硫酸催化葡萄糖制备乙酰丙酸的过程强化

采用高温下稀硫酸催化葡萄糖的方法制备乙酰丙酸。考察了反应温度、硫酸浓度和搅拌转速对葡萄糖转化率和乙酰丙酸收率的影响,并优化确定了最优反应条件。进一步,分析了最优反应条件下不同葡萄糖初始浓度对乙酰丙酸收率的影响。为了提高高浓度葡萄糖底物反应时乙酰丙酸的收率,采用两种不同的补料方法进行实验：分3次,依次加入7%、6%与5%的葡萄糖;每次均添加3%的葡萄糖,共6次。结果表明：①提高硫酸浓度、反应温度和搅拌速度有利于加快葡萄糖转化和乙酰丙酸生成;②高浓度葡萄糖底物不利于乙酰丙酸的生成,且浓度越高,乙酰丙酸收率越低;③通过补料操作,可使乙酰丙酸收率由 44.3%提高至65.9%。     

5-羟甲基糠醛在稀硫酸催化下的降解反应动力学

5-羟甲基糠醛脱羧生成乙酰丙酸是生物质资源出发制备乙酰丙酸过程中的关键步骤之一。为了研究低硫酸浓度下水解生物质制备乙酰丙酸工艺的可行性,系统地测定了在压力5 MPa、初始浓度1～9 mg·ml^-1、硫酸浓度0.05%～0.4%（质量分数）、温度150～190℃条件下,5-羟甲基糠醛在稀硫酸催化下的降解反应动力学数据,并以主反应生成乙酰丙酸、副反应生成腐黑质的平行反应动力学模型对数据进行了拟合,拟合结果表明,在实验范围内,主、副反应对5-羟甲基糠醛均为一级反应;主反应对H⁺浓度为1.16级,反应的活化能为78.5 kJ·mol^-1;副反应对H⁺浓度为0.722级,反应的活化能为98.0 kJ·mol^-1。研究结果表明,降低温度和提高硫酸浓度有利于提高生成乙酰丙酸的选择性。     

蔗渣纤维组分的常压一步分离

蔗渣纤维组分的分离是实现其综合利用的关键,对蔗渣纤维组分进行了常压一步分离研究。采用溶剂-酸-水体系分离工艺,响应面法优化最佳工艺条件。结果表明,溶剂浓度69.63%(体积分数)、酸浓度(体积分数)6.41%、反应时间4h,蔗渣半纤维素分离率为98.07%、木质素分离率为66.72%、纤维素得率为92.49%,验证试验半纤维素分离率99%、木质素分离率67.06%、纤维素得率92.08%,分离条件可靠、分离结果较理想。最佳分离工艺条件下木糖得率90.01%,木质素回收率62.15%、分离的生物质总的可利用率71.53%。     

沙柳酸催化水解制备乙酰丙酸及分离提纯

以沙柳为原料,硫酸为催化剂,考察了催化剂浓度、反应时间、反应温度、液固比对沙柳水解制备乙酰丙酸得率的影响,通过正交实验方法得到最佳的水解反应条件为：反应温度200 ℃,反应时间90 min,催化剂质量分数9%,液固比（mL∶g）15∶1,乙酰丙酸的最高得率为18.80%;各因素对水解反应影响的大小顺序为：反应时间＞催化剂浓度＞反应温度＞液固比。在静态条件下,用335弱碱性阴离子交换树脂对水解液进行分离提纯,在附吸温度为35 ℃、树脂投料量为15 g、盐酸洗脱剂浓度为0.5 mol/L时,乙酰丙酸的回收率为95.35%。     

半乳糖常压水解制备乙酰丙酸

以半乳糖为原料,常压下硫酸催化水解制备乙酰丙酸,探讨了半乳糖浓度、反应温度、反应时间、硫酸浓度等对乙酰丙酸产率的影响.结果表明,硫酸催化水解制乙酰丙酸的最优反应条件为:半乳糖浓度0.4 mol·L-1、反应温度130℃、反应时间60 min、硫酸浓度3.5 mol·L-1,在此条件下,乙酰丙酸产率最高达到64.2％.     

Etherification of hemicelluloses from sugarcane bagasse

Conditions for the preparation of etherified hemicelluloses from sugarcane bagasse with 2, 3‐epoxypropyltrimethylammonium chloride (ETA) using sodium hydroxide as a catalyst in aqueous solution were studied comparatively. The extent of the etherification was measured by yield percentage and degree of substitution. The effects of reaction time of 3–7 h, reaction temperature of 50–80°C, temperature of alkaline activation of 30–60°C, and time of alkaline activation of 0–60 min on the reaction yield and degree of substitution were investigated in detail. The overall yield and degree of substitution were varied from 35.2 to 41.9% and from 0.14 to 0.33, respectively, by changing the reaction temperature and duration as well as time and temperature of alkaline activation. The new materials were characterized by FT‐IR and 13C NMR spectroscopy, thermal analysis as well as GPC. It was found that the thermal stability of the hemicellulosic ethers decreased after chemical modification, and the molecular weights of the etherified hemicelluloses were lower than those of the native hemicelluloses. ¹³C NMR spectra gave the evidence for etherification reaction and the quaternization of hemicelluloses occurred mainly at C‐3 position. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

加拿大一支黄花基乙酰丙酸的制备研究

以加拿大一枝黄花为原材料,提取α-纤维素,并制备乙酰丙酸。在符合生物炼制观念的基础上,考察温度、时间、酸浓度、固液比对乙酰丙酸的产率和还原糖残留量的影响。采用气相色谱法进行产率的分析。结果表明,压力为2.0 MPa时,在最佳温度230℃,时间45 min,硫酸浓度为6%,固液比1∶20的条件下,乙酰丙酸的产率为27.62%。反应结束之后,还原糖基本完全转化,残留量为1.02%。     

Manufacture of Microcrystalline Cellulose from Eucalyptus globulus Wood Using an Environmentally Friendly Biorefinery Method

In this work, hemiceluloses and lignin were solubilized by successive steps of autohydrolysis and delignification, and the resulting solids were processed to obtain microcrystalline cellulose. Eucalyptus globulus wood chips were treated with hot, compressed water under selected conditions to cause the hydrolytic breakdown of heteroxylan into substituted saccharides. The xylan-depleted solids were treated with acetic acid under optimized conditions to remove lignin, leaving a solid phase with high cellulose content. This latter was subjected to Totally Chlorine Free (TCF) bleaching to yield microcrystalline cellulose. These sequence autohydrolysis-organosolv delignification-TCF bleaching enabled the selective separation of hemicelluloses (which were mainly converted into soluble saccharides), lignin (as compounds soluble into acetic acid), and microcrystalline cellulose, according to an environmentally friendly biorefinery method.     

固体超强酸催化剂S2O82-/ZrO2-TiO2-Al2O3制备乙酰丙酸

研制了固体超强酸催化剂S2O82―/ZrO2-TiO2-Al2O3,并以蔗糖为原料,催化水解法制备乙酰丙酸。通过单变量法考察了催化剂的焙烧温度、催化剂的投加量、蔗糖浓度、反应温度、反应时间等对乙酰丙酸相对收率的影响,并采用了正交实验来确定最佳工艺条件。研究结果表明,当催化剂的焙烧温度为550℃、蔗糖浓度为15 g/L、催化剂用量为蔗糖质量的15%、反应温度为200℃、反应时间为60 min时,乙酰丙酸的相对收率最大,达到72.28%。     

Valorization of chitosan into levulinic acid by hydrothermal catalytic conversion with methanesulfonic acid

As a potential renewable aquatic resource, chitosan is the second most abundant biopolymer. Methanesulfonic acid is a catalyst that is strongly acidic and biodegradable. We used chitosan and methanesulfonic acid to produce platform chemicals via an acid-catalyzed hydrothermal reaction. In the methanesulfonic acid-catalyzed hydrothermal conversion of chitosan, an optimal levulinic acid yield of 28.21±1.20% was achieved under the following conditions: 2% chitosan and 0.2 M methanesulfonic acid at 200 °C for 30 min. These results indicated that a combination of chitosan and methanesulfonic acid would be suitable for platform chemical production.     

Reactive adsorption for the selective dehydration of sugars to furans: Modeling and experiments

5‐hydroxymethylfurfural (HMF) can be produced from the acid‐catalyzed dehydration of fructose, but its yield is limited due to subsequent HMF degradation to side products. A reactive adsorption process is proposed to improve the yield to HMF. Separate experimental single‐component isotherms of fructose, HMF, formic acid, and levulinic acid on carbon BP2000 and reaction kinetics of the fructose dehydration to HMF in aqueous solution of HCl are presented to develop empirical isotherms and kinetic rate constants, respectively. These submodels are subsequently integrated in an adsorptive reactor at a range of temperatures (100–150^°C) with different loadings of adsorbent. It is shown that the adsorbent improves HMF yield compared to the single‐solution phase (adsorbent‐free case). Low temperatures and high‐adsorbent loadings improve HMF yield. Under certain conditions both reactive adsorption and the commonly used reactive extraction can result in a similar improvement in HMF yield. HMF recovery from the solid adsorbent has been identified as a major challenge that can be ameliorated through adsorbent and solvent selection. The framework outlined here can be applied to any aqueous phase chemistry where the desired product is an intermediate in a reaction cascade. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3378–3390, 2013     

木糖生产残渣制取乙酰丙酸及活性炭

用玉米芯制木糖后的废渣经加酸加热水解制取乙酰丙酸,收率为 １６．４％ ,产品纯度可达 ９０％ 。其残渣经硫酸炭化制得了木素活性炭,收率为 ８３％ ,脱色性能优于国家标准（ Ｇ Ｂ／ Ｔ １２４９６．２－ ９０）。本研究为以玉米芯为原料生产木糖的企业提供了一条综合利用、变废为宝的有效途径。     

Graft copolymerization of methacrylonitrile on kenaf fibers by cerric ion-toluene redox pair

The graft copolymerization of methacrylonitrile onto kenaf fibers by a cerric ion-toluene redox pair was investigated in aqueous media. Graft yield of up to 212% was found, but the grafting efficiency was not greater than 17.6%. At varying concentrations of toluene, the conversion in graft yield passed through a maximum and thereafter decreased by as much as 46% for a two-half increase in the concentration of toluene. Similarly, acetic acid showed an initial increase in graft yield in the concentration range of 0.58-1.17M and a reduction to zero graft at a 11.67M concentration of the acid. Under identical reaction conditions, acetic acid and its derivatives decreased the graft yield in the order trichloroacetic acid > monochloroacetic acid > acetic acid > formic acid. The effect of the chlorinated acids was considered as a composite consisting of normal transfer reactions and a hydrolytic effect, as strong acids, on the grafted polymers. The percentage graft yield showed a normal temperature dependence over the range 30-60°C with a calculated activation energy of 6.52 kcal mol⁻¹. The amount of grafted polymer increased with monomer concentration, but the average molecular weight decreased with the latter, suggesting an enhanced utilization of more grafting sites on the fibers. The water-retention capacity of the graft copolymer showed an 85% reduction in its value over a three fold increase in the graft yield. © 1996 John Wiley & Sons, Inc.     

Succinoylation of wheat straw hemicelluloses with a low degree of substitution in aqueous systems

The reaction of wheat straw hemicelluloses with succinic anhydride in aqueous alkaline systems was studied. The products showed a rather low degree of substitution, ranging from 0.017 to 0.21. The effects of reaction times of 0.5–16 h, temperatures of 25–45°C, and molar ratios of succinic anhydride to anhydroxylose units in hemicelluloses of 1:5–1:1 on the succinoylation yield and degree of substitution were examined. With the reaction kept within a pH range of 8.5–9.0, a temperature range of 25–28°C, a reaction duration of 1–2 h, and a 1:1 molar ratio of succinic anhydride to hemicelluloses were preferred. The structure of the resulting polymers was determined with Fourier transform infrared and ¹H‐ and ¹³C‐NMR spectroscopy, which indicated monoester substitution. The thermal stability of the esterified polymer increased with chemical modification. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 757–766, 2002     

Acetylation of sugarcane bagasse hemicelluloses under mild reaction conditions by using NBS as a catalyst

Sugarcane bagasse hemicelluloses were partially acetylated with acetic anhydride using N‐bromosuccinimide (NBS) as a catalyst under mild conditions in an almost solvent‐free system. The overall yield and degree of substitution (DS) were varied from 66.2 and 83.5% and between 0.27 and 1.15, respectively, by changing the reaction temperature and duration. It was found that the yield and DS increased with reaction temperature from 18 to 80°C and reaction time between 0.5 and 5.0 h. The results showed that treatment of the native hemicelluloses with acetic anhydride using NBS as a catalyst conveniently provided the corresponding biopolymer esters. The products were characterized by FTIR, ¹³C‐NMR spectroscopy, and thermal analysis. The new biopolymer acetates were thermally stable to over 200°C but underwent significant and rapid thermal degradation when heated above the onset of thermal degradation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 53–61, 2004     

REACTIVE EXTRACTION OF LEVULINIC ACID FROM AQUEOUS SOLUTIONS WITH TRI-n-OCTYLAMINE (TOA) IN 1-OCTANOL: EQUILIBRIA,KINETICS, AND MODEL DEVELOPMENT

Levulinic acid, a carboxylic acid containing a ketone structure, can be used as an acidulant in foods and beverages. Reactive extraction is a promising alternative for the recovery of carboxylic acids from aqueous streams. The design of an amine extraction process requires kinetic data for the acid-amine + solvent system used. In this study, equilibrium and kinetic data on the extraction of levulinic acid from aqueous solutions using tri-n-octylamine (TOA) in 1-octanol have been determined. The mass transfer coefficients of levulinic acid, TOA, and 2:1 levulinic acid-amine complex in 1-octanol were calculated from the acetic acid mass transfer coefficient, which was determined by measuring its fluxes of simple diffusion from kerosene to water. Based on the Hatta number and the criterion given by Doraiswamy and Sharma, the reaction regime has been found to be instantaneous reaction regime occurring at the interface on the organic phase side. An extraction model comprising equilibrium complexation constant w.r.t 2:1 levulinic acid-TOA complex formation, K_E2i (14.794 (m³ kmol^?1)²), and complex mass transfer coefficient, k_B2A (2.193 × 10^?6 m s^?1), has been developed.     

稻草酸水解制备乙酰丙酸的研究

以稻草为原料,高压酸水解法制备乙酰丙酸,采用气相色谱法测定水解液中乙酰丙酸的含量,考察了反应温度、反应时间、固液比和硫酸质量分数对乙酰丙酸得率的影响,通过单因素试验确定了最佳水解条件。结果表明,在高压 1.6 MPa 条件下,反应温度 170℃,反应时间 60 min,固液比1:10,硫酸的质量分数为 5% 时,所制得乙酰丙酸得率为 24.35%,此条件下水解残渣中纤维素和多戊糖均已完全反应。     

固体超强酸催化剂S2O82-/聚乙二醇-TiO2-M2O3(M=Al,Cr)制备乙酰丙酸

研制了固体超强酸催化剂S₂O₈^2-/聚乙二醇-TiO₂-M₂O₃(M=Al,Cr), 并以赤砂糖为原料,催化水解法制备乙酰丙酸。通过单变量法考察了催化剂焙烧时间、催化剂用量、赤砂糖浓度、反应温度和反应时间等对乙酰丙酸收率的影响,并通过正交实验确定最佳工艺条件。结果表明,在催化剂焙烧时间120 min、赤砂糖浓度为10 g·L^-1、催化剂用量为赤砂糖质量的15%、反应温度200 ℃和反应时间120 min条件下,乙酰丙酸收率达39.98%。     

Esterification of Renewable Levulinic Acid to n‐Butyl Levulinate over Modified H‐ZSM‐5

The synthesis of n‐butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass‐derived levulinic acid (LA) with n‐butanol over modified H‐ZSM‐5 (micro/meso‐HZ‐5) in a closed‐batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n‐butyl levulinate. Micro/meso‐HZ‐5 was found to be the most efficient catalyst, with 98 % yield of n‐butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second‐order pseudo‐homogeneous model with R² > 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol^?1.     

Valorization of galactose into levulinic acid via acid catalysis

We applied methanesulfonic acid (MSA) as a green catalyst to produce levulinic acid (LA) from monomeric sugars. To optimize reaction factors and assess the effect of reciprocal interactions, a statistical experimental design was applied. Optimized result of 40.7% LA yield was obtained under the following conditions: 60 g/L galactose, 0.4M MSA at 188 °C for 26.7 min. On the other hand, 66.1% LA yield was achieved under 60 g/L fructose and 0.4M MSA at 188 °C for 36 min conditions. For the effect of combined severity factor on the LA yield from galactose, the LA yield showed a peaked pattern, which was linearly increased until a CSF 3.2 and then diminished with a high CSF. Moreover, it was closely fitted to a non-linear Gaussian peak pattern with a high regression value of 0.989. These results suggest that MSA and galactose, derived from marine red macro-algae, can potentially be applied for the conversion into platform chemicals.