Degradation Kinetics of Xylose and Glucose in Hydrolysate Containing Dilute Sulfuric Acid

In preparation of fuel alcohol from biomass as feedstock, hydrolysis with dilute acid as catalyst is one way to produce fermentable saccharide, xylose and glucose. However, the acid is also the catalyst in degradation of xylose and glucose and the yield of sacchride is dependent on the kinetic behaviors of saccharide. The degradation kinetics of xylose and glucose in the hydrolysate was investigated under the conventional process conditions of hydrogen ion concentration from 0.05 to 0.2 mol/L and temperature from 150 to 200℃. With a numerical calculation method, the kinetic parameters were estimated, and the activation energy of xylose and glucose in the degradation reaction was obtained. The kinetic equations correlating the effect of hydrogen ion concentration on the rate constants of degradation reaction were established. Comparison between the calculated results from the equations and experimental ones proved that the established kinetic model could satisfactorily predict the degradation behavior of xylose and glucose in the acidic hydrolysate.     

磺酸功能化离子液体催化不饱和脂肪酸甲酯的环氧化研究

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.     

Kinetics of Sawdust Hydrolysi with Dilute Hydrochloric Acid and Ferrous Chloride

With dilute hydrochloric acid as catalyst and promoted by ferrous chloride, hydrolysis of waste sawdust to produce monosaccharides was conducted by using an one-step method in a batch-wise operation reactor. Based on the model of first order consecutive irreversible reactions, the kinetics equation incorporating the term of catalyst concentration was obtained that is suitable for describing the hydrolysis of sawdust. Activation energies were calculated for hydrolysis of sawdust and decomposition of monosaccharides.     

水-有机溶剂混溶体系中催化抗体催化拆分布洛芳脂

The asymmetric hydrolysis of racemic ibuprofen ester is one of the most important methods for chiral separation of ibuprofen. In this work, a catalytic antibody that accelerates the rate of enantioselective hydrolysis of ibuprofen methyl ester was obtained against an immunogen consisting of tetrahedral phosphonate hapten attached to bovine serum albumin (BSA). The catalytic activity of the catalytic antibody in the water-miscible organic-solvent system composed of a buffer solution and N, N-dimethylformamide (DMF) was studied. With 6% DMF in the buffer solution (containing catalytic antibody 0.25 μmol, 0.2 mol•L－1 phosphate buffer, pH 8) at 37°C for 10 h, a good conversion (48.7%) and high enantiomeric excess (>99%) could be reached. The kinetic analysis of the catalytic antibody-catalyzed reaction showed that the hydrolysis in the water-miscible organic-solvent system with DMF in buffer solution followed the Michaelis-Menten kinetics. The catalytic efficiency (Kcat/Km) was enhanced to 151.91 L•mmol－1•min－1, twice as large as that for the buffer solution only.     

高温液态水中葡萄糖无催化降解反应动力学

The decomposition kinetics of glucose was studied in high-temperature liquid water （HTLW） from 180 to 220℃ under a pressure of 10 MPa. It was found the main products from glucose decomposition were 5-hydroxymethylfurfural （5-HMF） and levulinic acid （LA）. The decomposition kinetics of 5-HMF and stability of LA in HTLW were further investigated. A kinetic model for glucose decomposition was proposed accordingly. In the model, a series of first-order reactions with the consideration of parallel by-reactions were used to illustrate the decomposition of glucose. The decomposition activation energies of glucose, 5-HMF, and LA were evaluated as 118.85, 95.40, and 31.29 kJ·mol^-1, respectively.     

Mechanically activated starch magnetic microspheres for Cd(Ⅱ) adsorption from aqueous solution

Magnetic starch microspheres(AAM-MSM) were synthesized via an inverse emulsion graft copolymerization by using mechanically activated cassava starch(MS) as a crude material, acrylic acid(AA) and acrylamide(AM) as graft copolymer monomers, and methyl methacrylate(MMA) as the dispersing agent and used as an adsorbent for the removal of Cd(II) ions from aqueous solution. Fourier-transform infrared spectroscopy(FT-IR), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), and vibrating sample magnetometry(VSM) were used to characterize the AAM-MSM adsorbent. The results indicated that AA, AM, and MMA were grafted to the MS, and the Fe_3 O_4 nanoparticles were encapsulated in the AAM-MSM adsorbent microspheres.The adsorbent exhibited a smooth surface, uniform size, and good sphericity because of the addition of the MMA and provided more adsorption sites for the Cd(II) ions. The maximum adsorption capacity of Cd(II) on the AAM-MSM was 39.98 mg·g~(-1). The adsorbents were superparamagnetic, and the saturation magnetization was 16.7 A·m~2·kg~(-1). Additionally, the adsorption isotherms and kinetics of the adsorption process were further investigated. The process of Cd(II) ions adsorbed onto the AAM-MSM could be described more favorably by the pseudo-second-order kinetic and Langmuir isothermal adsorption models, which suggested that the chemical reaction process dominated the adsorption process for the Cd(II) and chemisorption was the rate-controlling step during the Cd(II) removal process.     

Solvent extraction of lanthanum and cerium ions from hydrochloric acidic aqueous solutions using partly saponified 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester

In order to clarify the extraction process with saponified extractant, the solvent extraction experiments of rare earth elements(REEs), lanthanum and cerium, by using partly saponified 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester(EHEHPA, HL) from hydrochloric acidic solutions have been performed. The concentration of initial aqueous rare earth ion was in a range of 0.0010–0.1000 mol·L~(-1); EHEHPA in a range of 0.2877–0.8631 mol·L~(-1) with saponification rate of 0.3(mole fraction), and the initial aqueous p H in a range of 1.00–4.00. Firstly, the extracted species were determined by the saturation extraction capacity method. Secondly, according to the equilibrium aqueous pH values, the extraction processes were divided into three different categories: extraction with saponified EHEHPA, extraction with un-saponified EHEHPA, and hydrolysis process. Finally, for the first two processes, in order to predict the distribution ratio, two semi-empirical calculation models were developed with.The calculation results are in good agreement well with the experimental data.     

游离静止细胞中腈水合酶的失活动力学

Nitrile hydratase (NHase) is an important industrial enzyme used for acrylamide production from acrylonitrile. The deactivation kinetics of NHases in free resting cells of Rhodococcus sp. was presented based on a bi-steady state assumption. Effects of hydration temperature, product concentration and substrate concentration on NHase deactivation were investigated experimentally and correlated with a first order deactivation kinetics. The results showed that the hydration temperature and product concentration were major factors governing the deactivation of NHases under substrate-feeding conditions. When acrylamide concentration was higher than 250 g•L－1, the deactivation of NHases became serious and the bi-steady state assumption was not applicable. When the hydration temperature was controlled at a relatively higher level such as 28°C, the total deactivation rate constant was about 2.8-fold of that at 20°C.     

加压微波辅助水解甘草酸粗品制备甘草次酸(英文)

A pressured microwave-assisted hydrolysis(PMAH) technique has been developed for hydrolyzing the crude glycyrrhizic acid(GA) extracted from licorice root to prepare glycyrrhetinic acid(GRA).In order to optimize the efficiency of PMAH,several experimental parameters were investigated,including liquid-solid ratio,hydrolysis time,sulfuric acid concentration and hydrolysis temperature.The optimized hydrolysis conditions were as follows:pressured microwave-assisted hydrolysis of crude GA for 21 min(taking 15 min to reach 150 oC,and holding it for 6 min) at 150 oC(at a radiation power of 450 W) in 3%-5% sulfuric acid solution with the liquid-solid(ml?g?1 crude GA) ratio of 25︰1.As a result of the considerable saving in time and higher product yields(up to 90%),PMAH was proved more effective than conventional methods.     

炭基固体酸催化废油脂合成生物柴油动力学研究(英文)

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller(BET)surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.     

有机相酶法不对称水解乳酸乙酯

探讨了在有机介质中酶催化外消旋乳酸乙酯不对称水解制备L-乳酸的可行性。 研究了反应介质、不同来源的酶、摇床转速、水含量、乳酸乙酯浓度及温度等因素对反应的影响。结果表明,N435的活性和选择性较高,叔丁醇和异辛烷的混合溶剂（体积比为1∶1）为最合适的反应介质,其余最适条件为：摇床转数200 r•min^-1、水含量（水与底物的质量比）1∶5、乳酸乙酯浓度0.27 g•ml^-1、酶浓0.8 g•mol^-1、反应温度60℃,在此条件下反应16 h得产物ee值为90.02% ,产率为28.69%。 最后研究了乳酸乙酯不对称水解的动力学,结果表明反应符合米氏方程,属于双底物抑制的双乒乓机制,并考察了D-乳酸乙酯和D-乳酸在建立反应动力学模型时的影响。     

Acid hydrolysis of olive tree biomass

Olive tree cultivation generates a great amount of biomass residues which have no industrial application. Pruning residues are usually grindered or burnt on fields, causing economical costs and environmental concerns. An alternative issue for these renewable sugar-containing feedstocks may be the conversion into fuel ethanol by hydrolysis and fermentation.As a first step in the bioconversion process, the acid hydrolysis of olive tree pruning is studied and a mathematical model predicting both fiber content and sugar release as a function of operation variables is proposed. Sulphuric acid concentration in the range 0–32% (w/w), process temperature between 60 and 90 °C and hydrolysis time from 0 to 240 min were used as hydrolysis conditions. The process was modelled by first-order reaction kinetics. The apparent kinetic constant relating acid concentration to fiber hydrolysis and sugar release shows a potential dependence; on the other hand, an Arrhenius-type equation has enabled the evaluation of activation energy values of 26.4 and 25.9 kJ/mol for fiber hydrolysis and sugar generation, respectively.     

5-羟基乙酰丙酸的内酯化与缩聚反应

以乙酰丙酸(LA)为原料,通过改进的溴化、水解反应,合成5-羟基乙酰丙酸(5-HLA).基于5-HLA的羟基和羧基,将其作为单体,氯化亚锡为催化剂,经缩聚得到了一种新的脂肪族聚酯——聚5-羟基乙酰丙酸(PHLA).另以BF₃•OEt₂为催化剂,进行5-HLA的内酯化反应,得到了二聚体[BF]1,6,9,13-[BFQ]四氧双螺［4. 2. 4. 2］十四烷-2,10-二酮(又称阿尔泰内酯),它是中药九节菖蒲的化学成分之一.分别用气质联用、核磁、红外、元素分析和凝胶渗透色谱等方法对所得二聚体以及聚合物结构进行表征,讨论了有关的反应机理.     

大豆秸秆酶水解及L-乳酸发酵

用纤维素酶对氨预处理后的大豆秸秆进行酶水解,利用纤维素酶的作用使纤维素、半纤维素水解为可溶性糖,继而研究了用干酪乳杆菌及清酒乳杆菌进行L-乳酸发酵,通过微生物发酵将生成的可溶性糖转化为用于生产具有可生物降解性的聚乳酸塑料的原料乳酸,实现可再生资源的充分利用.结果表明,实验条件下,5%的大豆秸秆经酶水解后,还原糖浓度为242.25 mg•g^-1,纤维素糖化率为51.22%.清酒乳杆菌、干酪乳杆菌及该两种混合菌种发酵酶解液所得L-乳酸的转化率分别为 48.27%、56.42%和71.05%.     

Protein hydrolysis under anaerobic,saline conditions in presence of acetic acid

The hydrolysis of soluble proteins in an anaerobic, saline (24 g dm^?3 NaCl) and mesophilic (37 °C) environment was studied. The inhibitory effect of a volatile fatty acid, acetic acid (HAc), on the hydrolysis rate and hydrolytic biomass activity for a model saline wastewater with a high protein load (total organic carbon, 1153 mg dm^?3 and 1572 mg dm^?3 proteins) was studied. Initial inhibitor concentrations were tested in the range of 0–2000 mg dm^?3 HAc. The microbiological characterization was performed using a total microorganism count by epifluorescence, and hydrolytic bacterial activity was determined by plate count. The protein hydrolysis was modeled according to first order kinetics. The effect of biomass on hydrolysis was analyzed by varying its concentration in the range of 42–210 mg dm^?3 volatile suspended solids. The following apparent hydrolysis kinetic constants (K_h) for proteins at 37 °C were obtained: 1.3, 0.8, 0.6, 0.2 and 0.1 d^?1 for initial concentrations of 250, 500, 750, 880, and 1000 mg dm^?3 HAc, respectively. At concentrations of HAc greater than 1000 mg dm^?3, total inhibition of hydrolysis was observed. The intrinsic hydrolysis constant ( ) at 37 °C, without inhibition, was 2.3 d^?1. The hydrolysis kinetic constant was not affected by the biomass concentration. The hydrolysis kinetics constant was filted to three models: Luong, Levenspiel and non‐competitive inhibition. The model that best represented the experimental data was Luong, obtaining an inhibition constant (K_I) of 1087 mg dm^?3 of HAc and the exponent γ = 0.54. The hydrolysis was inhibited by the presence of HAc, which corresponds to an intermediate compound of the anaerobic process. Copyright © 2004 Society of Chemical Industry     

Sesame cake protein hydrolysis by alcalase: Effects of process parameters on hydrolysis, solubilisation, and enzyme inactivation

We investigated the effects of process parameters (substrate concentration, enzyme concentration, temperature and pH) on the hydrolysis and solubilization of sesame cake protein as well as enzyme stability. The sesame cake protein was hydrolyzed by Alcalase enzyme (a bacterial protease produced by a selected strain of Bacillus Licheniformis) that was chosen among five commercial enzymes examined. The optimum process conditions for hydrolysis and solubilization were obtained as 15 g L^?1 substrate concentration, 3 ml L^?1 enzyme concentration, 50 °C and pH 8.5. Under these conditions, the values of degree of hydrolysis and solubilization were found as 26.3% and 82.1%, respectively, and enzyme lost its activity by approx. 56% at the end of 120 min processing time. Modeling studies were performed to determine the kinetics of hydrolysis, solubilization and enzyme inactivation. The relationship between hydrolysis and solubilization was found linear for all experimental conditions examined. The inactivation energy of Alcalase at the temperature range of 45–55 °C was determined to be 25544 J mol^?1.     

PTA法易水解聚酯的合成及水解性能

用精对苯二甲酸法合成了一系列易水解聚酯(EHDPET)，重点考察了共聚酯的化学结构和碱水解过程中各工艺条件对其水解性能的影响，并对EHDPET的碱水解动力学进行了初步探讨。结果表明，提高间苯二甲酸乙二酯—5—磺酸钠、第四单体等各组分含量及添加助剂可提高减量率；加大碱浓度、提高温度及延长水解时间均可加快碱水解速率。     

Identification of two amino acids contributing the high enzyme activity in the alkaline pH range of an alkaline endoglucanase from a Bacillus sP

An alkaline cellulase ß-1,4-endoglucanase; NK1) froman alkalophilk Bacillus sp. shows great similarity in aminoacid sequence to a neutral cellulase (BSC) from Bacillus subtilis,despite a considerable difference in their pH activity profiles.Multiple amino acid exchanges by site-directed mutagenesis,using BSC as the reference, were performed on the residues inregion 5 of NK1, which was previously shown to be responsiblefor the high enzyme activity of this alkaline cellulase in abroad alkaline pH range. Two amino acid residues, Ser287 andAla296, were identified as being responsible for the activityin the alkaline range. The double mutation, Ser287 to Asn andAla296 to Ser, of NK1 made its pH activity profile almost thesame as that of BSC. On the other hand, the pH activity profilein the acidic range was not significantly affected by variousamino acid replacements including these two positions in region5. This observation, together with the information availableon other endoglucanases, suggests that the above two amino acidsubstitutions caused a profound effect through rearrangementof the hydrogen bond network forming the substrate-binding siteor the catalytic site.     

高温液态水中果糖无催化分解反应动力学

研究了压力10 MPa下、温度453.15～493.15 K范围内果糖在高温液态水中的无催化分解反应动力学.实验结果表明,在无任何催化剂条件下,果糖能顺利进行分解反应,且随着温度的升高,分解反应速率常数显著地增大.在本实验范围内,果糖分解反应的活化能为126.16 kJ•mol^-1.另外,对不同温度下反应时间对果糖分解的主要产物——5-羟甲基糠醛收率的影响进行了考察.通过控制反应条件可以有选择性地调节产物分布.     

固定化脂肪酶选择性富集鱼油ω-3多不饱和脂肪酸甘油酯

采用吸附与交联相结合的方法固定化米曲霉脂肪酶.脂肪酶固定化的参数条件：载体为硅藻土、吸附温度为25℃、吸附时间为6 h、pH值为7.0 KH₂PO₄-NaOH缓冲液、缓冲液离子强度为0.03 mol•L^-1、给酶量为900 U•（g硅藻土）^-1、交联剂为0.5％戊二醛、交联的时间为1.5 h,所得固定化酶酶活力为247 U•（g载体）^-1,蛋白载量为25 mg•（g硅藻土）^-1,水解鱼油操作半衰期为264 h.固定化脂肪酶富集鱼油中ω-3多不饱和脂肪酸甘油酯的最适条件是：温度38 ℃、油水比为1∶1、加酶量为150U•（g油）^-1、反应转速为200 r•min^-1、最佳富集时间为24 h.在此工艺条件下鱼油中EPA由3.0%提高到7.0%,DHA由4.3%提高到14.5%,EPA+DHA由7.3%提高到21.5%.