Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and Na OH.Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells(WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid(IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20%(mass) Ni SO4aqueous solution at 130 ℃ and [Bmim]Cl at 150 ℃, the purity of a-chitin can be up to 96.5%(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

A facile ionic liquid approach to prepare cellulose fiber with good mechanical properties directly from corn stalks

It is very difficult to directly spin the lignocellulose without pretreatment.Ionic liquids(ILs)are promising solvent to dissolve lignocellulose to prepare cellulose fiber.However,the degree of cellulose polymerization(DP)is reduced when lignocellulose is dissolved in ILs,and the lignin removal rate is low.The elongation at break and tensile strength of the fibers obtained by spinning the lignocellulose dissolved in ILs are poor.In this paper,preparing cellulose fiber directly from lignocellulose based on dissolving corn stalk via[C4mim]Cl-L-arginine binary system is achieved.It shows that the removal rate of lignin can reach 92.35%and the purity of cellulose can reach 85.32%after corn stalk was dissolved at 150℃C for 11.5 h when the mass fraction of arginine is 2.5%.The elongation at break of fiber reached 10.12%and the tensile strength reached 420 MPa.It is mainly due to the fact that L-arginine not only inhibits the degradation of cellulose but also promotes the delignination.Without any pulping or pretreatment,preparing cellulose fibers via direct dissolution and extrusion may provide a simple and effective way to prepare many novel cellulose materials.

Solubility determination and thermodynamic modeling of bis-2-hydroxyethyl terephthalate(BHET)in different solvents

Studies on the degradation process of waste polyethylene terephthalate(PET)have become increasingly mature,but there are relatively few studies on the separation of degradation products.The products contain many components and the separation of which is difficult.Therefore,the study on phase equilibrium thermodynamics of bis-2-hydroxyethyl terephthalate(BHET)is of great theoretical significance and practical value to provide basic data for the BHET crystallization separation.In this work,the degraded products were purified and characterized.The solubility of BHET in methanol,ethanol,ethylene glycol,water and the mixture of ethylene glycol+water were determined by static method.The experimental results were correlated with different models,such as ideal solution(IS)model,λh equation,Apelblat equation and NRTL model.Based on the van’t Hoff equation,the mixing Gibbs energy,enthalpy and entropy were calculated.From this work,the basic data which can be used to guide the crystallization process of BHET were obtained,including solubility data,correlation model and thermodynamic properties.

Sub/supercritical carbon dioxide induced phase switching for the reaction and separation in ILs/methanol

Separation of products from ionic liquid(IL) solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone(GVL) by selective hydrogenation of α-angelica lactone(AL) and separation of the products from the IL solvent were carried out by using subcritical CO_2 as a "switch" at room temperature. After the mixture was separated into two phases by subcritical CO_2, AL and nano Pd/C catalyst were only found in the lower IL-rich phase, GVL was produced with quantitative yield and enriched in the upper methanolrich phase. Pure GVL can be obtained by depressurizing to release CO_2 and evaporation to remove methanol of the upper phase, the lower phase containing IL, catalyst and methanol can be recycled for the next reaction. The strategy may provide a new approach to produce and separate products from IL solvents at mild conditions.

Insight into the role of ethylene glycol on thermodynamics and nucleation kinetics of dimethyl terephthalate in mixed solvent system

Dissolution and nucleation are two essential processes for industrial crystallization.This paper in-vestigates the effect of ethylene glycol addition on the crystallization behavior of dimethyl terephthalate(DMT)in solution.The DMT solubility in mixed solvent system(methanol-ethylene glycol)was deter-mined by isothermal satiation approach,and the solubility was associated using seven models.The model fitting results were consistent with the experimental values.Based on the results,the metastable zone width(MSZW)of DMT was detected by the polythermal approach;the modified Sangwal's theory was used to investigate the nucleation behavior,which can provide a new way of thought for better analysis of the crystallization behavior.The results demonstrated that MSZW was associated with various elements,such as cooling rate,saturation temperature and mass fraction of ethylene glycol.The addition of ethylene glycol slowed down the nucleation rate as shown by the broadening of MSZW.We derive the solid-liquid interface energy,the nucleation driving force,the critical nucleation size and the critical Gibbs free energy according to the classical nucleation theory.It is demonstrated that the nucleation driving force and the solid-liquid interface energy are dependent and jointly influence the MSZW.

Study on ionic liquids based novel method for separation and purification of silkworm pupa protein

Silkworm pupa protein(SPP)that obtained by traditional method usually had a high fat content,which would impose restrictions on the further use of SPP.Herein,various functionalized ionic liquids(ILs)were used to extract SPP from silkworm pupae,the structure-performance relationship of ILs with their SPP separation performance were explored at the same time.The research showed that the maximum extraction yield of SPP was up to 62.6%with less than 0.5%low fat content by using 1-ethyl-3-methylimidazolium chloride([Emim]Cl),when the dissolution experiment was conducted at 90°C for 24 h with ethanol bath as the regeneration solvent.Comparing with the structure of raw material,the regenerated SPP maintained the native protein backbone.Meanwhile,all regenerated SPP showed a decreased crystallinity,which also exhibited decreased fraction of theα-helix comparing to thatβ-sheet united with coil random structures.

双咪唑阳离子乙酸锌低共熔溶剂催化醇解PET

本文设计合成了具有高热稳定性、多活性位点及低金属含量的双咪唑阳离子乙酸锌低共熔溶剂[C_(2)(Mim)_(2)][OAc]_(2)-2Zn(OAc)_(2),用于催化聚对苯二甲酸乙二醇酯(PET)的乙二醇(EG)醇解反应.通过红外光谱(FTIR)、核磁共振(NMR)和热重(TGA)表征分析了低共熔溶剂催化剂的结构和热稳定性.通过对催化反应参数进行优化发现,当催化剂的用量为PET质量的5%、PET:EG的质量比为1:4时,在190℃的条件下反应70 min后,PET转化率可达100%,对苯二甲酸双羟乙酯(BHET)的产率达85.2%.通过对比反应前后PET的扫描电子显微镜(SEM)图,并利用原位红外监测PET的EG醇解过程推测PET的降解过程,研究了PET的EG醇解反应动力学,结合双咪唑阳离子与乙酸锌和乙酸根与EG之间的氢键作用,推测出[C_(2)(Mim)_(2)][OAc]_(2)-2Zn(OAc)_(2)在EG中催化降解PET可能的反应机理.

Principles and strategies for green process engineering

The evolution of human civilization is becoming increasingly synchronized with the development of science and technology. Every step toward advancement achieved by humans showcases our creativity and ability to realize ideas in practice. However, due to human activities aimed at goal fulfillment, Mother Earth has undeniably undergone many irreversible changes, which in turn have negatively impacted the environment [1].

Frontiers of Ionic Liquids

Researchers around the globe are no strangers to the term“Ionic Liquids(ILs)”.With diverse applicability in chemistry,materials,chemical engineering,medicines,biochemistry to name a few,ILs are doing exactly what the researchers in the field predicted they will do,during the first international meeting devoted entirely to ILs research held on Greek grounds in Crete,back in April 2000:ILs are sustainable and decrease the environmental burden(e.g.reduce reliance on fossil fuel feedstock and replace them with renewable,increase energy efficiency,improved and/or new chemical and separation processes,etc.),while still being economically feasible in an industrial scale.

Highly efficient enzymolysis and fermentation of corn stalk into L-lactic acid by enzyme-bacteria friendly ionic liquid pretreatment

Ionic liquids(ILs)have been widely used in the pretreatment of biomass.However,the effects of residual ILs on the enzymolysis and fermentation of biomass are still unknown.Therefore,a large quantity of water-washing is usually followed after biomass pretreatment to eliminate the inhibition of residual ILs on subsequent hydrolysis and fermentation steps.In this work,the effect of choline glycine([Ch][Gly])concentration on the activity of cellulase and Bacillus sp.strain P38 was systematically investigated to explore the impacts of residual ILs on enzymolysis and fermentation.The results confirmed that the activities of them were almost not inhibited in low concentrations(less than 0.5 wt%)of[Ch][Gly].Under optimal pretreatment conditions,the maximum cellulose digestibility was 99.23%.Enzymatic hydrolysate was suitable for L-lactic acid fermentation without appreciable inhibition,and the highest sugar-acid conversion rate of 96.33%was obtained by simplified detoxification.This work provides an economic route to produce fermentable sugar and L-lactic acid,which shows an industrial application prospect in lignocellulosic biorefinery.