistical modeling and optimization of the applied separation processes. The central composite rotatable design was applied to assess the effects of the principal technological parameters on the main reaction outputs.     

Enhanced saccharification of corn straw pretreated by alkali combining crude ligninolytic enzymes

BACKGROUND: This work investigated the monokaryogenesis of dikaryon strains of Trametes hirsuta by protoplasts regeneration for extracellular ligninolytic enzyme production. Saccharification of corn straw was enhanced by alkali pretreatment combining crude ligninolytic enzymes. RESULTS: Effectiveness of alkali pretreatment of corn straw on delignification was evaluated under different concentrations. About 45% lignin loss was achieved at the concentration of 1.5% NaOH. In addition, 79.0% sugar yield was obtained after combined pretreatment with NaOH and crude ligninolytic enzyme produced from monokaryotic strains of Trametes hirsuta. Scanning electron microscopy (SEM) images showed that the porosity and surface area increased significantly after combined pretreatment. The FTIR spectra indicated that great intensity changes occurred at the 890–900 cm^?1, 1509–1513 cm^?1 and 1595 cm^?1 bands. CONCLUSION: The proposed combined pretreatment removes lignin and enhances saccharification of corn straw effectively. Copyright © 2012 Society of Chemical Industry     

枫香树材硫酸盐浆氧脱木素工艺技术

通过对枫香树材硫酸盐浆氧脱木素用碱量、氧压、温度和时间四因素三水平方差分析工艺技术研究,在用碱量2%～4%、氧压0.3～0.7 MPa、温度90～120℃和时间60～120 min内,得到枫香树材硫酸盐浆氧脱木素较为适宜的工艺条件:用碱量3%,氧压0.7 MPa,温度105℃,时间60 min。其氧脱木素结果为:得率89.8%,卡伯值7.6,黏度559.2 mL/g,白度48.2%ISO。     

Delignification of intact biomass and cellulosic coproduct of acid‐catalyzed hydrolysis

The kinetics of acid‐catalyzed hemicellulose removal and also alkaline delignification of oat hull biomass were investigated. All three operational parameters namely, catalyst concentration (0.10–0.55 N H₂SO₄), temperature (110–130°C), and residence time (up to 150 min) affected the efficiency of hemicellulose removal, with 100% of hemicellulose removed by appropriate selection of process parameters. Analysis of delignification kinetics (in the temperature range of 30–100°C) indicated that it can be expressed very well by a two‐phase model for the crude biomass and also for the hemicellulose‐prehydrolyzed material. The application of acid‐catalyzed prehydrolysis improved the capacity of lignin dissolution especially at lower temperatures (30 and 65°C) and accelerated the dissolution of lignin. This acceleration of delignification by prehydrolysis was possible at all levels of temperature in the bulk phase; however, results were more significant at the lower temperatures in the terminal phase. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1783–1791, 2015     

Distribution of Anionic Groups in TMP Suspensions

Abstract

The distribution of anionic groups in fibres, fines, the colloidal fraction, and the dissolved fraction of thermomechanical pulp (TMP) suspensions was determined. The influence of extraction, alkaline treatment, and peroxide bleaching of spruce TMP were also studied.

Spruce TMP was extracted with hexane, treated with alkali, or bleached with peroxide. Suspensions were made at pH 5.5 or 8, and fractionated into long fibres, large fines, small fines, a colloidal fraction, and a dissolved fraction. The surface and total charge of the fractions were determined separately by polyelectrolyte titration. To determine the origin of the charges, the contents of fatty acids, resin acids, and acidic units in polysaccharides in the different fractions were determined by gas chromatography.

Extraction of TMP with hexane prior to fractionation increased the measured total and surface charge of the fibres. The removal of wood resin probably uncovered some anionic groups on the fibre surface, or improved the penetration of the polymers into the pores of the fibres. The total charge, determined with polybrene titration, of the fines and the colloidal fraction was lower when the resin had been removed, while the surface charge, determined with poly-DADMAC, was not greatly affected.

Alkaline treatment of the TMP increased both the total charge and the surface charge of the fibres and fines, mainly because of demethylation of pectins. Alkaline treatment also increased the total and surface charge of the dissolved substances, due to the release of pectic acids into the water phase. Alkaline peroxide bleaching further increased the total and surface charge of fibres and dissolved substances, most likely due to oxidation of lignin. The total charge and the surface charge of the colloidal substances, consisting mainly of wood resin, were only slightly affected by alkaline treatment and peroxide bleaching.

The anionic charge in TMP suspensions originated mainly from free uronic acids in the xylans, arabinogalactans, and pectic acids. The contribution from the fatty and resin acids was substantial only for the colloidal fraction.     

Delignification and Bleaching Response of Earlywood and Latewood

Abstract

The delignification response in cooking and the impact of bleaching on earlywood and latewood were studied. Spruce earlywood and latewood chips were pulped by the kraft process and subsequently treated with one bleaching chemical at a time. In cooking, latewood required a higher alkali charge to reach the same kappa number. No difference in the light absorption coefficient between the different fiber types was observed. After oxygen delignification the earlywood fibers had a higher light absorption coefficient at the same kappa number. The difference in light absorbing material was maintained when bleaching was performed with chlorine dioxide, ozone, and peracetic acid. Hydrogen peroxide decreased the light absorbing structures in the earlywood to the same level as for latewood. The earlywood pulp had a higher brightness at a given kappa number than the latewood. The higher brightness remained through all bleaching operations and was primarily due to a higher light scattering ability.     

Chlorate Formation in Chlorine Dioxide Delignification—An Analysis via Elementary Kinetic Modeling

Abstract

Elementary kinetic modeling was used to study the mechanism of chlorate formation in chlorine dioxide delignification. Reaction conditions reflecting typical industrial processes (T = 50°C, pH 1.5–4) were examined. Fe mediated Cl(III) decomposition and a reaction between hypochlorous acid and chlorous acid (or their equilibrium counterparts) were found to be the major reaction routes responsible for chlorate formation at pH < 3. The latter route accounts for chlorate formation at pH ≥ 3. The rate of chlorous acid (HClO₂) self-decomposition was too slow either to compete against the other routes (pH < 3) or to yield notable amounts of chlorate within the given time frame (pH ≥ 3). The results suggest that chlorate formation could be suppressed, without adverse effects on chlorine dioxide regeneration, by aiming for end pH 3–3.5, ensuring a moderate chloride ion concentration and by favoring concentrated solutions/suspensions.     

A Model for Chlorine Dioxide Delignification of Chemical Pulp

Abstract

A phenomenon based model for chlorine dioxide delignification of chemical pulp is introduced. The pulp suspension environment is modeled using the concept of two liquid phases, one inside and the other external to the fiber wall. Physico-chemical processes taking place during delignification are implemented with thermodynamic, mass transfer and reaction kinetic models. A broad library of chemical reactions is introduced. Inclusion of each reaction is justified. The model response is tested against experimental laboratory delignification results (o-delignified birch pulp). The experimental data consists of kappa number, hexenuronic acid, inorganic oxy-chlorine compound, and organochlorine (AOX, OX) measurements at several time points during five delignification experiments. The model predictions are mainly in good agreement with the experimental results. The predictions regarding hypochlorous acid driven processes (HexA removal, organochlorine formation, chlorite and chlorate concentration) are somewhat incoherent, indicating that knowledge regarding the intermediately formed hypochlorous acid is presently insufficient.