共查询到20条相似文献,搜索用时 11 毫秒
1.
F. Billaud V. Dominguez P. Broutin C. Busson 《Journal of the American Oil Chemists' Society》1995,72(10):1149-1154
The pyrolysis of a mixture of methyl esters from rapeseed oil has been studied in a tubular reactor between 550 and 850°C
and in dilution with nitrogen. A specific device for the condensation of cracking effluents was used for the fractionated
recovery of liquid and gaseous effluents, which were analyzed on-line by an infrared analyzer and by gas chromatography. The
cracking products in the liquid effluent were identified by gas chromatography/mass spectrometry coupling. The effects of
temperature on the cracking reaction were studied for a constant residence time of 320 ms and a constant dilution rate of
13 moles of nitrogen/mole of feedstock. The principal products observed were linear 1-olefins,n-paraffins, and unsaturated methyl esters. The gas fraction also contained CO, CO2, and H2. The middle-chain olefins (C10–C14 cut) and short-chain unsaturated esters, produced with a high added value, had an optimum yield at a cracking temperature
of 700°C. 相似文献
2.
Evidence of thermal decomposition of fatty acid methyl esters during the synthesis of biodiesel with supercritical methanol 总被引:1,自引:0,他引:1
Joaquín Quesada-Medina Pilar Olivares-Carrillo 《The Journal of Supercritical Fluids》2011,56(1):56-63
New evidence on the thermal decomposition of fatty acid methyl esters during biodiesel synthesis in supercritical conditions is presented. Thermal decomposition products were detected chromatographically, by applying the UNE-EN 14105:2003 standard, as a broad single peak during the determination of glycerides in the reaction samples. These degradation products could be quantified chromatographically by the above standard because the area of the peak was proportional to the disappearance of the polyunsaturated fatty acid methyl esters, which contain two or more double bonds (methyl linoleate and linolenate), generated during biodiesel synthesis from soybean oil. In the experimental conditions tested, thermal decomposition reactions of these unsaturated fatty acid methyl esters began to appear at 300 °C/26 MPa, and were more intense as the temperature rose. For its part, the main saturated fatty acid methyl ester (methyl palmitate) generated during the reaction was hardly decomposed at all in the experimental conditions tested and only began to disappear at 350 °C/43 MPa. 相似文献
3.
Mag. Katharina Durchschein Dr. Silvia Wallner Prof. Peter Macheroux Prof. Klaus Zangger Prof. Walter M. F. Fabian Prof. Kurt Faber 《Chembiochem : a European journal of chemical biology》2012,13(16):2346-2351
An unexpected, redox‐neutral C?C bond isomerization of a γ‐butyrolactone bearing an exo‐methylene unit to the thermodynamically more favoured endo isomer (kcat=0.076 s?1) catalysed by flavoproteins from the Old Yellow Enzyme family was discovered. Theoretical calculations and kinetic data support a mechanism through which the isomerization proceeds through FMN‐mediated hydride addition onto exo‐Cβ, followed by hydride abstraction from endo‐Cβ′, which is in line with the well‐established C?C bond bioreduction of OYEs. This new isomerase activity enriches the catalytic versatility of ene‐reductases. 相似文献
4.
Christoph K. Winkler Dorina Clay Nikolaus G. Turrini Horst Lechner Wolfgang Kroutil Simon Davies Sebastien Debarge Pat O'Neill Jeremy Steflik Mike Karmilowicz John W. Wong Kurt Faber 《Advanced Synthesis \u0026amp; Catalysis》2014,356(8):1878-1882
Asymmetric bioreduction of an (E)‐β‐cyano‐2,4‐dienoic acid derivative by ene‐reductases allowed a shortened access to a precursor of pregabalin [(S)‐3‐(aminomethyl)‐5‐methylhexanoic acid] possessing the desired configuration in up to 94% conversion and >99% ee. Deuterium labelling studies showed that the nitrile moiety was the preferred activating/anchor group in the active site of the enzyme over the carboxylic acid or the corresponding methyl ester.
5.
Evaluation of nonpolar methyl esters by column and gas chromatography for the assessment of used frying olive oils 总被引:1,自引:0,他引:1
C. Cuesta F. J. Sánchez- Muniz I. Hernández 《Journal of the American Oil Chemists' Society》1991,68(6):443-445
The measurement of unaltered methyl esters separated from polar methyl esters by column chromatog-raphy was used to evaluate
the alteration of an olive oil that had been used 15 times to fry potatoes. Unaltered methyl ester (the nonpolar fraction)
decreased significantly (94.9 ± 0.8%vs 98.2 + 0.5%; p < 0.05), while the polar fraction increased significantly (4.0 ± 0.7%vs 2.1 ± 0.7%; p < 0.05) after 15 fryings. The unrecoverable fraction also increased. In order to avoid column contamination
the gas Chromatographic analysis was only done on the nonpolar fractions. Linoleic and oleic acids showed a tendency to decrease
while saturated fatty acid tended to increase. The unsaturated/saturated fatty acids ratio decreased from an initial value
of 7.05 to 6.40 in the last frying. Quantitative gas Chromatographic analysis using both the percentage fatty acid composition
and the relative amount of unaltered methyl esters showed a significant oleic acid decrease after 15 fryings (75.8 ± 0.6vs 78.9 ± 0.2 mg/100 mg oil; p < 0.05).
To whom correspondence should be addressed 相似文献
6.
Janet M. Snyder Jerry W. King Michael A. Jackson 《Journal of the American Oil Chemists' Society》1997,74(5):585-588
The fat content of lipid-containing samples has been determined by extraction of the fat with supercritical carbon dioxide,
followed by enzyme-catalyzed methylation of the fat under supercritical conditions, prior to gas chromatography (GC) analysis.
This study was initiated to determine the effect of moisture content on the extraction and conversion of lipids in oilseed
and meat samples to their fatty acid methyl ester (FAME) derivatives. These samples were freeze-dried or mixed with Hydromatrix
and compared with untreated control samples by employing the above-described supercritical fluid extraction-reaction sequence.
Particular attention was focused on minor constituents, such as phospholipids and cholesteryl esters, to see if they could
be extracted and derivatized by the above technique. Recoveries and reaction conversions of the lipid species were determined
with the aid of GC, high-performance liquid chromatography, and supercritical fluid chromatography for analyses of the extracted
lipids. Total fat values were higher from the freeze-dried meat and oilseed samples than from samples mixed with Hydromatrix
or left untreated. Extraction of cholesteryl esters was better than 90%, and conversion of the cholesteryl esters to FAME
was 93% or higher. Extraction of phosphatidic acid was only 88% compared to more than 90% recoveries for the other phospholipid
species. FAME conversion was better than 96% for all phospholipid samples in the study. 相似文献
7.
Manolito E. Bambase Nobuyuki Nakamura Junko Tanaka Masatoshi Matsumura 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2007,82(3):273-280
Methyl esters from crude sunflower oil were produced via methanolysis reaction using sodium hydroxide catalyst. Methanolysis was carried out at different agitation speeds (200–600 rpm), temperatures (25–60 °C), catalyst loadings (0.25–1.00% by weight of oil), and methanol:oil mole ratios (6:1–20:1). Mass‐transfer limitation was effectively minimized at agitation speeds of 400–600 rpm with no apparent lag period. Lowering the temperature resulted in a fall in the rate of reaction prolonging the reaction time necessary to achieve maximum production of methyl ester. Using 0.50% hydroxide catalyst was found to be adequate, resulting in 97–98% conversion without compromising recovery due to soap formation. Increasing the methanol:oil mole ratio beyond the usual amount of 6:1 tended to speed up the initial rate of methanolysis and was found to lower the bonded glycerol content, especially the amount of diglyceride in the sample. Kinetic rate constants were derived from experimental results using second‐order rate expressions, and values of activation energy for glyceride methanolysis have been established. Copyright © 2007 Society of Chemical Industry 相似文献
8.
A continuous process for the conversion of vegetable oils into methyl esters of fatty acids 总被引:8,自引:4,他引:4
H. Noureddini D. Harkey V. Medikonduru 《Journal of the American Oil Chemists' Society》1998,75(12):1775-1783
A continuous process for the transesterification of triglycerides to methyl esters was investigated in a pilot plant. The
process was equipped with a motionless and a high-shear mixer. The experimental studies explored variations in the mixing
intensity, stoichiometry, and catalyst concentration on the overall conversion. The combined as well as individual effect
of mixers was examined. The developed process resulted in high conversions of vegetable oils into methyl esters. Conversion
of triglycerides to methyl esters in excess of 98% was achieved. Larger excess amounts of alcohol favored higher conversions.
The motionless and high-shear mixers each provided adequate mixing for the process. Higher catalyst concentrations resulted
in higher conversions but increased the solubility of methyl esters in the glycerol layer. This reduced the amount of methyl
esters separated by gravity settling.
Presented in part at the Third Liquid Fuel Conference, Nashville, September 15–17, 1996. 相似文献
9.
Catalytic Scope of the Thiamine‐Dependent Multifunctional Enzyme Cyclohexane‐1,2‐dione Hydrolase 下载免费PDF全文
Sabrina Loschonsky Simon Waltzer Dr. Sonja Fraas Tobias Wacker Prof. Dr. Susana L. A. Andrade Prof. Dr. Peter M. H. Kroneck Prof. Dr. Michael Müller 《Chembiochem : a European journal of chemical biology》2014,15(3):389-392
The thiamine diphosphate (ThDP)‐dependent enzyme cyclohexane‐1,2‐dione hydrolase (CDH) was expressed in Escherichia coli and purified by affinity chromatography (Ni‐NTA). Recombinant CDH showed the same C?C bond‐cleavage and C?C bond‐formation activities as the native enzyme. Furthermore, we have shown that CDH catalyzes the asymmetric cross‐benzoin reaction of aromatic aldehydes and (decarboxylated) pyruvate (up to quantitative conversion, 92–99 % ee). CDH accepts also hydroxybenzaldehydes and nitrobenzaldehydes; these previously have not (or only in rare cases) been known as substrates of other ThDP‐dependent enzymes. On a semipreparative scale, sterically demanding 4‐(tert‐butyl)benzaldehyde and 2‐naphthaldehyde were transformed into the corresponding 2‐hydroxy ketone products in high yields. Additionally, certain benzaldehydes with electron withdrawing substituents were identified as potential inhibitors of the ligase activity of CDH. 相似文献
10.
Improving the low-temperature properties of alternative diesel fuels: Vegetable oil-derived methyl esters 总被引:14,自引:0,他引:14
R. O. Dunn M. W. Shockley M. O. Bagby 《Journal of the American Oil Chemists' Society》1996,73(12):1719-1728
This work explores near-term approaches for improving the low-temperature properties of triglyceride oil-derived fuels for
direct-injection compression-ignition (diesel) engines. Methyl esters from transesterified soybean oil were evaluated as a
neat fuel and in blends with petroleum middle distillates. Winterization showed that the cloud point (CP) of methyl soyate
may be reduced to −16°C. Twelve cold-flow additives marketed for distillates were tested by standard petroleum methodologies,
including CP, pour point (PP), kinematic viscosity, cold filter plugging point (CFPP), and low-temperature flow test (LTFT).
Results showed that additive treatment significantly improves the PP of distillate/methyl ester blends; however, additives
do not greatly affect CP or viscosity. Both CFPP and LTFT were nearly linear functions of CP, a result that compares well
with earlier studies with untreated distillate/methyl ester blends. In particular, additives proved capable of reducing LTFT
of neart methyl esters by 5–6°C. This work supports earlier research on the low-temperature properties; that is, approaches
for improving the cold flow of methyl ester-based diesel fuels should continue to focus on reducing CP. 相似文献
11.
Crystal Structure of HydG from Carboxydothermus hydrogenoformans: A Trifunctional [FeFe]‐Hydrogenase Maturase 下载免费PDF全文
Dr. Yvain Nicolet Adrien Pagnier Laura Zeppieri Lydie Martin Dr. Patricia Amara Dr. Juan C. Fontecilla‐Camps 《Chembiochem : a European journal of chemical biology》2015,16(3):397-402
The structure of the radical S‐adenosyl‐L ‐methionine (SAM) [FeFe]‐hydrogenase maturase HydG involved in CN?/CO synthesis is characterized by two internal tunnels connecting its tyrosine‐binding pocket with the external medium and the C‐terminal Fe4S4 cluster‐containing region. A comparison with a tryptophan‐bound NosL structure suggests that substrate binding causes the closing of the first tunnel and, along with mutagenesis studies, that tyrosine binds to HydG with its amino group well positioned for H‐abstraction by SAM. In this orientation the dehydroglycine (DHG) fragment caused by tyrosine Cα?Cβ bond scission can readily migrate through the second tunnel towards the C‐terminal domain where both CN? and CO are synthesized. Our HydG structure appears to be in a relaxed state with its C‐terminal cluster CysX2CysX22Cys motif exposed to solvent. A rotation of this domain coupled to Fe4S4 cluster assembly would bury its putatively reactive unique Fe ion thereby allowing it to interact with DHG. 相似文献
12.
Fast pyrolysis of glucose‐based carbohydrates with added NaCl part 2: Validation and evaluation of the mechanistic model 下载免费PDF全文
Xiaowei Zhou Heather B. Mayes Linda J. Broadbelt Michael W. Nolte Brent H. Shanks 《American Institute of Chemical Engineers》2016,62(3):778-791
A mechanistic model considering the significant catalytic effects of Na+ on fast pyrolysis of glucose‐based carbohydrates was developed in Part 1 of this study. A computational framework based on continuous distribution kinetics and mass action kinetics was constructed to solve the mechanistic model. Agreement between model yields of various pyrolysis products with experimental data from fast pyrolysis of glucose‐based carbohydrates dosed with NaCl ranging from 0–0.34 mmol/g at 500 °C validated the model and demonstrated the robustness and extendibility of the mechanistic model. The model was able to capture the yields of major and minor products as well as their trends across NaCl concentrations. Modeling results showed that Na+ accelerated the rate of decomposition and reduced the time for complete thermoconversion of carbohydrates. The sharp reduction in the yield of levoglucosan (LVG) from fast pyrolysis of cellulose in the presence of NaCl was mainly caused by reduced decomposition of cellulose chains via end‐chain initiation and depropagation due to Na+ favoring competing dehydration reactions. Analysis of the contributions of reaction pathways showed that the decomposition of LVG made a minor contribution to its yield reduction and contributed less than 0.5% to the final yield of glycolaldehyde from fast pyrolysis of glucose‐based carbohydrates in the presence of NaCl. © 2015 American Institute of Chemical Engineers AIChE J, 62: 778–791, 2016 相似文献
13.
Density functional theory calculations elucidated the precise reaction mechanism for the conversion of diphenylacetylenes into benzonitriles involving the cleavage of the triple C≡C bond, with N-iodosuccinimide (NIS) as an oxidant and trimethylsilyl azide (TMSN3) as a nitrogen donor. The reaction requires six steps with the activation barrier ΔG‡ = 33.5 kcal mol−1 and a highly exergonic reaction free-energy ΔGR = −191.9 kcal mol−1 in MeCN. Reaction profiles agree with several experimental observations, offering evidence for the formation of molecular I2, interpreting the necessity to increase the temperature to finalize the reaction, and revealing thermodynamic aspects allowing higher yields for alkynes with para-electron-donating groups. In addition, the proposed mechanism indicates usefulness of this concept for both internal and terminal alkynes, eliminates the option to replace NIS by its Cl- or Br-analogues, and strongly promotes NaN3 as an alternative to TMSN3. Lastly, our results advise increasing the solvent polarity as another route to advance this metal-free strategy towards more efficient processes. 相似文献
14.
Sigurd Schober Ingrid Seidl Andreas Meinitzer Martin Mittelbach 《European Journal of Lipid Science and Technology》2009,111(8):829-834
A gas chromatographic method for the determination of fatty acid methyl esters with four or more double bonds in biodiesel was developed and tested. The method is based on gas chromatographic separation on a wax capillary column using methyl tricosanoate as internal standard. The performance of the method was proved with the participation of 11 European laboratories by a Round Robin test on six different biodiesel samples containing different amounts of polyunsaturated fatty acid methyl esters. The results showed that the precision is sufficient around the EN 14214 limit of 1 % (m/m). At lower concentrations the variation is too high. The scope of the application can be given between as 0.6 and 1.5%. 相似文献
15.
Antti Aro Truus Kosmeijer-Schuil Peter van de Bovenkamp Paul Hulshof Peter Zock Martijn B. Katan 《Journal of the American Oil Chemists' Society》1998,75(8):977-985
Trans fatty acids in foods are usually analyzed by gas-liquid chromatography (GLC) of fatty acid methyl esters (FAME). However,
this method may produce erroneously low values because of insufficient separation between cis and trans isomers. Separation can be optimized by preceding silver-ion thin-layer chromatography (Ag-TLC), but this is laborious. We
have developed an efficient method for the separation of 18-carbon trans fatty acid isomers by combining GLC of FAME with GLC of fatty acid 4,4-dimethyloxazoline (DMOX) derivatives. We validated
this method against conventional GLC of FAME, with and without preceding Ag-TLC. Fatty acid isomers were identified by comparison
with standards, based on retention times and mass spectrometry. Analysis of DMOX derivatives allowed the 13t, 14t, and 15t isomers to be separated from the cis isomers. The combination of the GLC analyses of FAME and DMOX derivatives gave results comparable with those obtained by
GLC of FAME after preceding Ag-TLC, while saving about 100 h of manpower per 25 samples. It allowed the identification and
quantitation of 11 trans and 8 cis isomers and resulted in 25% higher values for total C18:1
trans, compared with the analysis of FAME alone. The combination of DMOX and FAME analyses, as applied to the analysis of 14 foods
that contained ruminant fat and partially hydrogenated vegetable and fish oils, indicated that the most common isomers were
11t in ruminant fats, 9t in partially hydrogenated fish fats, and either 9t or 10t in partially hydrogenated vegetable fats. The combination of GLC analyses of FAME and DMOX derivatives of fatty acids improves
the quantitation of 18-carbon fatty acid isomers and may replace the laborious and time-consuming Ag-TLC. 相似文献
16.
The use of polymer‐supported Lewis bases such as PEG4600‐(PPh2)2 and poly(DMAP) in the Baylis–Hillman reactions of N‐tosylimines (ArCHNTs) 1 or the corresponding arenecarbaldehydes with α,β‐unsaturated ketones has been investigated. The corresponding Baylis–Hillman adducts are obtained in good yields. The polymer‐supported Lewis bases can be easily recovered by filtration and the Lewis base PEG4600‐(PPh2)2 can be reproduced by reduction with LiAlH4 and CeCl3. 相似文献
17.
18.
Novel model for the sintering of ceramics with bimodal pore size distributions: Application to the sintering of lime 下载免费PDF全文
Juan C. Maya Farid Chejne Suresh K. Bhatia 《American Institute of Chemical Engineers》2017,63(3):893-902
A mathematical model for the sintering of ceramics with bimodal pore size distributions at intermediate and final stages is developed. It considers the simultaneous effects of coarsening by surface diffusion, and densification by grain boundary diffusion and lattice diffusion. This model involves population balances for the pores in different zones determined by each porosimetry peak, and is able to predict the evolution of pore size distribution function, surface area, and porosity over time. The model is experimentally validated for the sintering of lime and it is reliable in predicting the so called “initial induction period” in sintering, which is due to a decrease in intra‐aggregate porosity offset by an increase inter‐aggregate porosity. In addition, a novel methodology for determination of mechanisms based on the analysis of the pore size distribution function is proposed, and with this, it was demonstrated that lattice diffusion is the controlling mechanism in the CaO sintering. © 2016 American Institute of Chemical Engineers AIChE J, 63: 893–902, 2017 相似文献
19.
Romain Guitard Véronique Nardello-Rataj Jean-Marie Aubry 《International journal of molecular sciences》2016,17(8)
Radical-scavenging antioxidants play crucial roles in the protection of unsaturated oils against autoxidation and, especially, edible oils rich in omega-3 because of their high sensitivity to oxygen. Two complementary tools are employed to select, among a large set of natural and synthetic phenols, the most promising antioxidants. On the one hand, density functional theory (DFT) calculations provide bond dissociation enthalpies (BDEs) of 70 natural (i.e., tocopherols, hydroxybenzoic and cinnamic acids, flavonoids, stilbenes, lignans, and coumarins) and synthetic (i.e., 2,6-di-tert-butyl-4-methylphenol (BHT), 3-tert-butyl-4-hydroxyanisol (BHA), and tert-butylhydroquinone (TBHQ)) phenols. These BDEs are discussed on the basis of structure–activity relationships with regard to their potential antioxidant activities. On the other hand, the kinetic rate constants and number of hydrogen atoms released per phenol molecule are measured by monitoring the reaction of phenols with 2,2-diphenyl-1-picrylhydrazyl (DPPH•) radical. The comparison of the results obtained with these two complementary methods allows highlighting the most promising antioxidants. Finally, the antioxidant effectiveness of the best candidates is assessed by following the absorption of oxygen by methyl esters of linseed oil containing 0.5 mmol L−1 of antioxidant and warmed at 90 °C under oxygen atmosphere. Under these conditions, some natural phenols namely epigallocatechin gallate, myricetin, rosmarinic and carnosic acids were found to be more effective antioxidants than α-tocopherol. 相似文献
20.
Yinteng Shi Lin Ai Haonan Shi Xiaoyu Gu Yujun Han Jixiang Chen 《Frontiers of Chemical Science and Engineering》2022,16(4):443
Carbon-coated Ni, Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method. It was found that the introduction of Co remarkably reduced the carbon microsphere size. The metallic Ni, Co, and Ni-Co alloy particles (mainly 10–12 nm) were uniformly distributed in carbon microspheres. A charge transfer from Ni to Co appeared in the Ni-Co alloy. Compared with those of metallic Ni and Co, the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level, respectively. In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330 °C, the decarbonylation/decarboxylation pathway dominated on all catalysts. The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts, and the yields of n-pentadecane and n-C6–n-C16 reached 71.6% and 92.6%, respectively. The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres. Due to the confinement effect of carbon, the metal particles showed high resistance to sintering under harsh hydrothermal conditions. Catalyst deactivation is due to the carbonaceous deposition, and the regeneration with CO2 recovered the catalyst reactivity. 相似文献