Changes in chemical characteristics of bamboo (Phyllostachys pubescens) components during steam explosion

Chemical changes in cell wall components of bamboo internode during steam explosion process were analyzed to investigate self-binding mechanism of binderless board from steam-exploded pulp. More than 30% of xylose on initial mass, which is a major hydrolyzate of bamboo hemicelluloses, was lost after steam explosion treatment. Bamboo lignin is characterized by the presence of ester- and/or ether-linked p-coumaric acid to lignin. The content of phenolic hydroxyl groups of lignin isolated from steam-exploded pulp was characterized 2.3 times higher than those of the extract-free bamboo internode due to the cleavage of β-O-4 linkages. Alkaline nitrobenzene oxidation of the bamboo lignin gave vanillin, syringaldehyde and p-hydroxybenzaldehyde as major products. The content of p-hydroxybenzaldehyde decreased after steam explosion treatment, indicating the cleavage of ester- and/or ether-linked p-coumaric acid. The total yield of erythronic and threonic acids in ozonation products of the extract-free bamboo internode lignin was 268 mmol (200 g lignin)⁻¹, while those of lignins in the steam-exploded pulp and powdery fraction were 96 and 129 mmol (200 g lignin)⁻¹, respectively, suggesting the significant cleavage of β-O-4 linkages during steam explosion treatment. The cleavage of β-O-4 linkages was also confirmed by ¹H- and ¹³C-NMR spectroscopic observations.     

Lignin Characteristics of Steam Exploded Bamboo Residue during Hot Pressing

bamboo(Phyllostachys edulis) residue was subjected to steam explosion treatment to produce superior fibers for binderless boards.Then,lignin was isolated from extract-free bamboo meal,steam exploded pulp,and binderless boards with characteristics being determined by thermo-gravimetry (TG),differential scanning calorimetry (DSC),and fourier transform infrared spectroscopy (FTIR).Results showed that:1) the yield of lignin directly extracted with dioxane-water from steam exploded bamboo pulp(SEBPL) and binderless board (SEBBL) was higher than that of milled bamboo lignin (MBL).Also,the yield of SEBBL was lower than that of SEBPL.2) FTIR results showed cleavage of ester and ether bonds between lignin and p-coumaric acid during steam explosion treatment.3) SEBBL showed two glass transitions at 115℃and 200℃, while MBL gave one glass transitions at 155℃.And 4) the modulus of rupture(MOR) and modulus of elasticity(MOE) decreased with an increase in steaming time;whereas internal bonding(IB) increased.In all cases the dimensional stability of boards did not exceed the maximum requirements for type GB/T 11718- 1999.     

Development of boards made from oil palm frond II: properties of binderless boards from steam-exploded fibers of oil palm frond

Binderless boards were prepared from steam-exploded fiber of oil palm(Elaeis guineensis Jacq.) frond at six levels of explosion conditions. Their properties were investigated and evaluated. The mechanical properties (i.e., modulus of rupture, modulus of elasticity, and internal bonding strength) of the boards increased linearly with increasing board density as the usual hardboard. The boards made from fibers treated under a steam explosion condition of 25 kgf/cm² (steam pressure) and 5 min (digestion period) exhibited the maximum strength. These boards at a density of 1.2 g/cm³ met the requirement of S-20 grade of JIS A 5905 — 1994 (fiberboard). Thickness swelling of the boards ranged from 6% to 14% under the JIS A 5908 — 1994 (particleboard) test condition and showed no significant changes with increasing board density. The main bonding strength of the board is believed to be due to a ligninfurfural linkage. Considering the chemical components of oil palm frond, which is rich in hemicellulose, there seems to be a good possibility for producing binderless boards using steam-exploded fibers of oil palm frond.This study was presented in part at the 2nd International Wood Science Seminar, Serpong, Indonesia, November 1998     

蒸煮爆破处理过程中毛竹材加工剩余物主要化学成分的变化研究

采用硫酸水解法(aldito-acetate procedure)、X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)分析了蒸爆过程中毛竹材加工剩余物纤维聚集态结构及主要化学成分的变化.研究结果表明,(1)毛竹材加工剩余物经蒸爆处理,60%左右的半纤维素水解,木质素低分子化且裸露到纤维表面,易被80%乙醇及木质素溶剂提取,从而实现毛竹材加工剩余物主要组分的有效分离.(2)毛竹材加工剩余物经蒸爆处理,80%乙醇抽提物得率提高,综纤维素得率减少,木质素含量减少:葡萄糖相对含量增加,半纤维素降解明显.(3)210℃处理10 min和220℃处理10 min的蒸爆浆的化学组成变化几乎没有区别,但两者与200℃处理10 min差别较大,210℃处理10 min是毛竹材加工剩余物适宜的处理温度.(4)FTIR结果显示蒸爆处理后在1040～1060 cm-1区的吸收峰分裂为明显的2个峰表明半纤维素降解,1166 cm-1处的吸收强度明显减弱,表明C-O-C键有不同程度的断裂.X-身寸线衍射分析结果显示毛竹材加工剩余物蒸爆处理后纤维素相对结晶度增加.     

Lignin characteristics of bast fiber and core in kenaf, bark and wood of paper mulberry and mulberry

The structural features of bast fiber and core lignins in kenaf (Hibiscus cannabinus), bark and wood lignin of paper mulberry (Broussonetia papyrifera (L.) Vent × Broussonetia kazinoki Sieb.) and mulberry (Morus bombycis) were characterized by alkaline nitrobenzene oxidation, ozonation and methoxyl group determination. Bj?rkman lignins were isolated from bast fiber and core, and bark and wood fractions of the plant samples, and structural characteristics were investigated by ¹H NMR and ¹³C NMR spectroscopies. Kenaf bast fiber gave very high molar ratio of syringaldehyde to vanillin (S/V) of alkaline nitrobenzene oxidation products, while methoxyl content was about the same as that of the core fraction. Results of ¹H NMR and ¹³C NMR of Bj?rkman lignin suggested the presence of aliphatic fragments in lignins isolated from paper mulberry and mulberry bark, but not in kenaf bast fiber. The lower yield of alkaline nitrobenzene oxidation products from bast fiber and bark might be due to the higher content of condensed structure of lignin compared to core fraction. Total yield of erythronic (E) and threonic (T) acids of ozonation products and the molar ratio of erythronic acid to threonic acid (E/T) of the bast fibers and bark were lower than the corresponding core and wood fractions, suggesting that the contents of arylglycerol-β-aryl ether intermonomer linkages in the bast fiber and bark lignin were lower than those of the core and wood fractions. Methoxyl content of bark lignin was lower than the corresponding wood lignin. The methoxyl content of the extract-free kenaf bast fiber was similar to that of the core fraction, while the values of paper mulberry and mulberry bark were about one-half of the corresponding wood fractions, respectively. In bark lignins, the methoxyl contents of Klason lignin and Bj?rkman lignin from bark were lower than those of the extract-free barks. This result suggests that the purity of Klason lignin and Bj?rkman lignins of bark may be rather low.     

Structure, composition and enzymatic hydrolysis of steam-exploded lespedeza stalks

Pretreatment of lespedeza stalks by steam explosion has been studied. The results indicate that steam-exploded pretreatment has strong effects on physical features, morphology, crystallinity, and composition of lespedeza stalks as shown by scanning electron microscopy (SEM), infrared (IR), and X-ray diffraction spectrometry methods. After steam explosion, the cellulose and lignin contents of lespedeza stalks varied only slightly, but the hemicellulose content had decreased from 29.34% to 7.48%. The cellulose obtained by steam-exploded pretreatment had a higher degree of crystallinity than that of the raw material. At the explosion condition of 2.25 MPa and 4 min, lignocellulose is easier to hydrolyze by enzyme than the original lignocellulose. The concentration of reduced sugar in the hydrolyzate liquid increased from 71.77 to 162.84 g·L–1.     

汽爆压力对无胶棉秆纤维板性能的影响

不添加任何化学助剂,在不同汽爆压力下进行棉秆解纤,将解纤后的纤维热压制成无胶纤维板.分析了汽爆压力对棉秆纤维形态、化学成分以及无胶纤维板产品性能的影响.结果表明,随着汽爆压力的增大,纤维分离程度提高,纤维中游离酸、游离糖及游离醇的质量分数含量增加,试板的内结合强度增大,但静曲强度和弹性模量则减小.     

不同热压方法对无胶竹碎料板力学性能影响

分别采用普通热压和喷蒸热压两种热压方法制备了无胶竹碎料板,对它们的物理力学性能进行了对比研究与分析.结果表明,与普通热压法相比,喷蒸热压法制备的无胶竹碎料板的静曲强度、弹性模量与内结合强度明显提高,吸水厚度膨胀率显著减小,这可能是因为两种热压法热压过程中竹碎料发生的化学变化不同所致.     

蒸汽爆破-乙醇蒸煮两步法预处理对麦秆结构的影响

对麦秆采用先蒸汽爆破后乙醇蒸煮的两步法进行预处理,研究预处理对麦秆组分及结构变化的影响。蒸汽爆破过程实验条件选取200 g绝干麦秆,压力1.75 MPa和时间3.5 min。乙醇预处理过程选取80 g蒸汽爆破麦秆(绝干),55%乙醇,两者固液比1∶5(g∶mL),温度170℃、时间30 min。通过高效液相色谱法测定,预处理最终产物组分中半纤维素降低89%左右,木质素降低35%左右。采用红外光谱、纤维形态分布分析及SEM分析对预处理过程中麦秆结构变化情况进行研究,结果表明:蒸汽爆破过程破坏了半纤维素酯键连接且半纤维素降解非常明显,但对纤维素链结构影响和降解作用相对较低;麦秆经过蒸汽爆破预处理后,纤维平均长度明显降低,而平均宽度却显著增加;再经乙醇预处理后纤维平均长度基本保持不变,但平均宽度降低;经两步预处理后麦秆纤维的天然物理结构由紧密到蓬松,纤维束呈松散状态且纤维表面基本无碎片附着物,利于后续加工利用。     

The suitable harvesting season and the part of moso bamboo (Phyllostachys pubescens) for producing binderless boards

The properties of the binderless boards of moso bamboo depending on the harvest seasons and the parts of the height were reported and the optimum harvesting conditions investigated. The binderless boards were prepared from the powdered bamboo harvested each month from June to May, and the parts in height. The hot water extract (HWE), lignin, α-cellulose, and hemicelluloses contents were examined. The board properties were evaluated with internal bonding (IB), water absorption (WA), and thickness swelling (TS). From the experiment, the boards prepared between March and October had higher HWE content and higher IB and lower WA and TS than the ones prepared in other months. The board from the top part showed lower IB and higher WA and TS than the bottom and the middle. The boards prepared from the residue after extraction of HWE showed lower IB than the unextracted samples. These results indicated that for producing board from bamboo, the suitable harvesting season is when HWE contents are higher and that the suitable parts in height for harvesting are the bottom and the middle where lignin contents are not low.     

漂白竹浆碱抽提制备溶解浆的研究

以漂白竹浆为原料,通过碱抽提技术制备竹溶解浆,并用X射线衍射仪研究竹浆中纤维素晶型结构的变化,用场发射扫描电镜(FE-SEM)观察纤维表面形貌的变化,采用凝胶渗透色谱(GPC)分析碱抽提后竹浆相对分子质量分布(MWD)。经碱抽提后,采用盐酸进行酸处理,以调控溶解浆的聚合度、灰分和白度。研究结果表明:在浆质量分数10%条件下,Na OH质量分数10%,温度30℃,时间60 min,半纤维素脱除率可达66.71%;FE-SEM观察到半纤维素的去除减少了纤维表面原纤化现象,增大纤维横向宽度,增加了纤维柔软性及卷曲性;GPC分析表明多分散系数(PDI)随半纤维素的去除逐渐下降,由7.71降至4.43,竹浆相对分子质量增加,提高了相对分子质量分布的均一性。酸处理过程使残余半纤维素质量分数降至7.02%,竹溶解浆纤维素纯度高达94.25%。     

Modeling wood fiber deformation caused by vapor expansion during steam explosion of wood

Steam explosion is a process used to enhance enzyme penetration and digestibility of wood. Wood chips are processed with high-pressure steam for a limited time, and the bonding between polysaccharides and lignin is weakened. After this processing, the pressure is rapidly reduced to induce steam explosion where the vapor inside a fiber expands and exerts pressure on the fiber walls. This pressure causes fiber deformation and breakage. In this study, fiber deformation caused by vapor expansion was simulated by single wood fibers using finite element modeling. When pressure is applied inside a fiber, it is likely to break from the corner and midway between two adjacent corners. The fiber is modeled with four layers (P, S1, S2, and S3). Although the P, S1, and S3 layers are very thin, they significantly prevent fiber deformation. The fibers with a thin wall and a low micro-fibril angle (MFA) deform more than the fibers with a thick wall and a higher MFA. It was found that the shape of the fiber plays an important role in its deformation. The areas of localized strain are the most likely places for fiber splitting. Essentially, fiber wall damage is more likely to occur in (1) thin-walled fibers, i.e., earlywood, (2) fibers with damaged P and S1 layers, (3) fibers with low MFAs, and (4) fibers with irregular cross-sections. Different chemical pretreatments, fractionation procedures, and selections of raw materials can accordingly be considered to produce easily steam-exploded materials.     

Steam explosion pretreatment used to remove hemicellulose to enhance the production of a eucalyptus organosolv dissolving pulp

The steam explosion (SE) pretreatment associated with the organosolv process was investigated to produce dissolving pulp from eucalyptus. Prehydrolysis Kraft (PHK) pulping was also done to produce viscose and acetate grade pulps as reference. The organosolv pulps were delignified in two steps with sodium chlorite. Viscose and acetate grade PHK pulps were bleached by OD₀(EH)D₁P and OD₀(EP)D₁PCCE sequences, respectively. Dilute acid-catalyzed (with acid addition) SE pretreatment dissolved more xylan than auto-catalyzed (no acid addition) SE pretreatment. Steam-exploded unbleached organosolv pulps showed lower residual lignin content and screened yield than unbleached organosolv pulps without SE pretreatment. Steam explosion pretreatment helped to decrease lignin content and damaged fiber length of unbleached organosolv pulps. The 1.0% H₂SO₄ organosolv pulp (organosolv dissolving pulp at bioconversion conditions) showed the highest reactivity. Even showing low viscosity for some applications, in general, the organosolv dissolving pulps produced in this study can be used for making lyocell fibers.     

竹原纤维和竹粉纤维形态和化学成分分析

以3年生毛竹材为原料,研究了毛竹竹粉和竹原纤维的纤维形态和化学成分。纤维形态分析结果表明:竹原纤维的宽度(143μm)与竹粉(136μm)相当,长度(22.63 mm)远高于竹粉(0.61 mm),使其长宽比(158.25)远高于竹粉(4.49)。化学成分分析表明:竹原纤维的纤维素含量(65.6%)比竹粉(37.3%)高得多,聚戊糖含量(17.1%)略低于竹粉(20.1%)。竹粉中的木质素含量为24.5%,是竹原纤维中木质素含量(11.5%)的2倍多。竹原纤维的高纤维素含量和低木质素含量是其广泛应用于制浆造纸行业的重要原因。     

Chemical structure and thermal properties of lignin modified with polyethylene glycol during steam explosion

Thermoplastic processing of lignin is restricted by its high glass transition temperature (T _g). In this study, lignin was modified with polyethylene glycol (PEG) during steam explosion to improve its thermoplastic properties, and the effects of steam explosion and PEG on the chemical structure and thermal properties of lignin were investigated. Structure characterization using Fourier transform infrared spectroscopy showed that hydroxyl and ether functional groups increased and the activity of lignin was improved by steam explosion. In addition, steam explosion treatment was more effective than heat treatment for promoting the reaction of PEG with lignin. Solid-state ¹³C NMR revealed that PEG was grafted onto lignin. The T _g of raw lignin was 164.1 °C; after steam explosion, lignin exhibited more than one T _gs. The T _g of lignin was reduced when the steam explosion temperature increased and decreased further, to around 60 °C, when PEG was used to modify lignin. Therefore, this work provides an effective approach to reducing the high T _g of lignin.     

竹浆GIF仿酶漂白木质素降解产物气相色谱-质谱解析

利用气相色谱-质谱联用(GC-MS)方法对GIF仿酶漂白中的木质素降解产物进行了分析,进一步探讨这种仿酶系统对木质素的降解机制.结果显示GIF仿酶处理使竹浆残余木质素进一步氧化降解,降解的主要方式有脱甲基作用、醌型结构的产生和开环、烷基-芳基醚键的开裂、侧链碳-碳连接的氧化断裂等.GC-MS检测所得的降解产物中,含羰基的化合物较多,这是GIF仿酶系统催化氧化的结果.一些醌式结构、共轭羰基和酚类的脱除,也使纸浆因发色基团减少而白度提高.此外,检测出一些糖类降解产物,说明GIF仿酶系统对纸浆碳水化合物有一定的降解作用.     

Surface analysis of explosion pulps by ESCA

Summary The oxygen (1s) ESCA peak for aspen explosion pulp consists of two components, O1 and O2. A tentative assignment was made for them. O1 with lower binding energy is assigned to oxygen in lignin; while O2 comes mainly from the oxygen elements in carbohydrates. Thus, an O1 area percentage might be viewed as a measure of lignin exposed on the fiber surface. Sulfur (2p) spectra show that the sulfur on the fiber surface of the pulps studied here is in the form of sulfonate groups. Compared to conventional pulps, the lower percentage of O1 and higher sulfur-to-carbon ratio for explosion pulps imply higher number of hydrophilic groups exposed on their fiber surface.     

Characterization and acetylation behavior of bamboo pulp

In the present study, the chemical–physical properties of bamboo pulp prepared with a sequential totally chlorine-free procedure were analyzed and compared with that of commercial wood pulp by SEM, FTIR, TGA, and X-ray. α-Cellulose content was determined to be 95%, a little less than that of commercial wood pulp. But the crystallinity of bamboo pulp is lower than wood pulp. Acetylation activity of bamboo pulp was determined to be higher than that of wood pulp, which was carried out in heterogeneous media with sulfuric acid as catalyst. The cellulose acetate prepared with bamboo pulp can be quickly dissolved in acetone without distinct difference with that of cellulose acetate prepared with wood pulp. The results indicate the potential utility of bamboo as an alternative to wood pulp for cellulose derivate fiber material.     

Mechanistic study of microstructural deformation and stress in steam-exploded softwood

Steam explosion pretreatment results in the formation of microcracks in the cell walls of wood. In the present study, steam explosion experiments were performed and structural changes in Norway spruce were identified using scanning electron microscopy. The cellular structure of the softwood spruce was simulated using the finite element method, and the effects of pressure generated during the steam explosion pretreatment on the deformation of the cells were investigated. The simulated model included earlywood, latewood, and ray cells. The effects of bordered and cross-field pits on the stresses in the cell wall were studied as well. Many similarities were observed between the microcracks in the steam-exploded wood and the high-stress regions predicted by the model. The experimental and simulation results showed that the radial cell walls in the earlywood cells experienced major deformation. The presence of the pits created stress localization and facilitated the formation of microcracks in the cell walls.     

Cultivation of shiitake in sugi wood meal II: effects of seasoning treatment for wood meal on mycelial growth

The effects of seasoning treatment for fresh sugi wood meal on the mycelial growth of shiitake was investi-gated. The mycelial growth of shiitake in sugi wood meal increased to the same level as that in extract-free sugi wood meal on the 12th day and to approximately 70% of that in konara wood meal on the 28th day of the seasoning treatment. A drastic decrease in extracts of fresh sugi wood meal occurred during the early stage of treatment, and the neutral fraction of methanol extracts decreased to less than 2%. The drainage of sugi wood meal media significantly increased during the later stage of treatment. No changes in the chemical components of sugi wood meal were detected during the seasoning treatment. The mycelial growth of shiitake in the fully seasoned sugi wood meal, which was prepared for commercial mushroom cultivation, was at almost the same level as that in the extract-free sugi wood meal. All of the seasoned sugi wood meals contained a neutral fraction of less than 1%. These results suggested that seasoning treatment can promote mycelial growth of shiitake in sugi wood meal by eliminating inhibitors and improving the physical properties of sugi wood.Part of this paper was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999