离子交换法分离乙酰丙酸的实验研究
摘要
乙酰丙酸是生物质资源直接水解的重要产物，可以用可再生资源大规模制备。廉价的乙酰丙酸有望成为一种基于生物质资源的新型平台化合物，用来制备各种具有价值的衍生物产品。
本文主要是研究用离子交换法从纤维素水解液中提取乙酰丙酸的工艺流程，制备乙酰丙酸纯品，并为大规模生产运行提供可靠的工艺参数。
本文通过将多种树脂对乙酰丙酸，甲酸及硫酸的离子交换吸附容量进行比较，选取D301弱碱性阴离子交换树脂作为吸附材料，对其吸附、洗脱过程进行了系统研究。
首先，以D301树脂为离子交换材料，以纯的乙酰丙酸溶液为研究对象，静态实验主要研究了吸附的热力学和动力学过程。热力学过程主要研究了吸附等温线，得到吸附过程为优惠型吸附，等温线方程符合R-P经验式吸附等温方程，计算得到离子交换过程的吸附焓变；间歇式动力学主要考察了树脂颗粒直径，搅拌速度，溶液浓度及体系温度对离子交换过程的影响，并用移动边界模型对实验数据进行了处理，通过研究可知，搅拌速率对离子交换过程没有较大影响，吸附速率随乙酰丙酸初始浓度的增加而升高，离子交换过程为颗粒扩散控制，计算得到离子交换过程的表观速率常数，反应级数以及表观活化能，并得到反应的总的动力学方程；动态实验主要研究了交换柱的吸附和洗脱过程，并在上柱液浓度、流量、离子交换柱高度等因素的优化实验基础上设计了离子交换柱参数。选定盐酸为洗脱剂，研究了盐酸浓度和流量因素对洗脱效果的影响。
其次，以D301树脂为离子交换材料，小麦秸秆经稀硫酸水解产生的乙酰丙酸溶液为研究对象，进行动态实验的研究，考察了离子交换柱的吸附和洗脱过程。确定了吸附与洗脱条件。吸附条件：离子交换柱高径比15.5，流速为1BV／h的穿透条件下，树脂的利用率为84.6％；洗脱条件：0.5mol／l的HCl在1BV／h的条件下洗脱；最终得到乙酰丙酸的收率为77.9％，纯度为92.3％。
用上述方法生产乙酰丙酸过程简单，对设备要求不高，生产成本低，适合大规模工业化生产的要求。
Levulinic acid (LA) can be prepared from biomass with large scale. Low cost LA can be used as a platform chemical for the production of a wide range of value-added products.
This paper deals with an economical, effective ion exchange method to recover levulinic acid from the hydrolyzed cellulose, provides process parameters for mass production.
In this paper, D301 alkalescence anion exchange resin was selected as a suitable adsorptive material based on the study of ion exchange capacities. The kinetics and thermodynamics behaviors of ion exchanging were studied by static method.
Firstly, the adsorption of LA by D301 alkalescence anion exchange resin was studied with the static method and the dynamic method. And the thermodynamics and kinetics behaviors of ion exchanging were studied by static method.
In the thermodynamics, the adsorption behavior of resin under different temperature was discussed. The results show that the ion exchange is a favorable and spontaneous adsorption process, and the adsorption isotherm data can be satisfactorily fitted with the Redliclr-Peterson equation. Heat adsorption (ΔH) of resin D301 was also gained.
In the kinetics, under optional reaction system, the influence on the ion exchange process including the granularities of resin, concentration of LA, speeds of stirring and temperature were investigated by batch ion-exchange method. Moving Boundary Model was applied to describe the kinetics of exchange process. The results show that the dominant procedure is ion diffusion through particles. The influence of stirring speed and temperature on the adsorption is little, the adsorption rate increases with the raise of primary concentration of LA. The rate constant of exchange (k_0), reaction order (n), the apparent activation energy reaction (Ea) and the total kinetics equation were obtained finally.
The adsorptive process in ion exchange column was studied by dynamic method. We researched the dynamic absorbing and eluting process of pure LA solution with resin D301, and the influence of different factors such as LA concentration, flow rate and resin bed height on absorption were determined. Moreover, the HCl was used as eluting solution in dynamic eluting process, and the influence of HCl concentration and the flow rate on elution were also investigated.
Secondly, levulinic acid (LA) can be prepared from the hydrolyzed cellulose with large scale. The adsorbing and eluting process were also studied by dynamic method. Under the condition of H:D 15.5, flow rate 1BV/h, the utilized rate of resin in absorbing process is 84.6%. Furthermore, LA with the purity 92.3% can be obtained by using 0.5M HCl as eluting solution with 1BV/h, and the yield of LA can reach to 77.9%.
Generally, the process for LA recovery is simple. The demands for equipment and the cost of production are low, and it is suitable for the industrialization with large scale.
本文主要是研究用离子交换法从纤维素水解液中提取乙酰丙酸的工艺流程，制备乙酰丙酸纯品，并为大规模生产运行提供可靠的工艺参数。
本文通过将多种树脂对乙酰丙酸，甲酸及硫酸的离子交换吸附容量进行比较，选取D301弱碱性阴离子交换树脂作为吸附材料，对其吸附、洗脱过程进行了系统研究。
首先，以D301树脂为离子交换材料，以纯的乙酰丙酸溶液为研究对象，静态实验主要研究了吸附的热力学和动力学过程。热力学过程主要研究了吸附等温线，得到吸附过程为优惠型吸附，等温线方程符合R-P经验式吸附等温方程，计算得到离子交换过程的吸附焓变；间歇式动力学主要考察了树脂颗粒直径，搅拌速度，溶液浓度及体系温度对离子交换过程的影响，并用移动边界模型对实验数据进行了处理，通过研究可知，搅拌速率对离子交换过程没有较大影响，吸附速率随乙酰丙酸初始浓度的增加而升高，离子交换过程为颗粒扩散控制，计算得到离子交换过程的表观速率常数，反应级数以及表观活化能，并得到反应的总的动力学方程；动态实验主要研究了交换柱的吸附和洗脱过程，并在上柱液浓度、流量、离子交换柱高度等因素的优化实验基础上设计了离子交换柱参数。选定盐酸为洗脱剂，研究了盐酸浓度和流量因素对洗脱效果的影响。
其次，以D301树脂为离子交换材料，小麦秸秆经稀硫酸水解产生的乙酰丙酸溶液为研究对象，进行动态实验的研究，考察了离子交换柱的吸附和洗脱过程。确定了吸附与洗脱条件。吸附条件：离子交换柱高径比15.5，流速为1BV／h的穿透条件下，树脂的利用率为84.6％；洗脱条件：0.5mol／l的HCl在1BV／h的条件下洗脱；最终得到乙酰丙酸的收率为77.9％，纯度为92.3％。
用上述方法生产乙酰丙酸过程简单，对设备要求不高，生产成本低，适合大规模工业化生产的要求。
Levulinic acid (LA) can be prepared from biomass with large scale. Low cost LA can be used as a platform chemical for the production of a wide range of value-added products.
This paper deals with an economical, effective ion exchange method to recover levulinic acid from the hydrolyzed cellulose, provides process parameters for mass production.
In this paper, D301 alkalescence anion exchange resin was selected as a suitable adsorptive material based on the study of ion exchange capacities. The kinetics and thermodynamics behaviors of ion exchanging were studied by static method.
Firstly, the adsorption of LA by D301 alkalescence anion exchange resin was studied with the static method and the dynamic method. And the thermodynamics and kinetics behaviors of ion exchanging were studied by static method.
In the thermodynamics, the adsorption behavior of resin under different temperature was discussed. The results show that the ion exchange is a favorable and spontaneous adsorption process, and the adsorption isotherm data can be satisfactorily fitted with the Redliclr-Peterson equation. Heat adsorption (ΔH) of resin D301 was also gained.
In the kinetics, under optional reaction system, the influence on the ion exchange process including the granularities of resin, concentration of LA, speeds of stirring and temperature were investigated by batch ion-exchange method. Moving Boundary Model was applied to describe the kinetics of exchange process. The results show that the dominant procedure is ion diffusion through particles. The influence of stirring speed and temperature on the adsorption is little, the adsorption rate increases with the raise of primary concentration of LA. The rate constant of exchange (k_0), reaction order (n), the apparent activation energy reaction (Ea) and the total kinetics equation were obtained finally.
The adsorptive process in ion exchange column was studied by dynamic method. We researched the dynamic absorbing and eluting process of pure LA solution with resin D301, and the influence of different factors such as LA concentration, flow rate and resin bed height on absorption were determined. Moreover, the HCl was used as eluting solution in dynamic eluting process, and the influence of HCl concentration and the flow rate on elution were also investigated.
Secondly, levulinic acid (LA) can be prepared from the hydrolyzed cellulose with large scale. The adsorbing and eluting process were also studied by dynamic method. Under the condition of H:D 15.5, flow rate 1BV/h, the utilized rate of resin in absorbing process is 84.6%. Furthermore, LA with the purity 92.3% can be obtained by using 0.5M HCl as eluting solution with 1BV/h, and the yield of LA can reach to 77.9%.
Generally, the process for LA recovery is simple. The demands for equipment and the cost of production are low, and it is suitable for the industrialization with large scale.
引文
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[4] Cuvelier, J. M. Ion exchange resins used in the food industry and in the drinking water preparation in Europe. Reactive Polymers, 1995, 24(2): 109-116.
[5] Lopez. F. Ion-exchange processes in the food industry. Environmental Protection Engineering, 1999, 25(12): 103-110.
[6] Graf, H. Rabaud, J. N. Eglyet al. Ion exchange resins for the purification of monoclonal antibodies from animal cell culture. Bioseparation, 1994, 4(1): 7-20.
[7] Leinonen, Heikki, Lehtoet al. Purification of nickel and zinc from waste waters of metal-plating plants by ion exchange. Reactive Polymers, 1994, 23(2, 3): 221-228.
[8] Jangbarwala, Juzer. Ion exchange resins for metal finishing wastes. Metal Finishing, 1997, 95(11): 33-34.
[9] 钱庭宝．离子交换剂应用技术 (第Ⅰ版)．天津科学技术出版社．1984，7．
[10] 《化学工程手册》编辑委员会．化学工程手册．化学工业出版社．1985，103．
[11] 马荣骏．离子交换在湿法冶金中的应用．冶金工业出版社．1991，78．
[12] 姜志新，谌竞清，宋正孝．离子交换分离工程．天津大学出版社．1992，77-79．
[13] 曾祥群，张志民．氨基酸提取工艺研究．发酵科技通讯．2001，30(1)：22-24．
[14] 龙万凯．我国赖氨酸工业技术新进展．化学工程．2003，31(5)：76-78．
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