Hydrolysis of bamboo fiber cellulose in formic acid

Bamboo fiber dissolution and hydrolysis in formic acid were studied. After hydrolysis, formic acid can be recovered in a clean state and reused. Solid water-soluble sugars were obtained. After being dipped into the formic acid solution for 30 min, the bamboo fibers started to swell. After one hour, the bamboo fibers gradually started to dissolve in the formic acid solution. The color of the liquor/solution turned green and dark. In the end, the bamboo fibers became thoroughly dissolved in the liquor after four hours. There was a clear hierarchical tissue structure on the fiber surface, as observed by AFM before treatment. The differential structure disappeared after 30 min of treatment. The fiber surface became plump and glossy. After six hours reaction at 60°C, the solid sugar mixture recovered contained glucose, cellobiose, cellotriose, cellotetrose, cellopentose and cellohexaose. A significant fraction of the sugar products consisted of monomeric glucose. More than 54.5% of the bamboo fiber mass had been transformed into monomeric glucose. __________ Translated from Biomass Chemical Engineering, 2007, 41(2): 5–10 [译自: 生物质化学工程]     

NaClO添加量对TEMPO氧化纳米微纤丝结构与性能的影响

以毛竹粉为原料,采用TEMPO催化氧化联合超声处理制备纳米微纤丝,通过改变Na Cl O与纤维素的质量比,研究了Na Cl O添加量对纳米纤维素的长径比、纤维形态以及羧基含量等特性的影响。结果表明:随着Na Cl O添加量的增加,纳米纤维素羧基含量逐渐提高,长径比增大;当Na Cl O添加量为15 mmol/g时,纳米纤维素羧基含量可高达1.646 mmol/g,横截面直径可达6～10 nm,长径比为273～455;随着纳米纤维素羧基含量的增加,纳米纤维素悬浮液的透光率和剪切黏度不断增大。虽然TEMPO催化氧化程度不断加深,但纳米纤维素的晶型并未遭到破坏,仍然呈现出典型的纤维素I晶体结构,而随着羧基含量的增加,纳米纤维素的结晶度和热稳定性有一定程度的下降。     

竹纤维乙酰化改性制备醋酸纤维素

竹纤维经乙酰化改性制备醋酸纤维素。研究了催化剂种类、原料固液配比、催化剂用量和反应时间对取代度和不溶物含量的影响,并采用傅里叶红外光谱(FTIR)和X-射线衍射(XRD)对乙酰化产物进行了表征。结果表明:竹纤维的羟基被乙酰基取代,其纤维素中晶格遭到破坏;固液配比1∶5,催化剂硫酸用量9%,反应2.5 h,乙酰化产物不溶物含量较少,取代度达2.8以上。     

Preparation of strongly acidic cation-exchange resins from gymnosperm acid hydrolysis lignin

The chemical preparation of strongly acidic cation-exchange resin from sulfuric acid lignin (Klason lignin) (SAL), a typical acid hydrolysis lignin, was investigated. Sulfonation of resinified SAL itself gave a resin with an ion-exchange capacity of 2.3 mEq/g. After resinification with formaldehyde, the phenolized SAL with a reactivep-hydroxyphenyl group yielded a resin with an ion-exchange capacity of 3.2 mEq/g. The latter capacity is superior to that of the corresponding commercial phenol-type resins (2–3 mEq/g), but did not reach the level of the corresponding commercial styrene-type resins (4-5 mEq/g).This paper was presented at the 43th Lignin Symposium, Fuchu, October 1998     

磷酸活化工艺条件对活性炭性质的影响

探讨了磷酸浓度、浸渍比、活化温度三个主要工艺参数对活性炭性质的影响。结果表明磷酸浓度、浸渍比和炭活化温度对磷酸活化法活性炭的碘吸附值、亚甲基蓝脱色力和焦糖脱色力都有影响:浸渍比(纯磷酸与绝干原料质量之比) 的影响最显著,但1.5:1之后影响不大;磷酸浓度对活性炭的碘吸附值影响显著,对亚甲基蓝脱色力的影响次之,而对焦糖脱色力的影响很小;炭活化温度对碘吸附值和焦糖脱色力的影响随磷酸浓度和浸渍比的不同而有较大的差异,但在不同的磷酸浓度和浸渍比的情况下炭活化温度的升高都提高亚甲基蓝脱色力。磷酸活化活性炭的孔隙结构能通过调整磷酸浓度、浸渍比和炭活化温度进行控制。     

纤维素溶解机理研究述评

纤维素是植物细胞壁的主要组分之一,是由葡萄糖通过1,4-β糖苷键连接而成的均一聚糖,广泛应用于生产酯类、醚类等纤维素基化工产品。纤维素基产品的制备及应用与其溶解程度密切相关,探究纤维素溶解机理,寻找一种绿色高效的纤维素溶剂至关重要。综述了当前国内外学者们对纤维素溶解机理的解释(氢键破坏理论)以及可能影响溶解的因素(化学热力学、化学动力学、结晶度、纤维素两亲性、电荷数和温度),在此基础上探讨了导致纤维素水溶性差的原因,提出了在复杂体系中除了氢键作用以外,还需要综合考虑范德华力、疏水性相互作用的影响。同时,总结了纤维素在离子液体中溶解机理方面存在的争议,其中关于氢键理论还存在一定问题,动力学控制理论尚不明确,阳离子在溶解过程所起的作用被忽视,指出离子液体阳离子的两亲性是纤维素溶解的关键因素。基于纤维素的两亲性及两亲性溶剂促进纤维素溶解的重要理论,提出了应重点寻找新型两亲性溶剂的观点,为未来寻求高效、环境友好、成本低廉的纤维素溶剂指明了方向。     

Relationship between production of hydroxyl radicals and degradation of wood, crystalline cellulose, and a lignin-related compound or accumulation of oxalic acid in cultures of brown-rot fungi

The degradation of wood, filter paper cellulose, and a lignin-substructure model, was measured in cultures of seven fungi usually regarded as brown-rot fungi. Hydroxyl radical production and the accumulation of oxalic acid in the cultures were also measured. Four of the fungi, Gloeophyllum trabeum, Tyromyces palustris, Laetiporus sulphureus, and Postia placenta, were typical brown-rot fungi, in that they preferentially degraded and eliminated the polysaccharides in wood and produced large amounts of hydroxyl radical. The rates of hydroxyl radical generation in cultures of the four fungi were directly proportional to the degradation rates of wood, cellulose, and the lignin-related compound, and inversely proportional to the amount of oxalic acid in the cultures. Two of the fungi, Daedalea dickinsii and Lentinus lepideus, did not degrade any of the substrates significantly and produced very little hydroxyl radical. Coniophora puteana had the highest rate of cellulose degradation, but did not degrade wood or the lignin model significantly and produced only negligible amounts of hydroxyl radical. These results indicate that brown-rot fungi produce large amounts of hydroxyl radical for the degradation of wood and crystalline cellulose.     

TEMPO/NaBr/NaClO氧化对纳米微晶纤维素性能的影响

利用TEMPO/NaBr/NaClO体系对硫酸水解漂白硫酸盐浆制备的纳米微晶纤维素(NCC)进行改性制备氧化NCC(TONCC)。采用电导滴定、X射线衍射(XRD)及原子力显微镜(AFM)对改性前后纳米微晶纤维素的表面性能及形貌进行表征,并将其作为造纸增强剂应用于废新闻纸脱墨浆,研究其对浆料强度性能的改善作用。结果表明,TONCC表面引入大量的羧基(0.806 mmol/g),而NCC表面羧基含量仅为0.02 mmol/g,外观由半透明变为透明。TONCC保持了纤维素I的晶型结构,分散性能得到改善,宽度略有减小。将改性前后的纳米微晶纤维素加入到废新闻纸脱墨浆中,与对照样相比,当NCC和TONCC用量为0.6%时,浆料的抗张指数分别提高了8.7%和14.2%;NCC和TONCC用量为0.8%时,撕裂指数提高了约12%。将NCC和TONCC与CPAM联合使用,浆料的抗张指数得到了进一步提升,用量为0.8%时,抗张指数分别为17.35和18.52(N·m)/g,分别比对照样提高了19.6%和27.7%。     

微波辐射法竹浆纤维素的中性TEMPO氧化及表征

采用微波辐射法和中性2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)自由基氧化工艺来预处理竹浆纤维素,之后用超声波机械处理制备微纤化纤维素。实验结果表明,在60℃下,TEMPO用量为0.15 mmol/g(以绝干浆计,下同),Na Cl O2用量为10 mmol/g,Na Cl O用量为1 mmol/g,微波氧化2 h,其羧基含量最高到达0.729 mmol/g,氧化效果最佳,超声波处理后微纤化纤维素得率高达85.7%。FT-IR分析表明纤维素氧化后引入羧基官能团;XRD结果揭示纤维素氧化反应只发生在纤维素的无定型区或结晶区表面;纤维素氧化前后的聚合度(Dp)结果表明相对于碱性氧化,微波辐射和中性TEMPO氧化对纤维的降解程度低,从而有效地保持了纤维素原本的长度。     

白腐菌预处理对丙酸蒸解玉米芯制备纤维素的影响

探讨了白腐菌预处理对丙酸蒸解法制取纤维素的影响.在白腐菌对玉米芯进行预处理过程中,赖锰过氧化物酶(MnP)、木质素过氧化物酶(LiP)、漆酶、木聚糖酶和纤维素酶的酶活分别在第5、 6、 7、 10和 15 d 达到最高值,分别为1.326、 10.25、 0.062 7、 0.33和 403 U/g.利用响应面分析法确定丙酸蒸解玉米芯最佳工艺条件为:料液比1∶ 10(g∶ mL),蒸解时间 70 min,丙酸质量浓度 900 g/L,产物中纤维素的质量分数为 91.09%.玉米芯经白腐菌预处理 10 d 后再用丙酸进行蒸解处理,产物中纤维素的质量分数和保留率分别为 97.12% 和 94.70%,而半纤维素和木质素的质量分数仅为 0.96% 和 0.92%.     

Effect of intermittent heat treatment on crystallinity in wood cellulose

The effect of intermittent heat treatment on cellulose crystallites in wood was studied to evaluate quantitatively the changes of crystallinity induced by intermittent and continuous heating. The changes in crystallinity were found to be strongly affected by the intermittent heat treatment. The increased crystallinity, the width of the crystals, and the piezoelectric properties were the same for the first intermittent heating as for continuous heating. Further intermittent heating for the same time duration and temperature had no effect on the above properties, probably due to the stopping of the thermal reaction during the interval. Our results suggested that intermittent heat treatment has certain critical cooling temperatures that stop the thermal reaction and are closely related to the duration of the interval. Samples once exposed to a certain duration of heat treatment and then cooled need more time, about twice that of the first duration of intermittent heating compared with continuous heating, to reach maximum crystallinity in wood cellulose.     

Canopy cover effects on cellulose decomposition in oak and pine stands

Cellulose mass loss was measured for four levels of canopy cover,i.e., clearcut, 25%, 75%, and uncut, in northern red oak (Quercus rubra) and red pine (Pinus resinosa) stands in northern Lower Michigan, USA. Cellulose mass loss was more rapid in the clearcut and 25% canopy cover treatments than in the 75% canopy cover and uncut treatments. After 4 month incubation of cellulose filter papers, mass loss rates averaged 75.2% in the clearcut, 56.3% in the 25% canopy cover, 46.9% in the 75% canopy cover, and 45.7% in the uncut stands. For the clearcut and the 25% canopy cover treatments, cellulose mass loss in the mineral soil layer was significantly higher than in the forest floor after 2 and 4 months of incubation, while cellulose mass loss of the uncut treatment was significantly lower in the soil layer than in the forest floor after 4 months of incubation. Cellulose mass loss was not significantly different between the oak and the pine stands (p > 0.05), but cellulose mass loss rates in other canopy cover treatments except for the clearcut were generally higher in red oak stands than in red pine stands. These results suggest that canopy manipulation increases cellulose decomposition and may stimulate nutrient cycling process in canopy removal stands. This study was supported in part by USDA Forest Service and Michigan Technological University.     

CNC负载ZnO纳米复合材料的吸附-光催化性能

以醋酸锌为原料、硫酸水解的纤维素纳米晶(CNC)为模板,通过沉淀法制备CNC负载ZnO纳米复合材料(CNC/ZnO),并进一步经550℃处理,得到CNC/ZnO的碳化产物(C CNC/ZnO)。采用透射电子显微镜(TEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FT IR)、紫外可见漫反射吸收光谱(UV Vis DRS)对其形貌结构、晶体结构、化学结构和光吸收性能进行表征,并测试其对亚甲基蓝(MB)染料的吸附 光催化性能。结果表明:CNC/ZnO纳米复合材料中,ZnO通过静电作用附着于CNC上,呈棒状及纵横交错排列,分散性得到显著提高;经550℃碳化后,ZnO仍以棒状排列方式沉积于碳化CNC上,排列方式未发生变化。引入CNC模板及碳化处理对ZnO晶体结构及光吸收性能产生重要影响,CNC/ZnO复合材料中,ZnO晶粒尺寸为8.4 nm,高于纯纳米ZnO(6.3 nm),其带隙能(Eg)为3.18 eV;C CNC/ZnO复合材料中,ZnO晶粒尺寸为7.8 nm,Eg值减小至1.75 eV。吸附 光催化性能测试表明:CNC/ZnO纳米复合材料对MB具有良好的吸附性能,黑暗条件下搅拌60 min,对MB的吸附去除率可达58%,开启光照60 min后,其对MB的吸附 光催化去除率增至88%;C CNC/ZnO复合材料对MB具有良好的吸附 光催化协同作用,黑暗下吸附60 min,对MB的吸附去除率为49%,光照60 min后,其对MB的吸附 光催化去除率可达99%。     

Estimation of the sulfur ester content of cellulose nanocrystals prepared by sulfuric acid hydrolysis: a reproducible and fast infrared method

A fast and reproducible method for estimating the sulfur ester content of cellulose nanocrystals (CNCs) prepared by a pilot plant (Alberta Innovates Technology Futures—Alberta, Canada) is discussed. CNCs from sulfuric acid hydrolysis form electrostatically stabilized suspensions because of the introduction of sulfate ester groups onto the surface of the crystallites during the chemical production. The surface charge of the crystals and indirectly the sulfur ester content has implications when considering several applications. In the past, tedious and time-consuming methods such as X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis have been used to estimate the sulfur content of CNCs. As of late, conductometric titrations have surpassed these techniques for estimating the sulfur content of CNC. In this communication, a technique is explored that is specific, fast, and reproducible across a number of samples for determining the quantity of C–O–S linkages in CNC samples. The method is based on integrating key peaks characteristic of sulfur functionalities obtained via Fourier transform infrared spectroscopy. The samples were analyzed as obtained, and no time was needed for extra sample cleanup prior to analysis. Finally, good correlation was obtained between the results obtained for the different samples and comparable to the results obtained from the widely used conductometric method.     

不同活化方法对微晶纤维素结构和氧化反应性能的影响

分别采用超声波与碱润胀对微晶纤维素进行活化,比较了两种方法对微晶纤维素(MCC)超分子结构和物理特性的影响,并通过与高碘酸钠的反应分析了不同活化方法对微晶纤维素选择性氧化性能的影响,初步探讨了其作用机理。结果表明,超声波作用后微晶纤维素的晶型没有发生改变,晶粒尺寸基本不变,但是超声波能使纤维素分子中的氢键受到破坏,结晶度下降,结构变得疏松,表面和内部结构受到一定的损伤,比表面积和可及度增大,反应活性提高;碱润胀后,微晶纤维素的晶型发生了改变,为纤维素Ⅰ型和Ⅱ型的混合体,但碱润胀有消晶的作用,使晶区发生破裂,晶粒尺寸大幅度下降,比表面积显著增加。两种活化方法都能显著提高纤维素的选择性氧化性能,超声波和碱润胀活化后氧化纤维素(DAC)的醛基含量分别由未活化时的71.3 %提高到85.0 %和88.8 %。     

马来酸乙基纤维素的制备与表征

为提高乙基纤维素的进一步应用,以乙基纤维素为原料,马来酸酐为衍生化试剂,制备了马来酸乙基纤维素,通过红外、核磁、X射线衍射、差示扫描量热(DSC)等手段对其结构及性质进行了表征,研究了反应各因素对产物取代度的影响,确定了马来酸乙基纤维素(ECMA)最佳反应条件为:马来酸酐与乙基纤维素中羟基总量物质的量之比为4:1,反应...     

Study of the Digestive Rate of Coarse Cellulose of Giant Pandas

IntroductionBal11booisl11ainfoodoftl1cgial1tpal1daint`.ildal1dman-fedgiantpandattasfCd111ucl1bal11boobcsldcsconccntratestl1atx`erel11adcofgrainPOwdcrtokccpltsfeedingl1abitsinwiId,buttl1cdigestivcratcofcoarsccclluloseisvery'low,il1botl1ttilda11d111a11-fcdpa11das.Wecanfindthattl1eba111boot'asall11ostl1otdigcstcdfrolllthefCccsthatcol1tai11edl11ucI1bal11boosticks.CI1cl1Yucllulletc.(l993)rcPortedt1lattl1edigcstit'eratcil1bal11boocoarsecelluloscisabout25%ol1lv.Tl1cautl1orsdesiglledthiscxPCrilll…     

Graft copolymerization of cellulose and 2-hydroxyethyl methacrylate in an ionic liquid

Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, 1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose I to cellulose II after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P (2-hydroxyethyl methacrylate) was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60°C; the rate of grafting reached 77.3%.     

球磨-酶解法制备纳米竹纤维的结构表征

采用机械球磨对竹纤维进行预处理,再经纤维素酶水解制备纳米竹纤维。通过光学显微镜(OM)、透射电子显微镜(TEM)、傅立叶红外光谱仪(FTIR)和X射线衍射仪(XRD)对竹纤维的形貌、组成、光谱学性能以及晶体特性进行了表征。实验结果表明:球磨法和酶解法在一定程度上都可以细化竹纤维;球磨预处理有助于竹纤维的酶解过程,且球磨-酶解法制备的纳米竹纤维粒径在100 nm左右;所制备的纳米竹纤维仍然保持竹纤维的基本化学结构,但球磨处理破坏了纤维素的结晶结构,其结晶度由64.15%降低到了38.55%。     

Study of crystalline behavior of heat-treated wood cellulose during treatments in water

The crystalline behavior of heat-treated wood cellulose treated at 85% relative humidity (RH), in water, or boiled in water after heat treatment was investigated. The normal increased crystallinity was significantly depressed for samples that were oven-dried and then treated in 85% RH or in water. In the case of boiling-water treatment, a more pronounced increased in crystallinity was initially observed, which then decreased gradually. The crystallinity decreased more than untreated wood for samples that were heat treated for long periods and was slightly higher than the decreased crystallinity from the beginning of the above two treatments. On the other hand, no significant change in crystallinity was observed for samples of increased crystallinity or decreased crystallinity that were treated under high-moisture conditions, for all three treatments. The results show that the crystalline state of wood cellulose heat treated under oven dry or high-moisture conditions behave differently if treated in water after heat treatment. Results suggested that the mechanism of crystallization might be different for samples that are subjected to heat treatment under oven-dry and high-moisture conditions.