(377u) Green and Sustainable Chromatographic Separation Strategy for Levulinic Acid from Biomass Hydrolysate | AIChE

(377u) Green and Sustainable Chromatographic Separation Strategy for Levulinic Acid from Biomass Hydrolysate

Authors 

Lin, X. - Presenter, Guangdong University of Technology
Zhang, K., Guangdong University of Technology
Zheng, J., Guangdong University of Technology
Liu, Y., Guangdong University of Technology
Zheng, X., Guangdong University of Technology
Xiao, J., Guangdong University of Technology
He, X., Guangdong University of Technology
Levulinic acid (LA) is a promising and versatile biorefinery platform chemical, which can be used to synthesize a broad range of desirable chemicals and fuel additives. To date, an enormous amount of patents and research articles have been devoted to manufacturing LA from biomass by using mineral acids, solid acids, or metal chlorides as catalysts. Unfortunately, in these catalytic transformations, LA released from biomass hydrolysate is accompanied by formic acid (FA) and 5-hydroxymethylfurfural (5-HMF). How to economically, safely, and efficiently separation of LA remain difficult challenge from the viewpoint of industrial application.

In this work, a novel amide group modified mic/mesoporous hyper-cross-linked resin, SY-01, was prepared using suspension polymerization of 2-hydroxyethyl acrylate (2-HEA), styrene (St) and divinylbenzene (DVB), followed by a Friedel–Crafts reaction and an amination reaction. The physicochemical properties of the SY-01 resin were characterized by scanning electron microscope (SEM), Fourier transform infrared (FT-IR) spectroscopy, Element analysis (EA) and nitrogen adsorption-desorption isotherms. The results show that the specific surface area of the resin is as high as 1334 m2/ g, and the microporous ratio and mesoporous ratio are 74.6 % and 9.48 %, respectively. Batch adsorption experiments showed that the affinity of SY-01 resin toward FA−LA−5-HMF were in the order of 5-HMF > LA > FA under noncompetitive and competitive systems. The highest adsorption capacity were 7.54 mg/g wet resin for FA, 103.51 mg/g wet resin for LA, and 107.73 mg/g wet resin for 5-HMF. The obtained thermodynamic parameters suggested that the adsorption of LA on SY-01 was spontaneous (ΔG0<3.788 kJ/mol), and exothermic (ΔH0 =-11.764 kJ/mol). For kinetic study, the adsorption of LA onto SY-01 resin at various operating conditions follows the pore diffusion model and the intraparticle diffusion is the rate-limiting step for the adsorption of LA onto SY-01 resin. More importantly, mesoporous formation accelerates the adsorption / desorption diffusion of LA in the resin. The effective pore diffusivity was dependent upon temperature, but independent of initial LA concentration, and were 3.306 ×10-10, 5.274 ×10-10 and 7.707 ×10-10 m2/s at 298, 318 and 338 K, respectively. In desorption process, the recovery efficiency of LA from SY-01 resin was 99.39% owing to the lower hydrogen bond energy as well as the reversibility of the hydrogen bond. Furthermore, a mathematical model based on the general rate model coupled with the noncompetitive single component and competitive multicomponent Langmuir isotherm was successfully developed to simulate the breakthrough curves of FA−LA−5-HMF from single, binary, as well as ternary-component mixtures. The proposed methodology for fixed-bed column multicomponent competitive adsorption model can be successfully implemented to completely design the separation unit of LA from aqueous solution or biomass hydrolysate. In summary, this work effectively solves the problems that the activated carbon can not be reused in the traditional adsorption and separation technology and that the ion exchange resin consumes a lot of acid, alkali and water in the process of elution and regeneration, reduces the environmental pollution and promotes the construction of beautiful countryside.