近临界水中水解鱼蛋白制备氨基酸

The hydrolysis technology and reaction kinetics for amino acids production from fish proteins in subcritical water reactor without catalysts were investigated in a reactor with volume of 400 ml under the conditions of reaction temperature from 180-320℃, pressure from 5-26 MPa, and time from 5-60 rain. The quality and quantity of amino acids in hydrolysate were determined by bioLiquid chromatography, and 17 kinds of amino acids were obtained. For the important 8 amino acids, the experiments were conducted to examine the effects of reaction temperature, pressure and time on amino acids yield. The optimum conditions for high yield are obtained from the experimental results. It is found that the nitrogen and carbon dioxide atmosphere should be used for leucine, isoleucine and histidine production while the air atmosphere might be used for other amino acids. The reaction time of 30 rain and the experimental temperature of 220℃, 240℃ and 260℃ were adopted for reaction kinetic research. The total yield of amino acids versus reaction time have been examined experimentally. According to these experimental data and under the condition of water excess, the macroscopic reaction kinetic equation of fish proteins hydrolysis was obtained with the hydrolysis reaction order of 1.615 and the rate constants being 0.0017, 0.0045 and 0.0097 at 220℃, 240℃ and 260℃ respectively. The activation energy is 145.1 kJ·mol^- 1.     

The effect of operating conditions on acylation of 2-methylnaphthalene in a microchannel reactor

Acylation of 2-methylnaphthalene(2-MN) is a very important reaction in organic synthesis,and the effiency of the continuous reactor is more than one of the batch reactor.Considering that the Friedel–Crafts acylation is a rapid exothermic reaction,in this study,we perform the acylation of 2-MN in a stainless steel microchannel flow reactor,which is characterized by high mass and heat transfer rates.The effect of reactant ratio,mixing temperature,reaction temperature,and reaction time on product yield and selectivity were investigated.Under the optimal conditions,2-methyl-6-propionylnaphthalene(2,6-MPN) was obtained in 85.8% yield with 87.5% selectivity.Compared with the conventional batch system,the continuous flow microchannel reactor provides a more efficient method for the synthesis of 2,6-MPN.     

Synthesis of allylamine in ethanol

Allylamine was prepared from the ammonolysis of allyl chloride or the reaction of allyl chloride with hexamethylenetetramine in ethanol. The selectivity of allylamine was improved from 21.4% to 67.6% when the reaction was carried out in ethanol instead of liquid ammonia. At the same time, the selectivity of allylamine was increased from 13.3% to 67.6% when the molar ratio of NH3 to allyl chloride was increased from 4. 5 ： 1 to 25 ： 1. However, the reaction of allyl chloride and hexamethylenetetramine in ethanol produced allylamine with high selectivity （100%） and high yield （87%）. The synthesis of allylamine from the reaction of allyl chloride and hexamethylenetetramine in ethanol was more straightforward and convenient.     

垂直管式反应器中超临界甲醇连续制备生物柴油I:相含率及反应中间产物的轴向分布(英文)

Production of biodiesel with supercritical methanol is a green synthesis process.A study was carried out in a vertical tubular reactor with a length of 3700 mm and a diameter of 20 mm at 275-375°C,15 MPa,and molar ratio of methanol to soybean oil of 40︰1.The phase holdup,intermediate product,yield and axial distribution of methyl ester(ME) were investigated.Methanol and oil were mixed non-uniformly due to the formation of biodiesel and difference in their densities,even when the reaction system was in the supercritical state.From top to bottom,the phase holdup of methanol increased and that of oil decreased.As temperature increased,the concentrations of monoglyceride and diglyceride decreased gradually and the ME yield increased.When the temperature reached 300°C,the critical temperature of the system,the ME yield was 50%.Further increase in temperature led to a sharp in-crease of ME yield.However,at 375°C after 1200 s of reaction time,the decomposition rate of ME was greater than its formation rate,reducing the ME yield.     

Rapid regeneration of chelated iron desulfurization solution using electrochemical reactor with rotating cylindrical electrodes简

A new electrochemical reactor with rotating cylindrical electrodes was designed and used to increase the regeneration efficiency of chelated iron desulfurization solution. The influence of operating parameters, such as the rotation speed of electrode, voltage, and inlet air and liquid flow rates, on the regeneration rate was investigated. Compared with the traditional tank-type reactor, the regeneration rate with the new electrochemical reactor was in- creased significantly. Under the optimum conditions, the regeneration rate was increased from 45.3% to 84.8%. Experimental results of continuous operation indicated that the new electrochemical regeneration method had some merits including higher regeneration efficiency, smaller equipment size and good stability in operation.     

Efficient,continuous oxidation of durene to pyromellitic dianhydride mediated by a V-Ti-P ternary catalyst: The remarkable doping effect

Continuous preparation of pyromellitic dianhydride(PMDA) from durene has been studied using a fixedbed reactor. The reaction was performed using a phosphorus-vanadium-titanium ternary catalyst.Relatively high selectivity and yield of PMDA was obtained. The in-situ characterization was combined with theoretical calculation to reveal the reaction mechanisms, and the remarkable doping effect was discussed.     

Isomerization of n-pentane catalyzed by amide-AlCl3-based ionic liquid analogs with various additives

The isomerization of n-pentane to generate high-quality blending components for clean gasoline was catalyzed by several amide-AlCl_3-based ionic liquid(IL) analogs with various amides as donor molecules. The catalytic performance of these IL analogs was evaluated in a magnetic agitated autoclave operated in batch mode.IL analog based n-methylacetamide(NMA)-AlCl_3 with the amide/AlCl_3 molar ratio of 0.65 showed excellent performance toward n-pentane isomerization because 0.65 NMA-1.0 AlCl_3 had a low viscosity and bidentate coordination structure. The influences of reaction time, reaction temperature, and stirring speed on the catalytic performance were also investigated. Optimal reaction conditions comprised the reaction time of 1 h, the reaction temperature of 40 °C, and the stirring speed of 1500 r·min~(-1). Under optimal condition, the n-C5 conversion,research octane number(RON) increment, total liquids yield, and isoparaffin yield in isomerized oil were56.80%, 13.51, 89.90 wt%, and 44.32 wt%, respectively. A new mathematical model was constructed to predict the relationships among RON increment, RON increment/n-C5 conversion ratio, and n-C5 conversion. The new model indicated that an appropriate conversion per pass of n-C5 did not exceed 50%–55%. Various cycloparaffin additives were used to improve the catalytic performance of 0.65 NMA-1.0 AlCl_3. The n-C5 conversion increased from 56.80% to 67.32%. The RON increment, total liquids yield, and isoparaffin yield reached 17.83, 97.36 wt%,and 63.74 wt%, respectively.     

Zn–Ca–Al mixed oxide as efficient catalyst for synthesis of propylene carbonate from urea and 1,2-propylene glycol

A series of Zn–Ca–Al oxides with different CaO and ZnO contents have been prepared and evaluated in the synthesis of propylene carbonate(PC) from 1,2-propylene glycol(PG) and urea in a batch reactor. The effect of catalyst composition, basicity and reaction process parameters such as temperature, catalyst dose, molar ratio of PG to urea, purge gas flow and reaction time has been studied to find suitable reaction conditions for the PC synthesis. The PC selectivity and yield under the desired conditions could reach 98.4% and 90.8%, respectively. The best performing catalyst also exhibited a good reusability without appreciable loss in the PC selectivity and yield after five consecutive reaction runs. In addition, a stepwise reaction pathway involving a 2-hydroxypropyl carbamate intermediate was proposed for the urea alcoholysis to PC in the presence of Zn–Ca–Al catalysts, according to the time dependences of reaction intermediates and products.     

1,6-己二胺与氨基甲酸甲酯非均相CeO2催化合成1,6-己二氨基甲酸甲酯（英文）

The efficient synthesis of dimethylhexane-1,6-dicarbamate (HDC) from 1,6-hexanediamine (HDA) and methyl carbonate over a series of heterogeneous catalysts (e.g., MgO, Fe2O3, Mo2O3, and CeO2) was investigated. The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments. Under optimized conditions, 100%HDA conversion with 83.1%HDCtotal and 16.9%polyurea was obtained using a one-step with high temperature procedure with CeO2 as the catalyst. A new two-step with variable temperature technol-ogy was developed based on the reaction pathway to reduce the polyurea yield. Using the proposed method, the HDCtotal yield reached 95.2%, whereas the polyurea yield decreased to 4.8%. The CeO2 catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods. ? 2014 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. Al rights reserved.     

Hydrolysis of Olive Oil with Immobilized Lipase in a Tapered Column Reactor

Lipase was immobilized in ion exchange resin and then used in the hydrolysis of olive oil to produce fatty acids and glycerol. The time course of hydrolysis of olive oil was investigated in a stirred tank reactor using both of the free and immobilized lipases to find the yield of activity of immobilized enzyme. Continuous hydrolysis of olive oil was also carried out in a tapered column reactor and a cylindrical column reactor with a bottom ID of 10 mm at different upward flow rates. It can be known from experimental results that the degree of hydrolysis of olive oil in the tapered column reactor is moderately better than that in the cylindrical column reactor, the pressure drop in the tapered column reactor is much smaller than that in the cylindrical column reactor.     

微通道反应器中二氯丙醇环化反应

研究了微通道反应器内二氯丙醇的环化制备环氧氯丙烷的反应,考察了反应温度、原料配比、停留时间等单因素对环氧氯丙烷收率的影响。实验确定了较优的工艺参数组合:环化反应温度50℃,二氯丙醇与氢氧化钠的摩尔比1∶1.2,停留时间45 s,NaOH质量分数20%时ECH的收率达到95.2%。在微通道反应的时空转化率要比常规反应高出两个数量级。与传统的工艺方法相比,微通道反应中环氧氯丙烷的收率提高了10%,降低了过程的能耗,废水排放量减少了45%。     

微通道反应器中二氯丙醇环化反应研究

研究了微通道反应器内二氯丙醇的环化制备环氧氯丙烷的反应,考察了反应温度、原料配比、停留时间等单因素对环氧氯丙烷收率的影响。实验确定了较优的工艺参数组合:环化反应温度50℃,二氯丙醇与氢氧化钠的摩尔比1∶1.2,停留时间45 s,NaOH质量分数20%时,ECH的收率达到95.2%。在微通道反应的时空转化率要比常规反应高出2个数量级。与传统的工艺方法相比,微通道反应中环氧氯丙烷的收率提高了10%,降低了过程的能耗,废水排放量减少了45%。     

内构件固定床反应器中不同水分煤的热解特性

通过在有无内构件(传热板和中心集气管)固定床反应器中研究不同水分含量煤的热解特性,考察了两反应器中煤料的升温特性、热解产物分布、焦油品质以及气体产物组成和半焦热值。结果表明,内构件可以强化传热和调节热解产物在反应器内的流动,相对无内构件反应器,有内构件反应器的反应时间缩短近一半。在有内构件反应器中,当煤水分增加,导致煤热解反应要求的时间延长,焦油中轻质组分(沸点低于360℃)含量明显升高,焦油收率先增加后降低,热解水和热解气产率升高,而无内构件反应器的热解产物无明显差异。当加热温度900℃时,煤水分从0.41%(本文中无特殊说明的均为质量分数) 增加至11.68%,焦油产率从9.21%增长到10.74%;当煤水分增加到15.93%,焦油产量下降到10.26%。两反应器气体平均组成随水分增加的变化趋势相似,气体热值均随水分增加呈下降趋势。     

微通道中环己酮氧化合成ε-己内酯的连续流工艺

在微通道反应器中,由H2O2、乙酸酐反应连续合成过氧乙酸氧化剂,再与环己酮经Baeyer-Villiger氧化连续合成ε-己内酯。先后考察了过氧乙酸氧化剂合成中乙酸酐与H2O2摩尔比、反应温度、停留时间等因素的影响,环己酮氧化反应中原料摩尔配比、反应温度、停留时间等因素对ε-己内酯合成的影响,优化了工艺条件。结果表明,当n(乙酸酐)∶n(H2O2)=1.2∶1、反应温度为70℃、停留时间为115s时,H2O2转化率达88.9%,过氧乙酸收率达86.7%;当n(过氧乙酸)∶n(环己酮)=1.1∶1、反应温度为90℃、停留时间为90s时,环己酮转化率达96.2%,ε-己内酯的收率达80.9%。与传统间歇釜式反应工艺相比,微通道反应工艺提高了ε-己内酯的收率和选择性,缩短了反应时间,减少了原料消耗,实现了连续化操作,提高了生产安全性。     

微通道反应器中乙酰乙酸甲酯的连续流合成工艺

传统的间歇反应合成存在温度不易控制、生产能力低、时间长等一系列问题,而微通道反应器可大幅度提高反应过程中的资源和能量的利用效率,减小过程系统的体积或提高单位体积的生产能力,实现化工过程强化、微型化和绿色化。本工作以双乙烯酮与甲醇为原料,探究在变径脉冲结构的微通道反应器中合成乙酰乙酸甲酯新方法。对催化剂类型、物料配比、停留时间、反应温度及催化剂用量进行了考察分析,最佳条件组合结果显示,当催化剂选择甲醇钠,且双乙烯酮:甲醇:甲醇钠=1:1.1:0.02(摩尔比),反应温度为90℃,停留时间为90 s时,双乙烯酮的转化率达100%,乙酰乙酸甲酯的选择性达96.8%,用此方法可以直接体现微通道反应器连续流合成的优势。     

F/F对嗜盐污泥以乙酸钠为底物生产PHB能力的影响

嗜盐混合菌生产PHB具有较好的成本优势。本研究接种入海口底泥发展嗜盐活性污泥,利用嗜盐活性污泥以两步法工艺生产PHB。在连续300 d的试验中从长期试验、发酵生产PHB以及表观动力学等方面探索了不同盛宴期/饥饿期(F/F)下筛选菌群的PHB积累能力。研究发现F/F作为重要的参数直接影响嗜盐活性污泥的PHB积累能力。在高F/F下非PHB积累菌群成为优势菌,而低F/F下促进高聚PHB嗜盐菌的选择和富集。在F/F≤0.33条件下筛选的嗜盐活性污泥最大PHB含量可以达到细胞干重的46.7%,PHB产率为0.358 mg PHB·(mg Ac)^-1。研究结果将对进一步实现嗜盐污泥生产PHB提供有益的指导。     

用十二烷基磺酸钠纯化重组大肠杆菌中的聚-β-羟基丁酸酯

引言聚-β-羟基丁酸酯（PHB）是微生物合成的一种高分子聚合物,它具有可生物降解性等特性,近年来深受世人瞩目．但由于PHB以颗粒状态存在于细胞中,因此分离提取很困难,生产成本很高．目前从微生物细胞中分离PHB的方法有溶剂萃取法、化学试剂法和酶法．虽然用次氯酸钠破细胞壁来分离PHB的化学试剂法操作简单、效率高,但次氯酸钠会引起PHB分子的严重降解,因此目前仍以溶剂萃取法和酶法为主．但这两种方法分别具有溶剂用量大和分离效率低的缺点．日本学者报道了用1％的油酸钠在120℃作用于菌体20min纯化PHB的方法．Ramsay等人先…     

用于ATRP反应体系的配位离子液体的合成

在微波反应器中通过有机多胺与氯化1-氯乙基-3-甲基咪唑离子液体[CeMIM]Cl的烷基化反应, 合成了具有配位功能离子液体[N₃MIM]Cl, 以替换传统的有机配体, 与催化剂CuBr配位形成催化体系, 催化离子液体中的原子转移自由基聚合(ATRP)。研究了反应工艺对离子液体合成的影响, 结果发现采用微波反应器加热, 反应时间短, 产物收率高。当反应物配比1.5:1、反应温度为75℃、微波反应3 h时, 产物[N₃MIM]Cl的收率达98.6%。采用电喷雾质谱和红外光谱测定离子液体结构, 证明该离子液体为[N₃MIM]Cl。将所合成配位离子液体替代有机配体, 用于离子液体中MMA的ATRP反应, 结果表明:配位离子液体可提高催化剂在离子液体中的溶解性, 使过渡金属催化剂容易与聚合产物分离。     

聚苯乙烯高温快速热解制备苯乙烯的研究

将聚苯乙烯(PS)溶于甲苯以雾化方式进料,在管式反应器中借助高温短停留时间快速热解制取苯乙烯,探讨了热解温度、停留时间、热解气氛、喷嘴口径等反应条件对热解的影响。结果表明,随停留时间增加,油相和苯乙烯收率总体呈上升趋势;苯乙烯收率随热解温度升高呈先增加后下降趋势,890 ℃时苯乙烯收率最大达到36.67 %;热解气主要为甲烷、乙烯和丙烯,其收率随停留时间和热解温度增加而增加;引入水蒸气可以减少反应结炭;喷嘴口径明显影响油相和苯乙烯收率。     

聚羟基丁酸酯的化学合成及生物降解性

提出了3 羟基丁酸乙酯本体聚合制备聚羟基丁酸酯(PHB)的工艺,设计了一套制备PHB的试验装置,确定了反应的试验方案。试验结果表明:在一定的反应时间范围内,随反应系统的压力降低及反应时间的延长,产物的摩尔质量逐步升高。还对化学法合成和生物发酵制备的PHB进行了生物降解性研究,确定了假单胞杆菌为降解PHB的主要菌类,化学合成的PHB可以被土壤中的细菌完全降解。