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Table of Content

    28 October 2014, Volume 34 Issue 5 Previous Issue    Next Issue
    Identification and Lignin Degradation of Pycnoporus sanguineus Strain NFZH-1 with an Endogenous Mediator
    FENG Nian-jie, ZHAI Hua-min, WANG Chuan-huai
    2014, 34 (5):  1-7.  doi: 10.3969/j.issn.0253-2417.2014.05.001
    Abstract ( 747 )   PDF (789KB) ( 632 )   Save
    The process of lignin degradation by white-rot fungi can be intensified by the presence of endogenous mediators. A high-yield laccase-producing fungus with an endogenous mediator is important for the commercial application of laccase. In the present study, we isolated two strains of Pycnoporus sanguineus, namely, NFZH-1 and NFZH-2 from mountain forest region in Nanjing, China, and their laccase production and delignifying characteristics was studied. We also studied these strains in comparison with the best-studied lignin-degrading fungus, Coriolus versicolor. P. sanguineus strain NFZH-1 with an endogenous mediator was identified. Thereafter, NFZH-1 was found to be a high yield laccase-producing strain as determined by the color-reaction and solid-state fermentation. The color zone diameter of NFZH-1 was found to be substantially greater than the mycelia colony one. Moreover, the color zone revealed a dark brown color-reaction using guaiacol as substrate. The laccase activities of P. sanguineus NFZH-1 were found to be 23 600 U/g, while no LiP and MnP were produced in solid-state fermentation. NFZH-1 demonstrated the capability to degrade 56.7% of Klason lignin and 36.6% of holocellulose in wheat straw within 30 days of incubation. Our results indicate that P. sanguineus NFZH-1 is a powerful and selective lignin-degrading strain.
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    Kinetic Analysis of Biomass and Coal Mono-pyrolysis as well as Co-pyrolysis by Coats-Redfern
    SUN Yun-juan, JIANG Jian-chun, WANG Yan-jie, YING Hao, DAI Wei-di, XU Le
    2014, 34 (5):  8-14.  doi: 10.3969/j.issn.0253-2417.2014.05.002
    Abstract ( 1185 )   PDF (1444KB) ( 820 )   Save
    In this paper, Coats-Redfern was used to analyze the dynamic characteristics of biomass with coal mono-pyrolysis and co-pyrolysis. It mainly researched the influence of heating rate and reaction order on pyrolysis integral curve. It found that in the temperature zone which weight lost rate of raw materials was 5 %-80 %, the higher reaction order and lower reaction temperature, the more influence of heating rate on the pyrolysis integral curve. With the heating rate increasing, the pyrolysis integral curve gradually moved to the high temperature zone. When the different reaction order in the same temperature range was chosen, biomass pyrolysis integral curves all showed well linear relation, especially the rice husk. But reaction orders had clearly influence on the results of the coal mono-pyrolysis and biomass co-pyrolysis with coal. At high reaction orders, it had the well fitting curve, but at the low ones, fitting curves drifted off the linear forms. With the coal rank increasing, the fitting curve obviously drifted off the linear forms. The fitting degree of biomass co-pyrolysis with coal was between the biomass mono-pyrolysis and coal mono-pyrolysis. In the lower temperature range, there was synergistic effect on co-pyrolysis of biomass and coal.
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    Hydrogen Reduction of Straw Alkali Lignin Catalyzed by Solid Superacid SO42-/ZrO2
    ZHANG Sheng-ming, LIU Liang, MA Yan-li, FANG Gui-zhen
    2014, 34 (5):  15-21.  doi: 10.3969/j.issn.0253-2417.2014.05.003
    Abstract ( 834 )   PDF (1255KB) ( 600 )   Save
    Solid superacid SO42-/ZrO2 was prepared by impregnation-calcination method and characterized by XRD, elementary analysis, FT-IR, SEM and Hammett indicator. The reduction reaction of alkali lignin catalyzed by SO42-/ZrO2 with different preparation conditions was conducted under different conditions. The number of functional groups of lignin before and after chemical reaction was determined. The results showed that SO42-/ZrO2 has higher superacidity and catalytic activity after being impregnated with 1 mol/L sulfuric acid and calcined at 550 ℃ for 3.5 h. Under the condition of catalyst dosage 5%, temperature 100 ℃, time 4 h, and H2 pressure 3 MPa, the contents of total hydroxyl, phenolic hydroxyl and alcoholic hydroxyl of alkali lignin were 9.34%, 3.28% and 6.06% after reaction, and increased by 55.15 %, 13.89 % and 93.00 %, respectively, compared with those before reaction. After reaction, the stability of phenyl structure, the content of active functional groups and the reactivity of lignin increased.
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    Preparation of Aldonic Acids by Whole-cell Catalysis and Its Identification
    WANG Xing, ZHOU Xin, XU Yong, YONG Qiang, YU Shi-yuan
    2014, 34 (5):  22-26.  doi: 10.3969/j.issn.0253-2417.2014.05.004
    Abstract ( 975 )   PDF (924KB) ( 675 )   Save
    Five calcium aldonates were firstly produced from glucose, xylose, arabinose, galactose and mannose respectively by whole cell catalysis using Gluconobacter oxydans in the shake-flask liquid system. Their purities were detected by high performance anion-exchange chromatography coupled with pulsed amperometric detector (HPAEC-PAD), and the molecular structures were identified by infrared spectroscopy (IR) and electrospray ionization mass spectrometry (ESI-MS). The results indicated that a strong absorbance of COO- deprotonated carboxylic group characteristic peak located at 1600 cm-1 was observed in IR. In ESI-MS spectra, the characteristic molecule-mass peaks in pentonic acids and hexonic acids were identified at 165.1 and 195.1, respectively. These values were consistent with the theoretical values.
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    The Adsorption Properties of Rice Husk-based and Silicon-freed Rice Husk-based Activated Carbon on Organic Compounds
    LIU Bin, GU Jie, QIU Pan, LU Yu-cong, ZHOU Jian-bin
    2014, 34 (5):  27-34.  doi: 10.3969/j.issn.0253-2417.2014.05.005
    Abstract ( 850 )   PDF (1212KB) ( 709 )   Save
    The activated carbons were prepared from rice husks and silicon-freed rice husks by composite activator. The difference between rice husk-based activated carbon (RAC) and silicon-freed rice husk based activated carbon (FAC) in pore structure and surface chemistry were analyzed. The synthesized activated carbon was used as adsorbents in water treatment. The adsorption properties, isotherms and kinetics of fuchsine on activated carbons were investigated. The results indicated that the BET surface area of RAC and FAC reached 1 924 and 2 433 m2/g, respectively. There FAC has more functional groups compared with RAC. RAC and FAC could improve the removal efficiency of fuchsine at high pH value. The adsorbents could be used in high salt concentration conditions. When the initial pH 7, initial mass concentration 400 mg/L and the adsorbents dosages 0.8 mg/g were used, the adsorption capacity of RAC and FAC was 439 and 483 mg/g, respectively. The Langmuir isotherm model was found to fit well with the adsorption process of RAC and FAC. Both the kinetics and desorption study indicated that the adsorption process was controlled by chemisorption.
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    Chroma Determination of APMP Pulping Wastewater by Ratio-derivative Spectrometry
    CHEN Hong-lei, YANG Gui-hua, CHEN Jia-chuan, LIU Yu, KONG Fan-gong, WU Qin
    2014, 34 (5):  35-40.  doi: 10.3969/j.issn.0253-2417.2014.05.006
    Abstract ( 794 )   PDF (929KB) ( 794 )   Save
    A new method is described to measure the chroma of APMP pulping effluent by using ratio-derivative spectrometry. Adjusting the pH value and removing suspended substance before detection of chroma were not necessary in this method, and the detection wavelength was 255 nm. Precision and accuracy were suitable, and relative deviation was within ±8 % when the chroma of samples was in the range of 50-1 130 C.U. In contrast to the traditional methods, the present test procedure was simplified and the error caused by human factors was minimized. No other chemicals were applied during the whole test procedure and the method was an environmental friendly approach for chroma determination. Ratio-derivative spectrometry was satisfactory for the chroma determination of APMP pulping effluent.
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    Solubility of Lignin in Ionic Liquid by Assistance of Microwave Energy
    LIU Shi-wei, ZHOU Hong-xia, LI Lu, YU Shi-tao, XIE Cong-xia, LIU Fu-sheng
    2014, 34 (5):  41-46.  doi: 10.3969/j.issn.0253-2417.2014.05.007
    Abstract ( 715 )   PDF (1939KB) ( 577 )   Save
    Five phosphite-based ionic liquids were synthesized, characterized, and used to dissolve lignin under oil bath and microwave heating. It was found that ionic liquid 1,3-dimethylimidazolium phosphate [Mmim] DMP had good solubility performance, and the solubility of lignin was 60.0g at 55℃for 30 min. The chemical structure, morphology and crystalline of re-generated lignin from microwave treatment were characterized by FT-IR, SEM, and XRD. The results indicated that the structure of re-generated lignin was unchanged, and the particle had good dispersity and strong diffractive feature. On the other hand, ionic liquid [Mmim] DMP had good reusability. When 100 g[Mmim] DMP was reused for five times, its recovery capacity and lignin solubility were 97.0 g and 57.8g, respectively.
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    Synthesis and Performance of Dehydroabietylamine-chitosan Cationic Surfactants
    PEI Li-jun, CAI Zhao-sheng, SHANG Shi-bin, SONG Zhan-qian
    2014, 34 (5):  47-52.  doi: 10.3969/j.issn.0253-2417.2014.05.008
    Abstract ( 747 )   PDF (785KB) ( 1092 )   Save
    In this paper, the new chitosan derivatives, i.e., dehydroabietylamine-chitosan cationic surfactants(a, b and c), were synthesized with chitosan (1 000, 1 500, 3 000) and dehydroabietylamine as starting material. The cationic surfactants were characterized by FT-IR and 1H NMR , respectively. The surface activities, emulsifying properties and antibacterial properties of the products were also investigated. The results showed that the critical micelle concentrations (CMC) of a, b and c are 3.98×10-4, 2.51×10-3 and 5.01×10-3 mol/L at 25 ℃, respectively. The γcmc of a, b and c are 38.6, 36.8 and 36.6 mN/m, respectively. The emulsifying time of these three surfactants are 44, 71 and 148s, respectively. The antibacterial properties of the target products were tested with the minimum inhibitory concentration method. The preliminary result indicated that those compounds have some antibacterial activity. In particular, the antibacterial activities of the compounds a, b and c against Escherichia aerogenesare are superior to the commercially available fungicides bromogeramine and ampicillin sodium and their minimum inhibitory concentration are 2, 2 and 4 mg/L, respectively. The antibacterial activities of products would be enhanced with the increase of the DS and would be decreased with the increase of the chitosan molecular weight.
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    Liquefaction of Fermentation Residue of Corn Stover in Polyhydric Alcohols
    WEI Bing, CHEN Fan-geng, LI Zhi-hao, CHENG Yuan-chao
    2014, 34 (5):  53-59.  doi: 10.3969/j.issn.0253-2417.2014.05.009
    Abstract ( 790 )   PDF (1334KB) ( 629 )   Save
    Fermentation residue of corn stover was liquefied in polyhydric alcohols in the presence of sulfuric acid as the catalyst at the temperature from 140 to 180 ℃. The liquefied product was used as polyol component for the preparation of rigid polyurethane foam. The results indicated that the highest yield of liquefaction was 64.54%, which was achieved in the mixed solvents of polyethylene 200 and glycol(mass ratio 7:3)with a liquid/solid mass ratio of 4:1, and a mass fraction of sulfuric acid 4 % at 160 ℃ after 2 h. The hydroxyl number and the viscosity of the liquefied product were 349 mg/g and 979 mPa·s, respectively. The benzene/ethanol extractives from fermentation residue was 96.59 % using the optimum reaction conditions. The liquefied product of the extractives, which has a hydroxyl number of 474 mg/g and a viscosity of 791 mPa·s, could be used for the preparation of rigid PU foam, too.
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    Detoxification and Ethanol Fermentation of the Acid-catalysed Steam-exploded Corn Stover Pre-hydrolyzate
    ZHU Jun-jun, YANG Jin-long, ZHANG Ling-ling, HUANG Xin, XU Yong, YONG Qiang, YU Shi-yuan
    2014, 34 (5):  60-66.  doi: 10.3969/j.issn.0253-2417.2014.05.010
    Abstract ( 737 )   PDF (890KB) ( 708 )   Save
    The pre-hydrolyzate obtained from the acid-catalysed steam-exploded corn stover (ASC) after washing with water was used as the raw material. The contents of fermentable sugars, carbohydrate degradation products and main lignin degradation products in the ASC pre-hydrolyzate were analyzed. The ethanol fermentation performance of the ASC pre-hydrolyzate before and after detoxification by three kinds of detoxification methods was also investigated. The results indicated that the ASC pre-hydrolyzate contained fermentable sugars including xylose (49.50 g/L) and few glucose (9.80 g/L), which could be fermented to produce ethanol. However, it was not beneficial to ethanol fermentation because of the existed inhibitors. The sugar utilization ratio and ethanol yield were only 87.96 % and 74.63 %,respectively, after 60 h fermentation. The ethanol fermentation of the ASC pre-hydrolyzate was greatly improved after the ASC pre-hydrolyzate detoxified by ethyl acetate extraction, yeast adsorption and sodium sulfite treatment. The sugar utilization ratio and ethanol yield of the ASC pre-hydrolyzate after detoxification by ethyl acetate extraction were 95.40 % and 90.71 %, respectively, after 36 h. The sugar utilization ratio and ethanol yield of the ASC pre-hydrolyzate after detoxification by yeast adsorption were 97.83 % and 81.98 %, respectively, after 48 h. The sugar utilization ratio and ethanol yield of the ASC pre-hydrolyzate after detoxification by sodium sulfite treatment were 95.55 % and 84.74 %, respectively, after 48 h. Although the detoxification effect of ethyl acetate extraction exhibited the best performance, yeast adsorption and sodium sulfite treatment were the most potential option from the point of industrial application perspective.
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    Synthesis and Biological Activity of Curcumin Derivatives
    KUANG Chun-tao KUANG Chun-tao, LI Xiang-zhou, XUE Hai-peng, DENG Nan, WANG Ling-zhi
    2014, 34 (5):  67-72.  doi: 10.3969/j.issn.0253-2417.2014.05.011
    Abstract ( 978 )   PDF (327KB) ( 743 )   Save
    Four curcumin derivatives were synthesized from curucmin and maleic anhydride by esterification, isomerization, chlorination and esterification. The yields of curcumin derivatives c1-c4 were 80.5%, 83.7%, 81.2% and 85.4%, respectively. Their structures were confirmed by IR, 1H NMR and 13C NMR. The antioxidative and antibacterial activities of target compounds c1-c4 were evaluated. The IC50 values for scavenging of DPPH· were 164.14±0.82, 166.98±0.66, 171.97±0.99 and 175.10±2.34 mg/L, respectively. Their antioxidative activity was lower than that of curcumin (36.22±0.22 mg/L). This proved the importance of phenolic OH. The target compounds c1-c4 displayed high antibacterial activity, especially compound c4. The minimal inhibiting concentration(MIC) of c4 against Staphylococcus aureus, Escherichia coli, Penicillium sp. and Aspergillus niger were 0.5, 0.5, 0.25 and 1.0 g/L, respectively. There is hope to obtain antibacterial candidates by curcumin modification with α, β-unsaturated carbonyl compounds.
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    Purification of Sugars Liquid of Corncob Hemicelluloses by Biological Treatment
    YU Yong-cheng, ZHAO Jian, LI Xue-zhi
    2014, 34 (5):  73-78.  doi: 10.3969/j.issn.0253-2417.2014.05.012
    Abstract ( 630 )   PDF (1028KB) ( 663 )   Save
    Biological treatment was used to remove glucose and galactose in this paper to purify the hemicellulose liquid sugars. Single factor and central composite experiments were used to optimize the medium components in the biological treatment. It was seen that the optimal results were obtained when 5.7 g/L (NH4)2SO4, 2.0 g/L KH2PO4 and 2.4 g/L yeast were applied. The removal of glucose and galactose were 100% and 67%, and the purity of xylose increased from 47% to 60% after the optimal biological treatment. Acclimatization of strain used in the biotreatment of the liquor was also conducted to handle the high sugar consistency liquor which was diluted 6 times.
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    Migration Behavior of Lignin during Bamboo Pre-hydrolysis
    LIN Ling, CAO Shi-lin, MA Xiao-juan, HUANG Liu-lian, LUO Xiao-lin, CHEN Li-hui
    2014, 34 (5):  79-83.  doi: 10.3969/j.issn.0253-2417.2014.05.013
    Abstract ( 709 )   PDF (880KB) ( 645 )   Save
    Understanding of the lignin migration behavior during bamboo pre-hydrolysis is essential for optimization of pre-hydrolysis technology and following cooking process. In this paper, the lignin migration behavior was investigated by Environment Scanning Electron Microscope (ESEM) and chemical composition analysis. The results showed that the interior lignin would gradually migrate to the bamboo surface. The infrared absorption characteristic peaks of lignin were enhanced while the peaks of hemicellulose were gradually disappeared during the pre-hydrolysis. The XPS analysis indicated that the C1(C—C/C—H) content increased from 24.0% to 45.5%, while C2(C—O)content decreased from 35.5% to 24.3% and the O/C ratio decreased from 0.43 to 0.34 as the bamboo was pre-hydrolyzed for 120 minutes. The higher lignin concentration was observed in the pretreated bamboo surface as compared to other raw material. The disparity between the lignin concentration of the whole bamboo and the lignin concentration of the bamboo surface increased with the pre-hydrolysis time, and lignin cocentration increased from 26.5 % to 43.3 % at the time of 120 min.
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    Screening of Tannic Acid Degrading Strain and Optimization of Its Fermentation Conditions
    MIN Fan-qin, WANG Cheng-zhang, YE Jian-zhong, LI Wen-jun, LU Li
    2014, 34 (5):  84-90.  doi: 10.3969/j.issn.0253-2417.2014.05.014
    Abstract ( 743 )   PDF (1121KB) ( 727 )   Save
    3 strains of tannic acid degrading were screened out from the 11 strains which were separated from naturally fermented Turkish galls extract by the methods of spread-plate, streaking and colony observing,etc. One superior tannic acid degrading strain was found, named strain 1#. The degradation rate of tannic acid reached beyond 65 %. In the fermentation broth, the concentration of gallic acid was 0.052 3 g/mL and the tannase activity was 0.920 U/mL. Fermentation conditions of strain 1# were optimized by using Response Surface Method. The effect of temperature, initial pH, incubation time was investigated. The results showed that the optimum temperature, initial pH values and incubation time of strain 1# was 31 ℃, 5 and 50 h. Under this condition, the tannase activity was increased from 0.920 to 1.170 U/mL, and improved by 27.2%.
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    Estimation of Pericarp Saponin Concent in Sapindus mukorossi by Using Near Infrared Reflectance Spectroscopy
    DIAO Song-feng, SHAO Wen-hao, LUAN Qi-fu, DONG Ru-xiang, JIANG Jing-min
    2014, 34 (5):  91-96.  doi: 10.3969/j.issn.0253-2417.2014.05.015
    Abstract ( 828 )   PDF (839KB) ( 709 )   Save
    In the paper we aimed to provide a rapid, simple and accurate model for estimating of pericarp saponin concent in Sapindus mukorossi, based on the near infrared reflectance spectroscopy (NIRs) and high performance liquid chromatography (HPLC). And 145 samples were collected from Tiantai County of Zhejiang Province. Based on the analysis data of HPLC and NIRs, two models of saponin concent determination were established, and the accuracy of the models were evaluated. The spectroscopic data of group A (the whole fruit) and group B (the powder pericarp) were obtained from the pretreatments of "SNV+1st derivative" and "MSC+1st derivative". The results showed that the spectral models based on this data and established by PLS, were the best and the most reliable. They also had prediction precision. The model by group B was better than the model by group A. The models with groups A and B could reach 0.654 and 0.993 of the correlation coefficient between the prediction and the HPLC measured values. The standard deviations of prediction were 0.982 and 0.294, respectively. Thus, the model with the whole pericarp could be used to measure low quantity and precious samples with the relative low accuracy. The model with powder pericarp was very proper and could directly replace HPLC method.
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    Preparation and Adsorption Behaviors of Konjac Glucomannan Gel Micropheres Crosslinked with Zr
    LI Jian-feng, LIAO Li-min, LI Xiang-rong, WANG Bi
    2014, 34 (5):  97-102.  doi: 10.3969/j.issn.0253-2417.2014.05.016
    Abstract ( 679 )   PDF (1268KB) ( 637 )   Save
    The zircon cross linked with carboxyl methyl konjac glucomannan gel microspheres (CMKGM-Zr) were prepared by crosslinking oxygen zirconium ion (ZrO2+) and carboxyl methyl konjac glucomannan (CMKGM) which was obtained through rectifying konjac glucomannan(KGM) with carboxyl-methyl. Structure of the CMKGM-Zr was characterized by scanning electron microscopy and the change between pre- and post-adsorption reaction was analyzed by infrared spectroscopy. On this basis, the adsorption capacity of CMKGM-Zr for benzoic acid was studied. And the parameters, including the adsorption time and pH were investigated. Further, according to adsorption isotherms of CMKGM-Zr for benzoic acid, thermodynamic parameters of the adsorption process were calculated and the experimental data were fitted. The results showed that the gel microspheres prepared with 2.0 % CMKGM and ZrO2+ were white irregular geometry of hollow spheres and the mechanical strength was 15.3 g. The reaction between ZrO2+ and —COO- occurred after adsorption of benzoic acid. When the temperature 298 K, pH 4.5, and the concentration of benzoic acid 200 mg/L were used, the adsorption equilibrium was established about 4 hours. And the dsorption capacity of CMKGM-Zr for benzoic acid reached the maximum of 79.964 2 mg/g. Freundlich equation was suitable for the adsorption of the studied system. Adsorption driving forces were the enthalpy change and entropy change.
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    DNA Extraction and Ribosomal DNA-ITS Sequence Molecule Barcode Identification from Wood Tissue of Dalbergia odorifera T. Chen
    YU Min, ZHANG Hao, LIU Sheng-quan, JIN Qing, LI Da-zhou
    2014, 34 (5):  103-108.  doi: 10.3969/j.issn.0253-2417.2014.05.017
    Abstract ( 792 )   PDF (959KB) ( 643 )   Save
    The wood of Dalbergia odorifera T. Chen originated from different sites of plantations were sampled as materials in this paper. DNA from the sapwood and heartwood of D.odorifera treated with various temperature was extracted and amplified for the internal transcribed space (ITS) sequences. The effects of various temperature treatments on DNA extraction and amplification for target sequences were analyzed. The rDNA-ITS sequences of D.odorifera from different habitats and D.rimosa Roxb, a closely related species, were sequenced and their divergences were analyzed. The results showed that there were varying extents of diffusion with the DNA extracts from the heat treatment of 25 ℃ and 65 ℃, and the DNA from the heat treatment of 105 ℃ was degraded and smaller than 250bp. The ITS sequences can be amplified successfully from wood after 25 ℃ heat treatments. The distribution of vriations in ITS2 regions of D.odorifera and D.rimosa was larger than ITS1 regions and there were 6 variable sites in both of ITS regions. D.odorifera and D.rimosa could be distinguished by cluster analysis. Therefore, it could provide theoretical reasons to identify wood of D.odorifera from adulterants by using the rDNA-ITS sequences.
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    Synthesis and Properties of Rosin-based Polyoxyethylene Amine Gemini Surfactants
    WANG Juan, WANG Dan, SHANG Shi-bin, SHEN Ming-gui, QI Fan
    2014, 34 (5):  109-114.  doi: 10.3969/j.issn.0253-2417.2014.05.018
    Abstract ( 742 )   PDF (893KB) ( 569 )   Save
    Four rosin-based polyoxyethylene amine gemini surfactants N,N'-methoxypolyethylene glycols-N,N'-dehydroabietylamine-α,ω-promethylene diamine (RPG550, RPG1000, RPG2000, and RPG5000) with different molecular weights, were synthesized from dehydroabietylamine through N-alkylation reactions. The structures of these compounds were confirmed by FT-IR and 1H NMR, and their surface activities were investigated and analyzed. The results showed the CMC and γcmc values of these four compounds were lower than that of commercial TX-10. The CMC values of RPG550, RPG1000, RPG2000, RPG5000 and TX-10 were 1.00×10-3, 9.75×10-4, 5.25×10-4, 1.90×10-4, and 2.03×10-3 mol/L, respectively. The γcmc values of these surfactants were 26.4, 27.5, 22.8, 22.2, and 31.6 mN/m, respectively. These compounds have excellent emulsifiability in the turpentine/water system and the liquid paraffin/water system. They also have good foam inhibition and defoaming power properties, and the foam inhibition property of RPG is significantly better than that of TX-10.
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    Preparation of NaY Molecular Seive Loaded with Salen-metal Complexes for Catalyzing the Epoxidation of α-Pinene
    MA Ai-hua, HU Ting-wei, SHAN Shao-yun, JIA Qing-ming
    2014, 34 (5):  115-121.  doi: 10.3969/j.issn.0253-2417.2014.05.019
    Abstract ( 810 )   PDF (1116KB) ( 652 )   Save
    Immobilization of Mn(salen) complex into the super-cage of Zeolite Y was achieved via traditional solvothermal method (SalenMnCl/Y) and microwave heating method (SalenMnCl/Y-MW), respectively. And FT-IR, XRD, TG and Specific surface area analysis were used to characterize the catalysts which were employed to catalyze the epoxidation of α-pinene to get α-poxypiene by peracetic acid under the low catalyst concentration. Comparative study of the performance of catalysts prepared by two methods was carried out. The optimal reaction condition was investigated by response surface methodology and used to evaluate the performance of the recycle catalyst . The results showed that although the catalysts prepared by two methods can both successfully catalyse α-pinene epoxidation, microwave heating method however is priority to traditional solvothermal method. The yield can reach 91.60 % with the catalyst of SalenMnCl/Y-MW under the following conditions,i.e., peroxide and α-pinene mole ratio 1.43, the reaction temperature 10 ℃ and the reaction time 3.75 h. Meanwhile, this type of catalyst can be recycled for 5 times and the yield also can reach 76 %. It indicates that this type of catalyst has good stability and can be recycled.
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    Synthesis and Properties of Fumaropimaric Acid-based Waterborne Polyurethane Modified by Epoxy Resin
    LIU He, XU Xu, SHANG Shi-bin, SONG Zhan-qian
    2014, 34 (5):  122-126.  doi: 10.3969/j.issn.0253-2417.2014.05.020
    Abstract ( 690 )   PDF (1742KB) ( 722 )   Save
    Fumaropimaric acid-based waterborne polyurethane (FWPU) emulsion modified by epoxy resin (EP) was synthesized. Influences of epoxy E-51 content on performances of emulsion and film were discussed. The results showed that when the content of E-51 was 3%, the tensile strength, water absorption, elongation at break and pendulum hardness of the film was 35.6 MPa, of 10.2%, of 410.2% and 0.89, respectively. The morphology and structure of the film and emulsion were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). It was verified by FT-IR analysis that the hydroxyl and epoxy groups in EP participated in reaction, and part of them formed network structure by crosslinking. The water resistance, thermal stability, mechanics performances and chemical resistance of films were improved with increase of EP content.
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    Production of L-Lactic Acid by Self-immobilized Rhizopus oryzae
    CHEN Xiao-pei, ZHANG Li, GU Xi-mei, LI Xin, YONG Qiang, YU Shi-yuan
    2014, 34 (5):  127-132.  doi: 10.3969/j.issn.0253-2417.2014.05.021
    Abstract ( 629 )   PDF (972KB) ( 655 )   Save
    The main factors affecting self-immobilization of Rhizopus oryzae NLX-M-1 for L-lactic acid production were studied in present study. The optimum fermentation conditions utilizing wood fiber-based glucose for R.oryzae self-immobilization were obtained. The optimal results were achieved as 100 g/L initial glucose, 2 g/L (NH4)2SO4, 2 %inoculum size (value fraction), 30 g/L CaCO3, 0.1 g/L KH2PO4, 0.25 g/L MgSO4·7H2O and 0.1 g/L ZnSO4·7H2O. Under this optimal condition, R.oryzae formed pellets with an average diameter of about 1 mm during the fermentation, the production of L-lactic acid was 76.6 g/L and the conversion rate was 81.6 %. R.oryzae in acid explosive residue hydrolyzate containing 60 g/L glucose became 1.2 mm pellets, and produced 36.4 g/L L-lactic acid with a conversion rate of 63.5 %.
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    Volatilization and Oxidation Properties of Fatty Acid Methyl Esters Based on TG-DSC
    MEI De-qing, ZHANG Yong-tao, TAN Wen-bing, YUAN Yin-nan
    2014, 34 (5):  133-138.  doi: 10.3969/j.issn.0253-2417.2014.05.022
    Abstract ( 736 )   PDF (890KB) ( 636 )   Save
    Based on the analysis of thermogravimetry-differential scanning calorimeter (TG-DSC), three pure fatty acid esters such as saturated methyl palmitate(C16:0), methyl stearate(C18:0) and unsaturated methyl oleate(C18:1) and their mixture from bio-fuel were chosen to investigate their volatilization and oxidation characteristics under N2 and O2 atmosphere. Under N2 atmosphere, it was found that the volatilization start temperature of C16:0 is 157.3 ℃, which is lower than that of C18:0. However, C18:1 is much easier to volatile than C18:0, and the volatilization start temperature of C18:0 and C18:1 are 193.7 ℃ and 175.9 ℃, respectively. Based on the thermal properties of three pure esters under N2 atmosphere and O2 atmosphere, it could be concluded that the C18:0 performed the best ignitability, and the ignition performance of C16:0 is close to that of C18:0, while the ignition performance of C18:1 is the weakest. All the TG-DSC curves of three pure esters present the endothermic peaks under N2 atmosphere because of volatilization and pyrolysis, while the exothermic peaks could be found under O2 atmosphere due to intense oxidation. The esters mixture has exhibited the similar thermo gravimetric characteristics and heat flow shapes with the pure esters under different atmospheres. The most abundant cardinal component in the esters mixture plays a dominant part on the fuel properties of the mixture esters.
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    Properties of Halogen-free Flame Retardant EVA Copolymer Emulsion Adhesive
    LIU Juan, YU Xiang-dong, WANG Chun-peng, BU Hong-zhong, CHEN Ri-qing
    2014, 34 (5):  139-144.  doi: 10.3969/j.issn.0253-2417.2014.05.023
    Abstract ( 872 )   PDF (961KB) ( 787 )   Save
    A series of halogen-free flame retardant EVA copolymer emulsion adhesives were synthesized with the blend of ATH, melamine phosphate (MP), and the complex system of MP and pentaerythritol (PER) as flame retardants respectively. Limiting oxygen index (LOI) and cone calorimeter test (CCT) for the characterization of burning behavior , thermal gravimetric analysis (TGA) for the evaluation of thermal decomposition behavior, and tensile strength related to mechanical property, were carried out and investigated . The results showed that thermal decomposition temperature was raised after adding flame retardant. When the amounts of ATH and MP were 30 % and m(MP):m(PER) was 3:1(the total amount of MP and PER was 30 %), the LOI and tensile strength of the system were more than 30 (38.6, 34.3 and 36.3) and 8.0 MPa (10.13, 13.18 and 11.28 MPa), respectively. They met the requirement. EVA emulsion modified with ATH had higher flame retardant efficiency than those modified with MP and MP/PER complex system. Its parameters of ignitor firing time, heat release rate, total smoke production and mass loss rate and so on were better. It was found that the addition of a small amount of PER in MP modified system could promote the generation of the intumescent carbonaceous residue.
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    Ultrasonic Extraction and Antioxidant Activity of Polyphenol from Synsepalum dulcificum Leaf
    LU Sheng-lou, FU Jia-zhen, LIU Hong, FU Chun-min, LIN You-ming, WANG Xiao-he
    2014, 34 (5):  145-151.  doi: 10.3969/j.issn.0253-2417.2014.05.024
    Abstract ( 931 )   PDF (1199KB) ( 1152 )   Save
    The purpose of this paper was to determine the optimum technology and conditions to extract polyphenol from the leaves of Synsepalum dulcificum. Based on the results of single factor experiments, by using the response surface method the S. dulcificum leaves polyphenols mathematical model was established. Meanwhile, the antioxidant activity of the extracted polyphenol was evaluated. The best technical conditions to extract polyphenol from S. dulcificum leaf were obtained as follows:the concentration of acetone solution 58%, ultrasonic time 72 min and extraction temperature 48 ℃, when the S.dulciticum leaf were 1.0 g and liquid-solid ratio was 30:1(mL:g). The predicted polyphenol extraction yield was 6.82%. Under the optimized condition, the experimental yield was 6.84 % which agreed with its predicted yield. The in vitro antioxidant assay results showed that S. dulcificum leaf polyphenol exhibited a dose-dependent scavenging activity against 2,2'-azinobis (3-ethyl- benzothiazoline-6-sulfonic acid ammonium salt(ABTS) radical, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical and ·OH radical. Its hemi-inhibiting concentrations (IC50) were 51.81,13.40 and 28.91 mg/L, respectively. Which suggested that S. dulcificum leaf had high antioxidant activity.
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    Determination of the Content and Structure of Polyprenols from Greek Pinus pinaster Leaves
    DUAN Xin, TAO Ran, WANG Cheng-zhang, XUE Zhi-ge
    2014, 34 (5):  152-156.  doi: 10.3969/j.issn.0253-2417.2014.05.025
    Abstract ( 648 )   PDF (730KB) ( 624 )   Save
    The isopentenyl unit numbers of polyprenols from Greek Pinus pinaster leaves was 14 to 20 by contrasting the retention time of polyprenol reference substance using HPLC. And the polyprenols structure was confirmed as ω-trans2-cisn-OH by 1H and 13C spectrum. The HPLC conditions of a Kromasil C18 ODS-1(150 mm × 4.6 mm, 5 μm) column, methanol-isopropanol (9:16, v/v) as the mobile phase at a flow rate of 0.50 mL/min, column temperature of 25 ℃, PDA detector with detective wavelength of 210 nm were used. The polyprenols from Greek P. pinaster leaves in the range of 1.10-12.10 μg had good linearity (r=0.996 3), the average recovery was 98.21 %, and RSD was 2.27 % (n=6). The result showed that the polyprenols content of dried leaves was 0.33 % . The method was accurate, reproducible and quick to determine the isopentenyl unit number and content of polyprenols from Greek P. pinaster leaves.
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    Extraction of Total Polysaccharides from Bamboo Shoots and Their Antioxidative Activities
    CHEN Li-hua, GAO Wen-yu, WANG Xiao-jing, SUN Hong-le
    2014, 34 (5):  157-161.  doi: 10.3969/j.issn.0253-2417.2014.05.026
    Abstract ( 809 )   PDF (748KB) ( 760 )   Save
    Total polysaccharides were extracted from bamboo shoots (i.e.TPBS) by ultrasonic-assisted extraction with water, and then purified by ethanol precipitation to remove pigment and protein. With the same concentration of ascorbic acid (Vc) as the control, the antioxidant activity of total polysaccharides were investigated by testing scavenging effects of ·OH and O2-·, reduction capability to Fe3+ and against the peroxidation of oils and fats. The results showed that TPBS of extract exhibited a strong ability to remove ·OH and O2-·, excellent deoxidation function of Fe3+ and good inhibitory effect on peroxidation of oils and fats. The scavenging rate of ·OH and O2-·was 47 % and 18 %, and protecting rate for oil and fat was 58 % and 30 %, respectively, at the concentration of 0.5 g/L TPBS. The scavenging rate of ·OH and O2-· was 55 % and 90 %, and protecting rate for oil and fat was 78 % and 65 %, respectively, at the concentration of 0.5 g/L Vc. Furthermore, the antioxidative activity was increased with polysaccharides concentration increasing.
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    Progress in Synthesis Technologies and Development Activities of 2th Generation Biojet Fuel
    LI Yu-ping, ZHANG Qing, WANG Tie-jun, MA Long-long, LIU Qi-ying
    2014, 34 (5):  162-168.  doi: 10.3969/j.issn.0253-2417.2014.05.027
    Abstract ( 869 )   PDF (912KB) ( 769 )   Save
    The progress in synthesis technologies and development activities of 2th generation biojet fuels were reviewed. The feature of synthesis technologies were discussed and compared. They included the processes of biobutanol/bioisobutanol-dehydration-oligomerization, lignocellulose hydrolysis-aqueous phase reforming, two-step hydrogenation (hydrodeoxygenation-hydroisomerization) of oils and fats and biomass gasification-Fischer Tropsch synthesis. The current status of feedstocks, biobutanol/bioisobutanol, Jatropha, Camelina sativa and algae, as well as the demonstration/pilot-scale plant for 2th generation biojet fuel production were described and analyzed from their technical and economic properties. Finally the development prospect was stated and proposed for its future application in jet planes.
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    Research Progress in the Expression of Cellulase
    HE Min-chao, XU Jing-liang, YUAN Zhen-hong, KONG Xiao-ying, ZHANG Yu, CHEN Xiao-yan, LIANG Cui-yi
    2014, 34 (5):  169-174.  doi: 10.3969/j.issn.0253-2417.2014.05.028
    Abstract ( 834 )   PDF (722KB) ( 705 )   Save
    Acquisition of a more excellent producing strain of cellulase is the major approach to decrease the cost of application in the field of cellulosic ethanol, pulp and paper, textile and so on. In order to review some valuable information on the construction of high yielding strain of cellulase, a variety of factors, including regulation of cellulase in Trichorderma reesei, optimization of promoter, the compatibility between cellulase gene and the host, the copy number of promoter and expressed gene, were discussed. Their influence on the expression of cellulse gene in T.reesei or Pichia pastoris was summarized.
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    Review on the Current Situation and Business Model Innovation of Biogas Industry in China
    SUN Kang-tai, ZHANG Hui, WEI Xun, QI Wei, GE Yi-qiang
    2014, 34 (5):  175-180.  doi: 10.3969/j.issn.0253-2417.2014.05.029
    Abstract ( 597 )   PDF (1183KB) ( 620 )   Save
    This article pointed out the significance of developing biogas industry. The current situation and business models of biogas industry emerging in China was described. Existing problems, developing trends and suggestions for biogas industry were also presented.
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