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1.
《International Journal of Hydrogen Energy》2022,47(11):7242-7251
In the present study, metal-free catalysts for efficient H2 generation from NaBH4 methanolysis was produced for the first time from apricot kernel shells with two-step activation. The first stage of the two-stage activation includes the production of activated carbon with the KOH agent (AKOH), and the second stage includes hydrothermally HNO3 activation with oxygen doping (O doped AKOH + N). The hydrogen production rate (HGR) and the activation energy (Ea) of the reaction with the obtained metal-free catalyst (10 mg) were determined as 14,444 ml min?1 g?1 and 7.86 kJ mol?1, respectively. The structural and physical-chemical properties of these catalysts were characterized by XRD (X-ray diffraction), SEM (scanning electron microscopy), elemental CHNS analysis, FT-IR (Fourier transform infrared spectroscopy), and nitrogen adsorption analysis. Also, the reusability results of this metal-free catalyst for H2 production are promising. 相似文献
2.
Vinnie?Mao Samir?K.?Konar David?G.?B.?BoocockEmail author 《Journal of the American Oil Chemists' Society》2004,81(8):803-808
The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single
phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts
were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and
1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction
phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0
wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase
reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results,
presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved
after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium
hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical. 相似文献
3.
Very fast H2 production from the methanolysis of NaBH4 by metal‐free poly(ethylene imine) microgel catalysts
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The polyethyleneimine (PEI) microgels prepared via microemulsion polymerization are protonated by hydrochloric acid treatment (p‐PEI) and quaternized (q‐PEI) via modification reaction with methyl iodide and with bromo alkanes of different alkyl chain lengths such as 1‐bromoethane, 1‐bromobutane, 1‐bromohexane, and 1‐bromooctane. The bare p‐PEI and q‐PEI microgels are used as catalysts directly without any metal nanoparticles for the methanolysis reaction of sodium borohydride (NaBH4). Various parameters such as the protonation/quaternization reaction on PEI microgels, the amount of catalyst, the amount of NaBH4, and temperature are investigated for their effects on the hydrogen (H2) production rate. The reaction of self‐methanolysis of NaBH4 finishes in about 32.5 min, whereas the bare PEI microgel as catalyst finishes the methanolysis of NaBH4 in 22 min. Surprisingly, it is found that when the protonated PEI microgels are used as catalyst, the same methanolysis of NaBH4 is finished in 1.5 min. The highest H2 generation rate value is observed for protonated PEI microgels (10 mg) with 8013 mL of H2/(g of catalyst.min) for the methanolysis of NaBH4. Moreover, activation parameters are also calculated with activation energy value of 23.7 kJ/mol, enthalpy 20.9 kJ/mol, and entropy ?158 J/K.mol. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
4.
针对尿素醇解法合成碳酸二甲酯(DMC)工艺中DMC含量较低的DMC-MeOH物系的分离,建立了模拟常压-加压精馏工艺流程的模型。物系的液相活度系数由Wilson方程计算,通过AspenPlus过程模拟软件对常压-加压精馏工艺进行模拟计算。计算结果表明,常压-加压精馏工艺的主要物流的计算结果与实验值基本吻合,所建立的模型可靠;在满足产品中w(DMC)=99.5%的条件下,工艺模拟优化的结果为:常压精馏塔和加压精馏塔(1.0MPa)的实际塔板数分别为21和11,进料板位置分别为第6和第4块塔板,回流比分别为3.5和1.1,塔顶采出与进料流量比分别为0.63和0.92。 相似文献
5.
Sara M. Badenes Francisco Lemos Joaquim M. S. Cabral 《Journal of chemical technology and biotechnology (Oxford, Oxfordshire : 1986)》2010,85(7):993-998
BACKGROUND: This work evaluates the use of a reversed micellar catalytic system containing a lipolytic biocatalyst, cutinase, to promote the reaction of triglycerides with methanol, ethanol or butanol for the production of biodiesel in isooctane. RESULTS: The specific activity of cutinase increased with increase of the alcohol chain length, and methanol showed a significant toxicity toward the enzyme leading to a specific activity decrease for high concentrations of this alcohol, which did not occur when ethanol or butanol were used. The composition of the mixture was analyzed and it was shown that, although the reaction could proceed without water, the presence of water allowed higher reaction rates and higher conversions, probably because water helps to maintain both the micellar structure and lipase conformation. Excess water, however, had a deleterious effect on conversion. CONCLUSION: The influence of water and methanol, apart from micelle structure, was found to be linked to partition effects of diglyceride and monoglyceride, which may also have a significant impact on the reaction rate. Copyright © 2010 Society of Chemical Industry 相似文献
6.
Depolymerization of poly(ethylene terephthalate) waste (PETW) was carried out by methanolysis using zinc acetate in the presence of lead acetate as the catalyst at 120–140 °C in a closed batch reactor. The particle size ranging from 50 to 512.5 µm and the reaction time 60 to 150 min required for methanolysis of PETW were optimized. Optimal percentage conversion of PETW into dimethyl terephthalate (DMT) and ethylene glycol (EG) was 97.8% (at 120 °C) and 100% (at 130 and 140 °C) for the optimal reaction time of 120 min. Yields of DMT and EG were almost equal to PET conversion. EG and DMT were analyzed qualitatively and quantitatively. To avoid oxidation/carbonization during the reaction, methanolysis reactions were carried out below 150 °C. A kinetic model is developed and the experimental data show good agreement with the kinetic model. Rate constants, equilibrium constant, Gibbs free energy, enthalpy and entropy of reaction are also evaluated at 120, 130 and 140 °C. The methanolysis rate constant of the reaction at 140 °C (10.3 atm) was 1.4 × 10?3 g PET mol?1 min?1. The activation energy and the frequency factor for methanolysis of PETW were 95.31 kJ mol?1 and 107.1 g PET mol?1 min?1, respectively. © 2003 Society of Chemical Industry 相似文献
7.
对胜利褐煤在甲醇、碱体系中的超临界反应行为进行了研究,考察了反应温度、反应时间和碱的种类分别对胜利褐煤转化率、产物收率和分布规律的影响.结果表明,反应温度显著影响褐煤的转化率和产物收率,产物主要为四氢呋喃可溶组分(占67%~85%)和甲苯可溶组分(占8%~22%);300℃时,胜利褐煤在甲醇-NaOH体系中转化率和收率最高(99%左右);反应时间显著影响褐煤的转化率和产物收率,80 min后褐煤的转化率和产物收率分别为99%和100%;反应过程中四氢呋喃可溶组分可转化为甲苯可溶组分、正己烷可溶组分和水溶性组分;碱的种类对褐煤超临界醇解转化率和产物收率有显著影响. 相似文献
8.
Yomi?WatanabeEmail author Praphan?Pinsirodom Toshihiro?Nagao Takashi?Kobayashi Yutaka?Nishida Yoshiaki?Takagi Yuji?Shimada 《Journal of the American Oil Chemists' Society》2005,82(11):825-831
Acid oil is a by-product in the neutralization step of vegetable oil refining and is an alternative source of biodiesel fuel.
A model substrate of acid oil, which is composed of TAG and FFA, was used in experiments on the conversion to FAME by immobilized
Candida antarctica lipase. FFA in the mixture of TAG/FFA were efficiently esterified with methanol (MeOH), but the water generated by the esterification
significantly inhibited methanolysis of TAG. We thus attempted to convert a mixture of TAG/FFA to FAME by a two-step process
comprising methyl esterification of FFA and methanolysis of TAG by immobilized C. antarctica lipase. The first reaction was conducted at 30°C in a mixture of TAG/FFA (1∶1, wt/wt) and 10 wt% MeOH using 0.5 wt% immobilized
lipase, resulting in efficient esterification of FFA. The reaction mixture after 24 h was composed of 49.1 wt% TAG, 1.3 wt%
FFA, 49.1 wt% FAME, and negligible amounts of DAG and MAG (<0.5 wt%). The reaction mixture was then dehydrated and used as
a substrate for the second reaction, which was conducted at 30°C in a solution of the dehydrated mixture and 5.5 wt% MeOH
using 6 wt% immobilized lipase. The activity of the lipase increased gradually when the reaction was repeated by transferring
the enzyme to a fresh substrate mixture. The activity reached a maximum after 6 cycles, and the content of FAME achieved was
>98.5 wt% after a 24-h reaction. The immobilized lipase was very stable in the first-and second-step reactions and could be
used for >100 d without significant loss of activity. 相似文献
9.
Fast formation of high-purity methyl esters from vegetable oils 总被引:4,自引:0,他引:4
David G. B. Boocock Samir K. Konar V. Mao C. Lee Sonia Buligan 《Journal of the American Oil Chemists' Society》1998,75(9):1167-1172
Experiments have confirmed that the base-catalyzed methanolysis of vegetable oils occurs much slower than butanolysis because
of the two liquid phases initially present in the former reaction. For the same reason, second-order kinetics are not followed.
The use of a cosolvent such as tetrahydrofuran or methyl tertiary butyl ether speeds up methanolysis considerably. However,
like one-phase butanolysis, one-phase methanolysis initially exhibits a rapid formation of ester, but then slows drastically.
Experiments show that the half-life of the hydroxide catalyst is too long to explain the sudden slowing of the reaction. Similarly,
lower rate constants for the methylation of the mono- and diglycerides are not a reasonable explanation. Instead the cause
has been identified as the fall in polarity which results from the mixing of the nonpolar oil with the methanol. This lowers
the effectiveness of both hydroxide and alkoxide catalysts. Increasing the methanol/oil molar ratio to 27 in the one-phase
system raises the polarity such that the methyl ester content of the ester product exceeds 99.4 wt% in 7 min. This has obvious
implications for the size of new methyl ester plants as well as the capacity of existing facilities. 相似文献
10.
Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase 总被引:11,自引:8,他引:3
Yuji Shimada Yomi Watanabe Taichi Samukawa Akio Sugihara Hideo Noda Hideki Fukuda Yoshio Tominaga 《Journal of the American Oil Chemists' Society》1999,76(7):789-793
Biodiesel derived from vegetable oils has drawn considerable attention with increasing environmental consciousness. We attempted
continuous methanolysis of vegetable oil by an enzymatic process. Immobilized Candida antarctica lipase was found to be the most effective for the methanolysis among lipases tested. The enzyme was inactivated by shaking
in a mixture containing more than 1.5 molar equivalents of methanol against the oil. To fully convert the oil to its corresponding
methyl esters, at least 3 molar equivalents of methanol are needed. Thus, the reaction was conducted by adding methanol stepwise
to avoid lipase inactivation. The first step of the reaction was conducted at 30°C for 10 h in a mixture of oil/methanol (1:1,
mol/mol) and 4% immobilized lipase with shaking at 130 oscillations/min. After more than 95% methanol was consumed in ester
formation, a second molar equivalent of methanol was added and the reaction continued for 14 h. The third molar equivalent
of methanol was finally added and the reaction continued for 24 h (total reaction time, 48 h). This three-step process converted
98.4% of the oil to its corresponding methyl esters. To investigate the stability of the lipase, the three-step methanolysis
process was repeated by transferring the immobilized lipase to a fresh substrate mixture. As a result, more than 95% of the
ester conversion was maintained even after 50 cycles of the reaction (100 d). 相似文献