响应面法优化生物质基磁性固体酸催化玉米秸秆直接水解制备糠醛的研究
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摘要
以获取玉米秸秆水解制备糠醛的最佳工艺条件为目的,研究在有机溶剂甲苯的存在下,以生物质基磁性固体酸作为催化剂,玉米秸秆为原料,利用Design-Expert.V8.0.6.1中的Response Surface模块设计4因素(萃取剂用量、催化剂用量、水解温度、水解时间)3水平的Box-Behnken试验,通过分光光度法测定水解液中糠醛得率,确定生物质基磁性固体酸催化玉米秸秆直接水解制备糠醛的最佳工艺条件。结果表明,通过Box-Behnken试验数据建立的二次多项式数学模型的P=0.0003<0.01,失拟项P=0.001<0.01,达到极显著水平,校正决定系数R~2=0.9922,预测值与实验值具有很好的拟合度。通过二次回归模型得到生物质基磁性固体酸催化玉米秸秆直接水解制备糠醛的最佳工艺条件为:萃取剂用量25 mL,催化剂用量2.5 g(以1 g生物质原料为标准),水解温度158.8℃,水解时间4.1 h。在该条件下直接水解玉米秸秆所得糠醛得率为5.07%,预测值为5.08%,两者相差0.01%,模型拟合度好,重复性好;说明用此方法直接水解玉米秸秆制备糠醛是可行的。
To obtain the optical technology conditions of biomass-based solid acid directly catalyzed hydrolysis of corn straw to prepare furfural,the research in the presence of organic solvent of toluene,biomass-based magnetic solid acid as catalyst and corn straw as raw material,using the model of response surface in the Design-Expert. V8.0.6.1 to design Box-Behnken test of four factors(amount of extraction agent,amount of catalyst,hydrolysis temperature,hydrolysis time)three levels,the spectrophotometry mothed was used to determinate of furfural yield in purpose of determine the process conditions of biomass-based magnetic solid acid directly catalyzed hydrolysis of corn straw to prepare furfural.The results showed that it was highly significant(P=0.0003<0.01)that through the Box-Behnken experimental data to establish the quadratic regression mathematical model and lack of fit for P=0.01<0.01,reached extremely significant level,which the coefficient of correlation was R~2=0.9922,the degree of fetting was provided with between the predicted values and experimental. The optical technology conditions of biomass-based magnetic solid acid directly catalyzed hydrolysis of corn straw to prepare furfural were provided inverse matrix of quadratic regression mathematics model,which was by following:amount of extraction agent was 25 mL,amount of catalyst was 2.5 g(1 g biomass raw materials as the standard),the hydrolysis temperature was 158.8 ℃,the hydrolysis time was 4.1 h. Under the condition of the directly hydrolysis corn straw from furfural yield was 5.07%,while the predictive value was 5.08%,which the relative deviation between them was 0.01%,this model is good and good repeatability. This shows that using this model to optimize the technology of biomass-based magnetic solid acid directly hydrolysis of corn stalk to prepare of furfural is feasible.
To obtain the optical technology conditions of biomass-based solid acid directly catalyzed hydrolysis of corn straw to prepare furfural,the research in the presence of organic solvent of toluene,biomass-based magnetic solid acid as catalyst and corn straw as raw material,using the model of response surface in the Design-Expert. V8.0.6.1 to design Box-Behnken test of four factors(amount of extraction agent,amount of catalyst,hydrolysis temperature,hydrolysis time)three levels,the spectrophotometry mothed was used to determinate of furfural yield in purpose of determine the process conditions of biomass-based magnetic solid acid directly catalyzed hydrolysis of corn straw to prepare furfural.The results showed that it was highly significant(P=0.0003<0.01)that through the Box-Behnken experimental data to establish the quadratic regression mathematical model and lack of fit for P=0.01<0.01,reached extremely significant level,which the coefficient of correlation was R~2=0.9922,the degree of fetting was provided with between the predicted values and experimental. The optical technology conditions of biomass-based magnetic solid acid directly catalyzed hydrolysis of corn straw to prepare furfural were provided inverse matrix of quadratic regression mathematics model,which was by following:amount of extraction agent was 25 mL,amount of catalyst was 2.5 g(1 g biomass raw materials as the standard),the hydrolysis temperature was 158.8 ℃,the hydrolysis time was 4.1 h. Under the condition of the directly hydrolysis corn straw from furfural yield was 5.07%,while the predictive value was 5.08%,which the relative deviation between them was 0.01%,this model is good and good repeatability. This shows that using this model to optimize the technology of biomass-based magnetic solid acid directly hydrolysis of corn stalk to prepare of furfural is feasible.
引文
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[14]任素霞,徐海燕,雷廷宙,等.稻壳水解制备糠醛的工艺条件研究[J].太阳能学报,2012,33(6):893-898.[14]Ren Suxia,Xu Haiyan,Lei Tingzhou,et al.Stuudy on production of furfural from rice husk[J].Acta Energiae Solaris Sinica,2012,33(6):893-898.
[2]Chen Jinzhu,Zhao Guoying,Chen Limin.Efficient production of 5-hydroxymethyl furfural and alkyl levulinate from biomass carbohydrate using ionic liquidbased polyoxometalate salts[J].RSC Advances,2014,4(8):4194.
[3]Audemar M,Ciotonea C,Vigier K O,et al.Selective hydrogenation of furfural to furfuryl alcohol in the presence of a recyclable cobalt/SBA-15 catalyst[J].ChemSusChem,2015,8(11):1987-1987.
[4]Wang Ronggeng.Development of furfural series products[J].Fine Chemical Raw Material and Intermediates,2003,(12):20-26.
[5]Frias J A D,Feng H.Pretreatment of furfural residues with switchable butadiene sulfone in the sugarcane bagasse biorefinery[J].Green Chemistry,2014,16(5):2779-2787.
[6]李凭力,肖文平,常贺英,等.糠醛生产工艺的发展[J].林产工业,2006,33(2):13-16.[6]Li Pingli,Xiao Wanping,Chang Heying,et al.Development of furfural production processes[J].China Forest Products Industry,2006,33(2):13-16.
[7]李志松.糠醛生产工艺研究综述[J].广东化工,2010,37(3):40-41.[7]Li Zhisong.A review of the study on furfural production process[J].Guangdong Chemical Industry,2010,37(3):40-41.
[8]Yin Yanfei,Fang Guigan,Shi Yingqiao,et al.Prduction and application of furfural from biomass[J].Biomass Chemical Engineering,2011,45(1):53-56.
[9]赵志福.常压两步法生产糠醛工艺条件研究[D].天津:天津大学,2009.[9]Zhao Zhufu.Study on the two-step process furfural production at atmospheric pressure[D].Tianjin:Tianjin University,2009.
[10]徐燏,肖传豪,于英慧.糠醛生产工艺技术及展望[J].濮阳职业技术学院学报,2010,23(4):150-152.[10]Xu Yu,Xiao Chuanhao,Yu Yinghui.Production technology of furfural and prospect[J].Journal of Puyang Vocational and Technical College,2010,23(4):150-152.
[11]荣春光.糠醛生产工艺研究及糠醛废渣的综合利用[D].长春:吉林大学,2012[11]Rong Chunguang.Studies on preparation of furfural and comprehensive utilization of furfural residue[D].Changchun:Jilin University,2012.
[12]Li Xueqin,Li Xiangyu,Wei Qi,et al.Preparation of magnetic biomass-based solid acid catalyst and effective catalytic conversion of cellulose into high yields of reducing sugar[J].Bioresources,2015,10(4):6720-6729.
[13]岳丽清.添加剂在玉米芯水解制备糠醛中的应用[D].郑州:河南工业大学,2012.[13]Yue Liqing.Application of additives in the preparation of furfural by hydrolysisi of corncobs[D].Zhengzhou:Henan University of Technology,2012.
[14]任素霞,徐海燕,雷廷宙,等.稻壳水解制备糠醛的工艺条件研究[J].太阳能学报,2012,33(6):893-898.[14]Ren Suxia,Xu Haiyan,Lei Tingzhou,et al.Stuudy on production of furfural from rice husk[J].Acta Energiae Solaris Sinica,2012,33(6):893-898.