Saccharification of cellulose by dry pyrolysis

Pyrolysis of cellulose was studied for the purpose of practical production of 1,6-anhydro-β-D-glucopyranoside (levoglucosan, LG). To minimize secondary degradation of levoglucosan, two methods were examined: (1) conductive heating by glass bottle, and (2) radiation heating from the surface by CO₂ laser beam, both under vacuum and in a nitrogen atmosphere. Glass-bottle pyrolysis under vacuum gave levoglucosan yield of 50%–55% in the optimum temperature range of 350°–410°C, where placing the cold trap in the vicinity of heated area was effective in improving the yield. In contrast, glass-bottle pyrolysis under nitrogen gave low yields of 17%–20%, probably due to slower diffusion of pyrolysis product from hot region. The CO₂ laser pyrolysis under vacuum gave the product as aerosol (white smoke), causing difficulty in recovery of the product, and the maximum yield was 5%–17%. In this case the treatment under nitrogen flow was effective for recovery of aerosol, and the maximum yield reached approximately 25%.     

Carbonization of bamboo and consecutive low temperature air activation

Raw moso bamboo (Phyllostachys pubescens) was examined to optimize the carbonization and the consecutive air activation procedure. Influence of sample size, nitrogen flow rate, heating rate and final temperature on the carbon yield and the pore structure was investigated for the raw bamboo. The short length cutting along bamboo trunk and the increase in heating rate to 40°C/min and nitrogen flow rate up to 500 ml/min was found to be advantageous for the carbonization of raw bamboo at 500°C, resulting in a surface area of 230 m²/g with a bamboo char yield of 25% on dry base. In the next step, effects of air treatment temperature, ash content and its composition on the pore development were studied for the prepared bamboo char in comparison with coconut shell char. Additional increase in surface area by 200 m²/g with 97% yield could be achieved conducting the 2-hour air treatment at 280°C for the bamboo char, whereas only a 100 m²/g rise in surface area was attained for the coconut shell char, partly due to the difference in K₂CO₃ content in the char.     

Extraction and decomposition of hiba wood into valuable chemicals using stepwise temperature supercritical carbon dioxide treatment

Hiba (Thujopsis dolabrata) wood was treated with supercritical carbon dioxide (scCO₂) at stepwise temperature increments from 50° to 400°C continuously so that extractives (dichloromethane-soluble and -insoluble phases) and solid residues were obtained. The yield of extractives from hiba wood increased with increasing extraction temperature. The volatile compounds in the dichloromethane-soluble phase from scCO₂ extraction at 50°C contained only terpenoids. However, the volatile compounds in the dichloromethane-soluble phase from scCO₂ extraction at 300°C not only contained terpenoids but also phenols, furans, hydrocarbons, and organic acids. The yield of β-thujaplicin, which is a useful compound in hiba wood, increased with increasing extraction temperature from 50°C to 300°C; the optimal conditions for extracting β-thujaplicin were 300°C and 19.61 MPa. Further study of degradated compounds from the cellulosic and lignic materials of hiba wood after stepwise high-temperature scCO₂ treatment above 300°C may provide clues to its efficient use.     

Influence of inorganic matter on wood pyrolysis at gasification temperature

The influence of inorganic matter on the pyrolysis of Japanese cedar (Cryptomeria japonica) wood was studied at a gasification temperature of 800°C with demineralization through acid washing. Some influences on the formation of char, tar, and low molecular weight products coincided with results reported at temperatures lower than the gasification temperature. However, the carbonization behavior of the volatile products and the yield of polysaccharide fraction were not able to be explained as a sum of the pyrolysis of cellulose, hemicellulose, and lignin even after demineralization. These results suggest some interactions between wood constituent polymers other than the influence of inorganic matter.     

Pyrolysis reactions of Japanese cedar and Japanese beech woods in a closed ampoule reactor

The chemical structures of hemicellulose and lignin are different for two distinct types of wood, i.e., softwood and hardwood. Such differences are expected to affect pyrolysis behavior. In this article, the differences are discussed for Japanese cedar wood (a softwood) and Japanese beech wood (a hardwood) pyrolyzed in a closed ampoule reactor (N₂/600°C/40–600 s). Oven-dried samples were used to eliminate the influence of initial water. Demineralized samples (prepared by acid washing) were also used to determine the influence of the minerals contained in the wood samples. As a result, some features were disclosed for secondary char (coke) formation, char reactivity, tar formation, and subsequent decomposition.     

Complete gasification of cellulose in glow-discharge plasma

The behaviors of cellulose (commercially available filter paper) were investigated in glow-discharge plasma, where pyrolysis does not occur because of low temperatures. Cellulose filter papers were decomposed in a glow-discharge plasma with nitrogen flow even at low temperatures of around 50 °C and disappeared completely after a treatment of approximately 90 h without char formation. Tar formation was not observed on any surfaces inside the plasma chamber and vacuum lines. Hence, it was concluded that all cellulose was decomposed into gaseous products. An in-situ analysis of gaseous products by quadrupole mass spectrometry suggested the formation of H₂, H₂O, CO and CO₂ from cellulose. These findings indicate that a clean and complete gasification of cellulose can be achieved with glow-discharge plasma.     

Gas-phase pyrolysis of methyl glucosides and levoglucosan

Levoglucosan, the major intermediate in cellulose pyrolysis, is stable up to around 500?°C in the gas phase. To study whether this stability is a characteristic property of levoglucosan, the gas-phase reactivity was compared with those of methyl α- and β-glucosides at 200–500?°C (residence time 1.2–2.0 s). The methyl glucosides decomposed even at 200 and 300?°C to form levoglucosan exclusively. This selective transglycosylation was explained with a concerted mechanism. Fragmentation of the glucosides forming C1–C3 carbonyl compounds started at 400?°C, a temperature lower than that of levoglucosan (500?°C). Thus, levoglucosan is a special carbohydrate that is stable in the gas phase, and the stability is explained by the steric hindrance of the bicyclic ring. Formation of the anhydrofuranose isomer and furans was negligible from the gas-phase pyrolysis of these compounds, suggesting that these are produced mainly from the molten-phase pyrolysis. These results show the roles of gas- and molten-phase reactions during carbohydrate pyrolysis, providing insights for upgrading biomass pyrolysis/gasification processes.     

Vanillin production from native softwood lignin in the presence of tetrabutylammonium ion

Vanillin is one of the industrially important compounds that can be produced from lignin. This study presents production of vanillin and vanillic acid (oxidized form of vanillin) through aerobic oxidation of Japanese cedar (Cryptomeria japonica) at 120 °C for 72 h in aqueous alkali solutions with several Bu₄N⁺ and OH^? concentrations (1.25, 2.50, and 3.75 mol/L), where Bu₄N⁺ is an enhancer of the vanillin formation reported in our previous study. The concentrations of Bu₄N⁺ and OH^? were adjusted by the additions of Bu₄NCl and solid NaOH into the base medium Bu₄NOH·30H₂O, which forms 1.25 mol/L aqueous solution of Bu₄NOH at the elevated temperature. Vanillin and vanillic acid were produced with the maximum yields of 21.0 and 1.7 wt% (lignin-base), respectively, at the 1.25 mol/L Bu₄N⁺ and 3.75 mol/L OH^? concentrations. This vanillin yield is close to that obtained by the alkaline nitrobenzene oxidation (26.5 wt%), indicating significantly high selectivity of our lignin degradation with Bu₄N⁺ toward vanillin formation. We also proposed a novel Bu₄NOH·30H₂O-free reaction medium, where Bu₄NOH·30H₂O as the base medium were substituted with an aqueous solution of Bu₄NCl and NaOH to avoid using expensive Bu₄NOH·30H₂O. The treatment of the Japanese cedar with this alternative medium exhibited the moderately decreased vanillin yield of 14.6 wt%, which is, however, much higher than the vanillin yield obtained with a simple 1.25 mol/L NaOH solution.     

Thermal treatment of sawdust and coal-tar pitch mixture to produce porous carbon materials by chemical activation

In this work, different activated carbons were prepared from composites based on birch sawdust and coal-tar pitch by chemical activation with zinc chloride, phosphoric acid, and potassium hydroxide followed by carbonization. The influence of different chemical agents (ZnCl₂, KOH, and H₃PO₄), final temperature of carbonization and media on yield and structural properties of the carbonic product was studied. It was shown that chemical agents allow increasing yield of carbonic residue. Composite modification by H₃PO₄ or ZnCl₂ facilitates the formation of molded porous carbonic residue during the carbonization process. However, addition of KOH to the composite leads to formation of powder-like carbonic residue having a specific surface area of 1,600 m² g^?1 at 800 °C. It was established that all samples aged in air medium at 800 °C have higher values of specific surface area in comparison with the same samples aged in argon medium at similar conditions.     

TGA modeling of the thermal decomposition of CCA treated lumber waste

 To guide the development of thermal decomposition methods for disposal of CCA treated wood, reactions during the thermal decomposition of CCA treated wood were modeled using thermogravimetric analysis (TGA), with special focus placed on arsenic volatilization. Simple inorganic compounds, such as As₂O₅, CuO, and Cr₂O₃, were used to model the thermal behavior of the inorganics in CCA treated wood. In air and nitrogen, arsenic (V) oxide began to volatilize at 600 °C during temperature ramps at 5 °C/min. During a 5 °C/min ramp in a hydrogen mix, arsenic (V) oxide began decomposition at 425 °C. Arsenic volatile loss from CCA treated wood can depend strongly on the gases produced by wood thermal decomposition. In the presence of As₂O₅, chromium (III) oxide and copper (II) oxide formed arsenates in air and nitrogen. Chromium arsenates began decomposition as low as 790 °C. This suggested that chromium arsenates in CCA treated wood formed during original preservative fixation may decompose as low as 790 °C. Copper arsenates were stable up to 900 °C in air, but showed only a limited range of stability in nitrogen. Depending on process conditions, the formation of copper arsenates may limit arsenic loss during thermal decomposition of CCA treated wood up to 900 °C. The thermal decomposition of inorganic oxides was influenced by interactions with wood and wood decomposition products. In a dry YP sawdust/As₂O₅ mix, arsenic (V) oxide volatilized at 370 °C during inert pyrolysis at 5 °C/min and at 320 °C during smoldering combustion at 5 °C/min. Thermal dwells of a dry YP/As₂O₅ mix showed no arsenic loss at 250 °C, but significant loss occurred during higher temperature dwells. During inert pyrolysis at 5 °C/min, the formation of complexes and hydrates were shown to prevent arsenic loss up to 400 °C. Received 14 July 1999     

Über den Einfluß der Temperatur auf die Entwicklung und Vermehrung des Bekreuzten Traubenwicklers,Lobesia botrana Den. et Schiff. (Lepid., Tortricidae)

By breeding grape moth,Lobesia botrana Den. et Schiff., in laboratory conditions the effect of constant temperatures on the growth and reproduction of the pest was investigated. On the basis of collected data the sum of effective temperatures for every stage of growth as well as the threshold temperature for the growth were calculated. For the embryonic development the temperatures are 74,0°C±2,3°C and 8,8°C; for the larval development in males 384,6°C±30,1°C and 7,3°C, in females 362,3°C±20,9°C and 9,4°C; for the chrysalis stage in males 162,1°C±23,5°C and 7,1°C, in females 151,5°C±24,0°C and 9,1°C. The sums of effective temperatures of the particular growth stages were completed by their quantil values (Q₃₀, Q₅₀, Q₇₅, Q₉₅). The threshold temperature for the life of moths was set up as 11,0°C in males and 12,8°C in females. The reproduction activity in the majority of females begins at temperatures above 15°C. The effect of the temperature on the actual fertility has proved to be significant. The optimal temperatures for the oviposition are within the range of 20,0°C–27,0°C. The relation between the actual fertility and temperature is at these temperatures determined by the regression line equation Y=?5,75·X+293. Temperatures below or above the limits of this interval are less favourable for the oviposition because they lead to a decreasing of actual fertility. The limit temperature (15°C) of reproduction activity in the majority of females is considered to be the lowest extreme temperature for the oviposition.     

Surface modification of birch veneer by peroxide bleaching

This study examined effects of surface modification with hydrogen peroxide (H₂O₂) on adhesive bond performance in birch veneer bonded with phenol–formaldehyde resin. The veneer was treated with 5% of H₂O₂ at 80 °C in the presence of alkali with the objective of improving adhesive bond performance and reducing the resin demand. The effects of the surface modification were determined by surface color measured with a spectrophotometer, bond performance tests with ABES (automated bonding evaluation system) and surface hydrophobicity with sessile contact angle measurements. Results demonstrated that veneer surface became significantly whiter, which also increased in lightness and decreased in redness and yellowness. ABES test revealed that a remarkable increase in bond performance in the treated veneer and the maximum bond strength with the treatment at 60 min, which was nearly twice as high as reference sample (5.42 → 9.94 N/mm²), was obtained. A notable decrease in contact angle measurements was also observed in the treated veneers (0° in 0.5 s). The surface modification of birch veneer with H₂O₂ + alkali demonstrated greater potential for the improvement of physical characteristics in veneer surface. Other aspects of H₂O₂ consumption during the treatment are also discussed.     

Green color protection of bamboo culms using one-step alkali pretreatment-free process

This study evaluated the protection effectiveness of alcohol-borne reagents for the green color of ma bamboo (Dendrocalamus latiflorus Munro) and moso bamboo (Phyllostachys pubescens Mazel). The results show that the types and concentrations of alcohol-borne reagents, the kinds of solvent, and the conditions of treatment greatly affected the green color of these two bamboo species. Without alkali pretreatment, an excellent green color protection (a* = −14.5) was obtained when the ma bamboo culms were treated with 0.5% methanol-borne copper chloride (CuCl₂) at 60°C for 30 min. Similar results were also obtained when ma bamboo culms were treated with 0.5% methanol-borne copper nitrate [Cu(NO₃)₂] at 60°C for 2 h (a* = −13.5). For moso bamboo, an attractive green color in the bamboo culms was achieved by treating the specimens with 1% methanol-borne copper acetate [Cu(CH₃COO)₂] at 60°C for 30 min. The a* value of treated specimens was −13.3. In addition, results demonstrated that ultrasonic treatment was more effective on green color protection than conventional water bath treatment. When moso bamboo was treated with 1% copper acetate at 60°C in an ultrasonic bath for only 15 min, a remarkable green color with an a* value of −13.6 was obtained on the bamboo epidermis.     

Extraction of cellulose with subcritical and supercritical ethanol

lntroductionAsaresuItofthepublic'sincreasingenvironmentalawareness,theresearchesfocusedondevelopingprocessesthatutilizeIowtoxicorganicsoIventshavefIourishedinthepast1oyears.Mostofthesere-searcheshaveexaminedthepossibilityofusingsu-percriticaIandslightIysubcriticalfluidsaseXtractionandreactionsolvents(Reaves1999).SupercriticalfIuidextractionoflignoceIluIosicma-teriaIsfrombiomassissimilartopyrolysis,whichisusedtoconvertbiomasstousefuIchemicalsorfluidfuels(Goto199o).ThepyroIysisofbiomasscan…     

Optimization of ultrasound-assisted extraction of camptothecin from <Emphasis Type="Italic">Camptotheca acuminata</Emphasis> seeds

Naturally occurring camptothecin(CPT) is an important source of chemotherapeutic agents.The extraction from Camptotheca acuminata is still the main approach to obtain CPT compared with total synthesis.In the present study,ultrasound-assisted extractions(UAE) of CPT from C.acuminata seeds with alkaline solutions were investigated and CPT yield were determined by High Performance Liquid Chromatography.The conditions of alkaline species and concentrations,extraction time,extraction temperature and ultrasonic power were optimized.Results show that both Na3PO4 and Na2CO3 solutions gain good extraction yields,whereas Na3PO4 solution has stronger basicity and need higher concentration than Na2CO3 solution does,thus aqueous Na2CO3 is more beneficial for the extraction.The optimal condition was ultrasonically extracted with 0.5% aqueous Na2CO3 at 50°C and ultrasonic power of 400 W for 60 min.Comparing with UAE with ethanol,the extraction with 0.5% Na2CO3 solution achieves higher yield.Moreover,aqueous Na2CO3 as a solvent has various advantages including non-toxicity,inflammable,non-corrosive and low cost,which ensure this UAE method is a superior method with high utilizing prospect.     

Ice nucleation and frost resistance of Pinus canariensis seedlings bearing needles in three different developmental states

Frost resistance and ice formation in different developmental states of needles of P. canariensis seedlings were assessed. Regrowth after frost damage was used to determine the overall frost survival capacity. Two distinct freezing exotherms (E1, E2) were registered. E1 was between ?1.7 and ?2.0 °C. Initial frost damage (LT₁₀) was 1.5–2.7 °C below E1. E2 was between ?5.6 and ?6.0 °C, and either corresponded with LT₅₀ or occurred in between LT₁₀ and LT₅₀. Current year needles were less frost resistant than 1-year-old needles. The overall recuperation capacity of seedlings revealed that frost survival may be underestimated when only needle damage is assessed. Freezing of seedlings with or without roots had no effect on the frost resistance of needles but recuperation capacity was significantly affected. Seedlings survived ?10 °C during summer indicating that they withstand the lowest naturally occurring frosts in Tenerife.     

温度对大叶桃花心木(Swietenia macrophylla King)幼苗叶片的光合影响

本文研究了大叶桃花心木（Swietenia macrophylla King）一年生幼苗在经过夜温处理后的光响应曲线和在饱和光强下的CO2反应曲线.结果表明:在大气CO2浓度下,叶片的最佳光合作用温度在25-31℃之间,而在饱和CO2浓度下为31-35℃.在25℃以下光合速率开始降低,主要是由于羧化效率的降低,而当温度超过31℃时,光合速率下降,是因为羧化效率的降低和呼吸速率的增加.CO2浓度对光合的促进作用在低温下受到抑制,这意味着未来在CO2浓度增高的情况下,高浓度的CO2对热带常绿植物光合的促进在冬天低温情况下表现不十分明显.图4参23.     

Improvement of softening treatment technology of bamboo

In order to improve the efficiency of softening bamboo block when manufacturing bamboo veneer, chemistry reagents such as NaHCO₃ are often adopted during bamboo softening treatment. But the results of Fourier transform infrared spectroscopy (FTIR) showed that the band intensity at 1,733 cm⁻¹, assigned to C=O stretching vibration in xylan, was reduced in the spectrum of softening-treated bamboo with NaHCO₃ compared with that of not softening-treated bamboo and softening treatment of bamboo without NaHCO₃. That is to say, that the hemicellulose of bamboo was destroyed after softening treatment with NaHCO₃, which meant that softening treatment of bamboo with NaHCO₃, is not a perfect softening treatment method. Thus, in this paper a softening technology at 120°C for 30 min in a closed container was adopted. The results of FTIR show that there was almost no difference in FTIR spectra between no softening treatment of bamboo and softening treatment of bamboo at 120°C for 30 min, which meant that softening treatment at 120°C for 30 min had no effect on the composition of bamboo. The results of dynamic mechanical analysis (DMA) show that T _g of not softening-treated bamboo was 120°C, while T _g of softening-treated bamboo at 120°C for 30 min was 88°C. T _g of softening-treated bamboo at 120°C for 30 min decreased by 26.7% compared with that of not softening-treated bamboo. The results of hardness show that the hardness of bamboo strip after a softening treatment for 30 min at 120°C decreased by 42.0–54.6% compared with that of not softening-treated bamboo. The results of hardness and DMA show that the effect of softening treatment of bamboo at 120°C for 30 min was resultful.     

温度对杉木林土壤呼吸的影响(英文)

Soil samples collected from the surface soil (0(10 cm) in an 88-year-old Chinese fir (Cunninghamia lanceolata) forest in Nanping, Fujian, China were incubated for 90 days at the temperatures of 15°C, 25°C and 35°C in laboratory. The soil CO2 evolution rates were measured at the incubation time of 2, 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70, 80 and 90 days. The results showed that CO2 evolution rates of soil samples varied significantly with incubation time and temperature during the incubation period. Mean CO2 evolution rate and cumulative amount of CO2 evolution from soil were highest at 35°C, followed by those at 25°C, and 15°C. Substantial differences in CO2 evolution rate were found in Q10 values calculated for the 2nd and 90th day of incubation. The Q10 value for the average CO2 evolution rate was 2.0 at the temperature range of 15-25°C, but it decreased to 1.2 at 25- 35°C. Soil CO2 evolution rates decreased with the incubation time. The cumulative mineralized C at the end of incubation period (on the 90th day) was less than 10% of the initial C amounts prior to incubation.     

Optimization study for preparation of activated carbon from Acacia mangium wood using phosphoric acid

A study on the preparation of activated carbon from Acacia mangium wood was conducted, and the operating factors, such as activating agent concentration, activation temperature and activation time, were optimized using response surface methodology. In order to determine the effects of the operating factors namely H₃PO₄ concentration (6.48–48.5 %), activation temperature (364–1,036 °C) and activation time (19–146 min) on the characteristics of activated carbon, a three-level rotatable central composite design was used. The second-order mathematical model was proposed by regression analysis of the experimental data gathered from 20 batch runs. The optimum H₃PO₄ concentration, activation temperature and activation time were found to be 40 %, 900 °C and 45 min, respectively. At optimum conditions of the operating factors, the percent yield and surface area were 20.3 % and 1,767 m²/g, respectively. The activated carbon was found to be largely composed of mesopores. About 95 % of the total surface area was attributed to mesopores.