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Current Issue
2014 Vol.31 Issue.4,
Published 2014-07-15
Article
Article
1
Cu, Co Doped Manganese Composite Metal Oxides for NO
x
Storage and Reduction at Low Temperatures
LI Xin-Gang, GUO Li, XIAN Hui
Mn-M-O (M=Cu or Co) composite metal oxides were prepared by a co-precipitation method and their abilities concerning the NO
x
storage capacity (NSC) in lean burn atmospheres and NO
x
storage reduction (NSR) in the periodically alternative lean burn/fuel rich atmospheres were investigated. The results indicated that the Mn-O sample showed good catalytic activity: the NO-to-NO
2
conversion was 83.4%, and the NSC was 124.2 μmol/g. However, it had the drawback of the poor reduction activity in the fuel rich atmospheres. The doping with the Cu or Co element can remarkably decrease the mean crystallite sizes, increase the thermal aging resistance, and consequently enlarge the specific surface areas of the catalysts. This induced the enhancement of the NO storage capacity and the NO reduction ability at low temperatures. The H
2
-TPR results demonstrate that doping with Cu or Co element can result in the shift of the reduction peak of the H
2
-TPR profiles toward lower temperature. It indicated an increase in the oxygen activity, which further improved the redox ability of the doped Mn based oxides. The Mn-Cu-O sample displayed the best NSR activity due to its good NO reduction activity in the fuel-rich atmospheres.
2014 Vol. 31 (4): 1-5 [
Abstract
] (
2695
) [
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1KB] [
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1649KB] (
1519
)
6
Sulfonic Acid Carbon Material Supported Ru Catalysts for Cellulose Hydrolysis and Hydrogenation
XIE Xian-Na, WANG Hua, HAN Jin-Yu, NIU Yu-Fei
Bifunctional catalysts of sulfonic acid carbon materials supported Ru were prepared, with different carbon source precursors, namely, cellulose derived carbon, actived carbon and mesoporous carbon materials CMK-3 under different sulfonic acid conditions. The structures of catalysts were characterized by FTIR spectrum, XRD, elemental analysis, thermogravimetric analysis and N
2
physical adsorption-desorption. The catalytic performance of hydrogenation reactions of cellulose were studied. Results show that, compared with cellulose derived carbon, activated carbon and mesoporous CMK-3 sulfonic acid carbon materials possess good combination ability with —SO
3
H，high catalytic activity and good polyols selectivity. Under 170 ℃ for 10 h, hexitols can yield up to 84.0%. When recycled, catalytic activity of activated carbon sulfonic acid materials supported Ru catalyst decreases, but keeps on selectivity of polyols; mesoporous carbon sulfonic acid materials supported Ru catalyst has problems with the loss of S, and conversion rate remaines about the same, but the product selectivity is reduced.
2014 Vol. 31 (4): 6-12 [
Abstract
] (
2984
) [
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1KB] [
PDF
1638KB] (
1845
)
13
Beta Zeolite Catalytic Isomerization of
endo
-Dicyclopentadiene
ZHANG Yu, HAN Hong, ZOU Ji-Jun
Hβ-catalytic isomerization of
endo
-dicyclopentadiene (
endo
-DCPD) to
exo
-dicyclopentadiene (
exo
-DCPD) in liquid phase was studied. With the absence of zeolite, DCPD is converted into oligomers and the formation of
exo
-DCPD is neglectable. With the presence of Hβ, considerable amount of
exo
-DCPD is formed. Passivation of the external surface with amorphous silica layer improves the selectivity of isomerization reaction with a little decline in conversion. This means that the isomerization reaction occurs inside the pore of zeolite, meanwhile the external acidity accelerates the undesired oligomerizations. Hβ with low SiO
2
/Al
2
O
3
ratio contains highest concentration of weak Lewis acid, and exhibits highest activity, confirming that weak L acidity is the active site for the isomerization. The calcination temperature has great influence on the acidity and porous structure of zeolite. The amount of weak L acid is not enough at low temperature, while the framework and pores are destroyed at high temperature. Calcination at 500 ℃ produces enough weak L acid and keeps relatively well crystallinity, thereby providing best catalytic performance.
2014 Vol. 31 (4): 13-17 [
Abstract
] (
2110
) [
HTML
1KB] [
PDF
1134KB] (
1966
)
18
Thermodynamic Analysis of Reaction for Synthesis of Guaiacol from Catechol and Methanol
GAO Hai-Xia, KONG Yan
Due to the economic, environmental, cheap materials, which can realize continuous production, etc, the guaiacol synthezied by catechol and methanol via gas phase monoether reaction has attracted much attention. In order to effectively use of resources, the reaction process was discussed by thermodynamic analysis in detail. Based on the standard enthalpy of formation (Δ
f
H
θ
m
), the standard entropy of formation (Δ
S
θ
m
) and the heat capacity (
C
p,m
) of catechol, methanol, guaiacol and water, the thermodynamic data on the vaporphase synthesis of guaiacol with catechol and methanol at 400—800 K were calculated, including reaction enthalpy (Δ
r
H
m
), Gibbs free energy (Δ
r
G
m
) and equilibrium constant (K). Then, the relationship between temperature and the above three variables were studied. According to the calculation, in the range of 400—800 K, the reaction is exothermic and spontaneous, also have higher equilibrium constants. The results showed that it was important for optimization of reaction process as well as the design of catalysts over the gas phase synthesis of guaiacol at lower temperatures.
2014 Vol. 31 (4): 18-21 [
Abstract
] (
4118
) [
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1KB] [
PDF
1134KB] (
2350
)
22
Synthesis of 5-Nonylsalicyaldehyde by Duff Reaction
ZHAO Ying-Qian, WANG Li-He, LI Xiao-Jun
5-Nonylsalicylaldehyde was the important intermediates in the synthesis of 5-nonylsalicylaldoxime, which as copper extraction agent had many applications in industry. In this paper, 5-nonylsalicyaldehyde was synthesized from 4-nonylphenol, hexamethylenetetramine in acetic acid via Duff reaction. Compared to the other synthesis methods, the synthesis method of 5-nonylsalicyaddehyde used Duff reaction has much advantages, such as simple operation, short reaction period, single product and easy to be purified. The effects of reactant mole ratio, reaction temperature, reaction time on the reaction yield were studied. The optimum reaction conditions were as follows:
n
(4-nonylphenol):
n
(hexamethylenetetramine)=1:2 and the reaction mixture was dissolved in acetic acid and stirred at 90 ℃ for about 6 h. Under these conditions, the yield of 5-nonylsalicyaldehyde was 98.7% based on 4-nonylphenol with a purity of 92.0% (analyzed by HPLC). Structure of the product was elucidated by
1
H-NMR analysis.
2014 Vol. 31 (4): 22-25 [
Abstract
] (
2876
) [
HTML
1KB] [
PDF
1338KB] (
1726
)
26
Graphene Oxide/Polyvinylidenefluride (PVDF) Films
LI Xin, LI Bao-An, WANG Shi-Chang
The graphite oxide was synthesized by Hummers method. Graphene oxide was prepared by sonicating the graphite oxide solution. Graphene oxide/PVDF films were fabricated by means of the evaporation method. The morphology and structural analysis were carried out by using TEM, FTIR and XRD. The tensile strength and thermal conductivity of graphene oxide/PVDF films with different content of graphene oxide were studied. The results suggest that graphene oxide has various oxygen bearing functional groups. Graphene oxide is well dispersed in PVDF matrix. And the graphene oxide in the films can improve the tensile strength and thermal conductivity. The thermal conductivity increases with increasing content of graphene oxide first, and then it gradually decreases. When the content of graphene oxide is 0.4%, the thermal conductivity reaches maximum.
2014 Vol. 31 (4): 26-30 [
Abstract
] (
5815
) [
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1KB] [
PDF
1862KB] (
2292
)
31
Growth Process of Polyaniline Film Prepared by Electrochemical Reaction
ZHANG Wei-Guo, SHANG Wei-Zheng, LI Xiang, WANG Hong-Zhi, YAO Su-Wei
Potentiostatic, galvanostatic and potentiostatic pulse methods were used to prepare polyaniline film in acidic solution of aniline respectively. The growth process of the polyaniline on the electrode was characterized by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results show that the initial polymerization of polyaniline is three-dimensional instantaneous nucleation dominated by electrochemical kinetics and the whole process is divided into five periods, including nucleation induction, electrochemically-controlled instantaneous nucleation, diffusioncontrolled instantaneous nucleation, 1-D radial continuous nucleation, 1-D axial continuous nucleation. The nucleation and growth process of polyaniline is divided into three stages: the formation of the spherical particle, network nanofiber and nanorod structure.
2014 Vol. 31 (4): 31-35 [
Abstract
] (
4312
) [
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1KB] [
PDF
1871KB] (
1685
)
36
Microwave-Assisted Synthesis of Methoxycarbonyl-
β
-Cyclodextrin Carbonate
ZHANG Yi-Min, LIU Hong-Sha, ZHANG Hui-Ying, ZHU Yan-Fang
A novel microwave-assisted procedure for the synthesis of methoxycarbonyl-
β
-cyclodextrin carbonate is described in the work. Methoxycarbonyl-
β
-cyclodextrin carbonate was obtained through reaction of green reagent dimethyl carbonate and
β
-cyclodextrin with anhydrous potassium carbonate as catalyst in N, N-dimethylformamide under microwave radiation. The structure of the product was characterized by IR and
13
C-NMR. A typical CO peak at 1 751 cm
-1
in IR spectrum and
13
C-NMR signal of CO and CH
3
O— indicated distinctly the structure of
β
-CD-OCOOCH
3
. The average degree of substitution of the products and the raw material conversion are 2.423 and 93.22%, respectively, determined by electrospray mass spectrometry and high performance liquid chromatographic. The experimental results showed that the novel process for the synthesis of
β
-cyclodextrin carbonate, compared with the conventional heating process, has the advantages of low energy consumption, high yield and short reaction time, etc.
2014 Vol. 31 (4): 36-40 [
Abstract
] (
1527
) [
HTML
1KB] [
PDF
1926KB] (
1693
)
41
Synthesis and Gel Properties of Allyl Sorbitol Gelators
SUN Hai-Jun, SONG Jian, DUAN Yuan-Chao
1, 3:2, 4-di-p-methylbenzylidene-D-sorbitol (MDBS) is known to be an efficient sorbitol derivative gelator. A series of allyl sorbitol gelators have been designed in contrast to MDBS. Self-assembly and gel mechanism of gelators in solvents were studied by force between gelators, molecular and hydrophilic interaction. 4 gelators' behavior to 30 solvents and minimal gelation concentration was investigated. It was found that the gelation behavior was related to the molecular structure of gelators. The introduce of allyl significantly improved the ability of gelators. (UV Vis) spectroscopy results revealed the main driving forces for the formation of gels. The fibrous and three-dimensional network of the gels was observed by scanning electron microscopy (SEM).
2014 Vol. 31 (4): 41-45 [
Abstract
] (
2183
) [
HTML
1KB] [
PDF
1726KB] (
1675
)
46
Optimization of Formulation and Preparation Parameters for Nimesulide Loaded NLC by Orthogonal Design
DU Guang-Sheng, LI De-Xin, WEI Zhen-Ping
High pressure homogenization method was used to prepare Nimesulide loaded nanostructured lipid nanoparticles (NLC). Single factor design was chosen to study the influence of solid-liquid lipid ratio, amount of lipid, amount of emulsifier, drug-lipid ratio, homogenization pressure and homogenization cycles on quality of the prepared nanoparticles. Orthogonal design was used to optimize the preparation parameters. The optimal preparation method was 3:10 of oleic acid glycerin monostearate(GMS) ratio, 1:40 of drug-lipid ratio, 1.4 g of TPGS, 90 MPa of homogenization pressure. Particle size and entrapment efficiency of NLC prepared by optimal conditions were 132.6±1.4 nm and 82.35±1.23%, respectively. The scanning electron microscope showed that the nanoparticles were of spherical shape. The in vitro release study showed that release behavior accorded with Higuchi model.
2014 Vol. 31 (4): 46-51 [
Abstract
] (
2569
) [
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1KB] [
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1534KB] (
2155
)
52
Optimization of Heat-Integrated Crude Oil Distillation System Using Shortcut Model
LUO Yi-Qing, WANG He, YUAN Xi-Gang
A shortcut model based on Fenske-Underwood-Gilliland method and enthalpy balance for crude oil distillation is proposed in this paper. The shortcut model is used to describe and optimize the existing crude oil distillation process, and the pinch analysis is adopted to identify the target of energy recovery. With the objective function of maximum annualized net profit, an optimization approach based on PSO algorithm is developed, which considers product profit and heat integration simultaneously. A case study of an existing crude oil distillation process is carried out, and the operation condition under maximum net profit is obtained. Compared with the rigorous simulation, the results prove that the shortcut model can provide relatively accurate calculation for crude oil distillation.
2014 Vol. 31 (4): 52-57 [
Abstract
] (
2366
) [
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1KB] [
PDF
1824KB] (
1596
)
58
Large Scale Purification Process of Coke Oven Gas：Challenge and Prospect
YAN Chang-Qing, DANG Le-Ping, CUI Wei-Min, Wei-Hong-Yuan
Large-Scale coke ovens demand the marching capability of gas purification process， and which is also an inevitable requirement according to the national energy conservation and emissions reduction targets. Based on a planning project of a large iron and steel enterprises, with phosphate absorbing anhydrous ammonia process and vacuum carbonate process as a refining process example, a systematic analysis is performed on the large scale of the coke oven gas refining process from following aspects: the advantages, key technology and challenges, and technical feasibility.
2014 Vol. 31 (4): 58-63 [
Abstract
] (
1569
) [
HTML
1KB] [
PDF
1734KB] (
2445
)
64
Analysis of Heat Exchanger Network for Ethylene Heat Pump System
ZHANG Lai-Yong, GUO Xu-Qiang, JIANG Bo, YANG Qing-Lan, SUN Chang-Geng
Pinch technology is widely used in analysizing heat exchanger network in petrochemical industry. Based on the basic theory and design principles of the pinch analysis, ethylene heat pump system of largescale ethylene plant was analyzed by Aspen Energy Analyzer. The research including two aspects, one is avoiding heat transfer across the pinch point by adding a heat exchanger; the other is changing operation pressure parameters of the ethylene tower. The result shows that a design process should not pursuit only the minimization of heat transfer crossing the pinch point and low energy consumption, the investment, operation cost and investment recovery period should be considered and the energy consumption could be evaluated economically and reasonably.
2014 Vol. 31 (4): 64-68 [
Abstract
] (
2427
) [
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1KB] [
PDF
2508KB] (
1850
)
69
Progress in Microbial Biosynthesis of Tacrolimus
WAN Tao, HUANG Di, WEN Jian-Ping
The present paper introduces recent progress in Tacrolimus’s physical and chemical characteristics as well as immunosuppressant activity in detail. For this purpose, the paper mainly summarizes research on fermentation production technology, the biosynthesis gene clusters and metabolic pathways. Furthermore, some successful cases of improvement about production of Tacrolimus based on metabolic engineering technology are reviewed. In future, the combination of systems biology and synthetic biology would provide rational guidance to promote the production efficiency of Tacrolimus and construct the high-yield producing strains with the improved key enzymes.
2014 Vol. 31 (4): 69-74 [
Abstract
] (
2384
) [
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1KB] [
PDF
1996KB] (
2355
)
75
LmbB
2 Catalyzes Bioconversion of Tyrosine to Synthesize L-DOPA
MA Qiang-Qiang, ZHAO Guang-Rong
L-DOPA is a first-selected drug for Parkinson′s disease in clinical treatment. This article utilizes gene
lmbB
2 from Streptomyces lincolnensis to construct the engineer Escherichia coli for production of L-DOPA. When 300 mg/L of tyrosine and 3g/L of L-ascorbic acid are added in M9 medium, after fermentation for 32 h at 37℃, the yield of L-DOPA were 285mg/L, and the bioconversion rate was 95%.
2014 Vol. 31 (4): 75-79 [
Abstract
] (
2170
) [
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1KB] [
PDF
2353KB] (
2132
)
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