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    30 March 2022, Volume 56 Issue 2 Previous Issue   
    Research Report
    Comparation of Producing Long Chain Terminal Olefin Chemicals Through Cross-metathesis Among 2 Types of Fatty Acid Methyl Ester
    Yuanbo HUANG, Hengyi SHU, Zhifeng ZHENG, Shouqing LIU, Hailong MA, Hao LI
    2022, 56 (2):  1-8.  doi: 10.3969/j.issn.1673-5854.2022.02.001
    Abstract ( 110 )   HTML ( 6625 )   PDF (539KB) ( 80 )   Save

    In order to realize the direct application of olefin cross-metathesis on preparation of long-chain terminal olefin compounds from the crude fatty acid esters of vegetable oils, methyl oleate(MO) and methyl linoleate(ML) were used as raw materials to prepare long-chain terminal olefin compounds 1-decene(CM1), 1-heptene(CM2) and methyl 9-decenoate(CM3) through olefin cross-metathesis reaction. 4 typical Grubbs catalysts, 10 short carbon chain fluid substrates were chosen and different reaction temperature, time, catalyst dosage and moles ratio of substrate as the reaction conditions were investigated and contrasted. The results showed that the second-generation Hovey-Grubbs catalyst(C3) and the second-generation Grubbs catalyst(C2) were suitable catalysts for raw materials MO and ML, respectively. Eugenol was the most appropriate partner among the 10 substrates for producing aim products. The influences of temperature, time, catalyst dosage and ratio of substrate were investigated, the suitable reaction conditions were reaction temperature 0 ℃, time 20-60 min, catalyst dosage 0.5%-1% and the mole ratio of fatty acid ester to substrates 1∶10-1∶20, the highest conversion of MO and ML were 99%, and the yields of CM1, CM2 and CM3 were 80%, 92% and 73%, respectively.

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    Demethylation/Hydroxyethylation Combined Modification of Corn Straw Lignin
    Kaixin ZHANG, Yalan YU, Yuting DUAN, Changwei WU, Lei XUE, Pengfei HUO
    2022, 56 (2):  9-13.  doi: 10.3969/j.issn.1673-5854.2022.02.002
    Abstract ( 50 )   HTML ( 929 )   PDF (1511KB) ( 34 )   Save

    The corn straw lignin was modified by demethylation/hydroxyethylation with sodium sulfite and glyoxal, to further improve the hydroxyl content and activity of lignin. The combined modification effect on lignin was characterized by Fourier transform infrared spectroscopic(FT-IR), thermogravimetric, differential scanning calorimetry(DSC) and acetylation titration. The results showed that the corn straw lignin modified by demethylation/hydroxyethylation had excellent activity. The total hydroxyl mass fraction of the modified lignin was 88.33% higher than that of the original lignin, and the phenolic hydroxyl group increased by 14.70%, which indicated that the reaction activity was significantly enhanced. Microscopic characterization by Fourier tansform infrared spectroscopy showed that the hydroxyl content of lignin was increased in many ways by combined modification, which had a significant effect on the increase of hydroxyl content. It was found by thermogravimetric and differential scanning calorimetry (DSC) analysis characterization that compared with the original lignin, the combined modified lignin(G-DL) degraded more thoroughly, with an exothermic peak at 77 ℃ and an exothermic value of 459.82 J/g. The activity of the reaction was higher than that of demethylated lignin(DL) and raw lignin.

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    Effect of a Tapping Irritant Agent on Oleoresin Yield and Physiological Indexes of Pinus yunnanensis Franch.
    Ruiling WANG, Chunhua WU, Xiangyi LIU, Jianxiang LIU, Zhifeng ZHENG
    2022, 56 (2):  14-18.  doi: 10.3969/j.issn.1673-5854.2022.02.003
    Abstract ( 37 )   HTML ( 797 )   PDF (432KB) ( 28 )   Save

    In order to improve the tapping yield of Pinus yunnanensis oleoresin, a nutritional tapping irritant agent was used. The efficiency of the agent and the influence of it to the physiological indexes of P. yunnanensis needles were investigated. The results showed that the maximum tapping yield increase reached to 41.08% with an average increase rate of 34.76%. The wet weight, dry weight, total chlorophyll content and soluble protein content of P. yunnanensis needle increased by 11.02%, 10.26%, 13.03% and 40.96%, respectively. The contents of superoxide dismutase(SOD), peroxidase(POD) and catalase(CAT) in the needle cells of P. yunnanensis also increased, which increased the resistance of P. yunnanensis. The content of malondialdehyde(MDA) and the relative electrical conductivity in pine needles decreased, which increased the stability of endomembrane system and enhanced the ability of P. yunnanensis to resist adversity.

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    Catalytic Cracking of Coconut Oil for Biofuel Production
    Shengchao DAI, Deqing MEI, Weidong ZHAO, Dengpan ZHANG
    2022, 56 (2):  19-26.  doi: 10.3969/j.issn.1673-5854.2022.02.004
    Abstract ( 44 )   HTML ( 711 )   PDF (804KB) ( 59 )   Save

    High-grade biofuels were produced from coconut oil through liquid phase cracking(LPC) and gas phase catalytic cracking(GPCC). With LPC of coconut oil, the maximum biofuel yield reached 76.5% under the pyrolysis temperature of 450 ℃, intake rate of 30 mL/min and reaction time of 40 min. However, the acid value of biofuel was above 100 mg/g. Thus the GPCC processing craft of pyrolysis liquid which was one of the cracking products was constructed with the CaO/bentonit as combined catalyst to reduce the acid value. The results showed that the maximum yield rate of biofuel reached 69.5% under the pyrolysis temperature of 400 ℃ and CaO dosage of 15% in the combined catalyst, and the acid value of the biofuel was 26.8 mg/g. Meanwhile, the minimum acid value of biofuel was 2.8 mg/g under the pyrolysis temperature of 450 ℃ and CaO dosage of 30% in the combined catalyst, and the yield of biofuel reached 64.1%. Through GC-MS analysis, it could be known that the major components in the liquid product via LPC were hydrocarbons, ketones, and acids, and their mass fractions were 32.6%, 24.2% and 43.3%, respectively. Compared with former, the hydrocarbons in GPCC liquid products increased by 23.3 percentage points, and the unfavorable acids and ketones decreased by 18.8 and 4.6 percentage points, respectively. The kinematic viscosity and oxygen content of biofuel obtained from the LPC of coconut oil decreased, while the acid value and low calorific value increased. Furthermore, the GPCC biofuel had lower acid value, lower oxygen content and higher calorific value than those of the LPC biofuel. As a whole, the GPCC biofuel had more similar properties with 0# diesel compared with the LPC biofuel.

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    Preparation of TEMPO Oxidized Nanocellulose and Its Effect on Paper Properties
    Ran YANG, Yule WU, Ying GUAN, Hui GAO
    2022, 56 (2):  27-32.  doi: 10.3969/j.issn.1673-5854.2022.02.005
    Abstract ( 42 )   HTML ( 781 )   PDF (2497KB) ( 24 )   Save

    The bleached eucalyptus pulp and waste newspapers were used as raw materials to prepare oxidized nanocellulose by 2, 2, 6, 6-Tetramethylpiperidine-1-oxyl (TEMPO)/NaBr/NaClO oxidation system, and the effects of the addition amounts of two oxidized nanocellulose on paper properties were investigated in this study. The results showed that the average fiber length and aspect ratio of eucalyptus oxidized nanocellulose(75-95 nm, 6.5-8.5) were both higher than that of waste newspaper oxidized nanocellulose(45-75 nm, 4-6). The tensile index of the eucalyptus and waste newspaper oxidized nanocellulose paper increased from 21.16 (N·m)/g to 31.37 and 27.22 (N·m)/g, the burst index increased from 1.32 (kPa·m2)/g to 1.84 and 1.79 (kPa·m2)/g, and the tear index increased from 6.61 (mN·m2)/g to 8.03 and 8.12 (mN·m2)/g. It was more helpful to improve the paper strength by the two kinds of oxidized nanocellulose by the addition of cationic starch. The tensile index of paper was increased by 51.09%, the burst index 50.00%, and the tear index 27.62%.

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    Catalytic Cracking of Acidic Oil by Alkaline Earth Metal Oxides and Its Kinetics Study
    Feng LONG, Xia JIANG, Xincheng CAO, Peng LIU, Junming XU
    2022, 56 (2):  33-39.  doi: 10.3969/j.issn.1673-5854.2022.02.006
    Abstract ( 35 )   HTML ( 917 )   PDF (628KB) ( 57 )   Save

    Alkaline earth metal oxides(MgO, CaO and BaO) were used as cracking catalysts, and a 3L cracking reactor made in the laboratory was used to crack and deoxidize acidic oil to prepare hydrocarbon fuels. The results showed that the yields of liquid fuel obtained from catalytic cracking of acidic oil by three kinds of alkaline earth metal oxides were 70%-80%; CaO and MgO as cracking catalysts could effectively deoxidize and produce more liquid fuel under lower reaction temperature and the acid value of the fuel was lower than 20 mg/g. Barium stearate, calcium stearate, and magnesium stearate was used as model compounds to study the kinetics of the pyrolysis reaction of waste oils, the thermogravimetric analysis was performed first, and then the kinetic parameters of the thermogravimetric results were calculated by using the distributed activation energy method. The results showed the pyrolysis activation energies of barium stearate, calcium stearate, and magnesium stearate decreased sequentially, which were 268, 204 and 127 kJ/mol, respectively. Above results indicated that the use of MgO as catalyst to crack acidic oil could collect more liquid fuel in the lower temperature section, and the waste oil was converted at lower temparture, which could effectively reduce the energy consumption during the conversion reaction.

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    Review Comment
    Development Trend and Strategic Countermeasures of Forestry Resources Gasification, Heat Supply and Power Generation Industry
    Hao SUN, Yunjuan SUN, Mingzhe MA, Kang SUN, Jianchun JIANG
    2022, 56 (2):  40-48.  doi: 10.3969/j.issn.1673-5854.2022.02.007
    Abstract ( 62 )   HTML ( 917 )   PDF (613KB) ( 117 )   Save

    Biomass gasification, heat supply and power generation industry is an efficient and comprehensive utilization of processing residues of forestry resources. The annual amount of forestry processing residues in China is about 210 million tons. The heat supply and power generation using renewable forest resources would improve the energy structure in our country, strengthen energy security, enhance the level of energy conservation and emissions reduction, promote the construction of new socialist countryside and sustainable development of forestry. However, several issues generally exist during the development of biomass gasification, heat supply and power generation industry, such as difficult collection, storage and transport of raw materials, poor automation and intelligent level of manufacturing process, immature standardized production technology, and lack of high-value and comprehensive utilization technology. So several suggestions were proposed, including strengthening the construction of forestry characteristic resource base, innovation of distributed industry development mode, breakthrough on the bottleneck technical problems, strict examination and approval of market access, intensive industry standard and government management, and improved policy support, in order to establish an industry system, including stable raw material supply, green manufacturing of high quality gas and efficient application of biochar. Moreover, the forestry residues annually utilized in gasification industry will be more than 5 million tons of standard coal, and the total output value will reach 10 billion yuan per year until 2035.

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    Research Progress in the Synthesis of 2, 5-Furandicarboxylic Acid from 5-Hydroxymethylfural Catalyzed by Transition Metals
    Jifeng BAI, Hongzhu LU, Yu YANG, Manfang CHENG, Jingyun WANG
    2022, 56 (2):  49-59.  doi: 10.3969/j.issn.1673-5854.2022.02.008
    Abstract ( 53 )   HTML ( 693 )   PDF (1103KB) ( 88 )   Save

    With the continuous improvement of the concept of green synthesis, transition metal catalysts with high catalytic activity, stability and low price replacing strong oxidizers and precious metal catalysts to catalyze the oxidation of 5-hydroxymethyl furfural(HMF) to prepare fine chemicals gradually become the focus of the researchers. This article reviewed recent researches on the use of cheap transition metal-based catalysts to catalyze the oxidation of 5-hydroxymethylfurfural(HMF) to 2, 5-furandicarbaldehyde(FDCA). The latest research in this field was described, with emphasis on introducing. The application of manganese-based, copper-based, iron/cobalt-based, nickel-based and other catalytic systems, such as manganese-based metal oxide, CuCl2 catalytic system, Fe3O4-CoOx magnetic catalyst, etc, in the HMF oxidation reaction were discussed. In addition, on the basis of the introduction of the above-mentioned catalysts, the development prospects of cheap transition metal-based catalysts catalyzed by HMF oxidation to prepare FDCA were also prospected.

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    Research Progress of Fatty Acid Composition, Purification and Application of Woody Oil
    Xia JIANG, Jiaping ZHAO, Peng LIU, Kui WANG, Junming XU, Jianchun JIANG
    2022, 56 (2):  60-68.  doi: 10.3969/j.issn.1673-5854.2022.02.009
    Abstract ( 88 )   HTML ( 719 )   PDF (560KB) ( 66 )   Save

    Woody oil is a traditional industrial oil in China, which has a wide range of industrial applications. It can be used as a source of high-quality edible vegetable oil, and also as a raw material for biodiesel production. It is widely used in feed additives and cosmetics industry.The content of C12-C18 unsaturated fatty acids in woody oil is high, which is easily absorbed by the human body. Different extraction technologies(pressing method, water enzymatic method, ultrasonic assisted method, leaching method, etc.) have little effect on the fatty acid composition and content of woody oilseeds. This article firstly briefly introduced the resources and applications of 7 woody oils, including rubber seed oil, walnut oil, coconut oil, Litsea cubeba kernel oil, peony seed oil, camellia seed oil and palm oil. The fatty acid composition of seven woody oils and their extraction and purification technology were summarized, and the extraction technologies of medium and long carbon chain unsaturated fatty acids in woody oils were emphatically introduced, and the applications of purified lauric acid, oleic acid, linoleic acid, and linolenic acid were reviewed and prospected.

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