Energy-Efficient Production of 1-Octanol from Biomass- Derived
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Green Chemistry Energy -efficient production of 1 -octanol from biomass - derived furfural-acetone in water Journal: Green Chemistry Manuscript ID: GC-ART-05-2015-001119.R2 Article Type: Paper Date Submitted by the Author: 01-Jul-2015 Complete List of Authors: Xia, Qineng; East China University of Science and Technology, Research Institute of Industrial Catalysis Xia, Yinjiang; East China University of Science and Technology, Research Institute of Industrial Catalysis Xi, Jinxu; East China University of Science and Technology, ; East China University of Science and Technology, Research Institute of Industrial Catalysis Liu, Xiaohui; East China University of Science and Technology, Wang, Yanqin; East China University of Science and Technology, Chemistry Please do not adjust margins Page 1 of 8 Green Chemistry Green Chemistry ARTICLE Energy-efficient production of 1-octanol from biomass-derived furfural-acetone in water † Received 00th January 20xx, Accepted 00th January 20xx Qineng Xia, Yinjiang Xia, Jinxu Xi, Xiaohui Liu and Yanqin Wang* DOI: 10.1039/x0xx00000x An energy-efficient catalytic system for the one-pot production of 1-octanol from biomass-derived furfural-acetone (FFA) under mild conditions in water was developed, by sequential hydrogenation/hydrogenolysis over a hydrophilic Pd/NbOPO 4 www.rsc.org/ catalyst. A strategy of creating an intentional “phase problem” has been employed to prevent the over hydrogenolysis of 1-octanol into n-octane and therefore increased the selectivity to 1-octanol. The effects of reaction conditions as well as a variety of noble-metal loaded bifunctional catalysts have been systematically investigated to maximize the yield of 1- octanol. Moreover, the addition of liquid acids to the catalytic system further enhanced the selectivity towards the formation of 1-octanol. There is a strong correlation between the acid strength of acidic additive and sum yield of 1- octanol and octane. With the addition of TfOH, a highest yield of 1-octanol (62.7%) was obtained from one-pot conversion of biomass-derived FFA over Pd/NbOPO 4. furfural to FFA by aldol condensation in the presence of excess Introduction acetone. After evaporation of acetone, neat FFA was then hydrogenated into 4-(2-tetrahydrofuryl)-2-butanol (THFA) over Biomass has been considered as a promising alternative to Ru/C under 120 oC and 120 bar H pressure. Finally, 1-octanol petroleum resources and extensive efforts have been made 2 and dioctyl ether were obtained by selective deoxygenation and worldwide to convert renewable biomass into fuels and value- 1-4 ring opening over Ru/C in [EMIM][NTf2] with acidic additive added chemicals. Lignocellulose is the most abundant [BSO3BIM][NTf2] under 150 oC and 120 bar H pressure. 30 biomass resources on earth which consists of cellulose, 2 5 The strategy of synthesis 1-octanol from biomass-derived hemicellulose and lignin. In lignocellulose conversion, 5- platforms with retrosynthetic analysis concept was creative. hydroxymethylfurfural (HMF) and furfural are two extremely However, the process could be further improved if a more eco- important biomass platform chemicals, which are typically friendly solvent and a more efficient catalytic system was produced by acid-catalyzed dehydration of fructose and xylose 6-10 employed. respectively. So far, a great number of strategies and More recently, we reported that n-octane can be produced approaches have been put forward to convert furfural directly from FFA with yields higher than 90% under mild compounds into the downstream value-added products, such as 11-14 15-17 18-20 21, conditions in cyclohexane over multifunctional niobium methylfurans, long-chain alkanes, diols and acids. 31 22 phosphate supported Pd catalyst. The proposed reaction In recent studies, furfural-acetone (FFA, C8) was produced pathway showed that 1-octanol had been produced before it by the aldol condensation of furfural with acetone and was used 15,16,23-25 was finally converted into n-octane. From this point of view, if as platform molecule for gasoline-fuel synthesis. It is the catalyst or the reaction condition was properly modified to noted that acetone is also available from renewable biomass prevent 1-octanol finally going to n-octane, the one-pot through acetone-butanol fermentation and can be regarded as a 26,27 efficient production of 1-octanol from FFA could be envisaged. biomass-derived chemical. In literature, NbOPO has been extensively studied as a water- 1-Octanol is a particularly attractive industry product widely 4 tolerant solid acid and has been applied in dehydration, 32-34 used in detergents, surfactants and fragrances production as 35,36 37 28 hydrolysis and esterification . It also possesses strong well as chemical synthesis. It also serves as an important 38 29 hydrophilic character due to its large metal size. Therefore, if solvent in biomass conversion. Currently, 1-octanol is mainly 28 water was used as a solvent for the production of 1-octanol produced from petroleum-based process. Recently, Julis and 30 from FFA using hydrophilic Pd/NbOPO as catalyst, it would Leitner reported for the first time that 1-octanol could be 4 actually cause a man-made “phase problem” to prevent the synthesized from furfural and acetone. They first converted over-hydrogenolysis of 1-octanol, because 1-octanol would separate spontaneously from water phase once it was generated Key Lab for Advanced Materials, Research Institute of Industrial Catalysis, East owing to their immiscibility, while hydrophilic Pd/NbOPO 4 China University of Science and Technology, # 130, Meilong Road, Shanghai, 200237, P. R. China. E-mail: [email protected] would stay in aqueous phase throughout the reaction, which † Electronic Supplementary Information (ESI) available. See will separate with 1-octanol. DOI: 10.1039/x0xx00000x This journal is © The Royal Society of Chemistry 20xx Green Chem ., 2013, 00 , 1-3 | 1 Please do not adjust margins Please do not adjust margins Green Chemistry Page 2 of 8 ARTICLE Green Chemistry Catalyst characterizations The N2 adsorption/desorption isotherm of NbOPO 4, X-ray diffraction (XRD) pattern, X-ray photoelectron spectroscopy (XPS) pattern and transmission electron microscopy (TEM) image of Pd/NbOPO 4 are provided in supporting information. The NH 3-TPD was carried out in an apparatus (PX200, Tianjin Golden Eagle Technology Co. Ltd.) equipped with a thermal conductivity detector (TCD). The samples (100 mg) Scheme 1 one-pot production of 1-octanol from biomass-derived were loaded into a U-shaped quartz tube. Prior to TPD FFA over Pd/NbOPO in water . 4 measurements, the samples were pretreated in flowing N 2 (45 -1 ml·min ) for 1 h at 500 °C, and then cooled to 50 °C. NH 3 was Herein, we describe an energy-efficient catalytic system for adsorbed onto the samples by exposure to flowing 10% NH 3 in -1 the one-pot production of 1-octanol from biomass-derived FFA, N2 gas mixture (50 ml·min ) for 45 min at 50 °C. Residual and using hydrophilic Pd/NbOPO as catalyst and water as a physical adsorbed NH 3 was removed by purging the samples 4 -1 solvent, as shown in Scheme 1. The over-hydrogenolysis of 1- with flowing N 2 (45 ml·min ) at 90 °C for 1 h. Desorption of octanol to n-octane can be largely avoided and 1-octanol can be NH 3 was performed by heating the samples at a rate of 10 -1 -1 easily separated from water after being produced, which makes °C·min under flowing N 2 (45 ml·min ) from 90 °C to 550 °C. this catalytic system much more energy-efficient for the industrial production. Moreover, strong acidity is found to be in Catalytic reaction and product analysis favor of the cleavage of secondary C-O bond compare to The one-pot production of 1-octanol from FFA was carried primary C-O bond, which can be attributed to the greater out in a 50 mL Teflon-lined stainless-steel autoclave. Typically, stability of secondary carbenium ion structures than primary 0.2 g of FFA, 0.1 g of Pd/NbOPO 4 and 4 g of water were put 39 carbenium ion structures in water. Therefore, liquid acids into the autoclave. The reaction was hydrogenated at room were added to further increase the system acidity, which temperature and 2.5 MPa H 2 pressure for 3h first to saturate enhance the selectivity of secondary C-O bond cleavage, FFA and then reacted at elevated temperature (e.g., 190 °C) for leading to the primary alcohol formation. With the addition of another 18 h. After the reaction, the reactor was quenched in an TfOH, a highest yield of 1-octanol (62.7%) was obtained from ice/water bath. The products in liquid phase were extracted by 4 one-pot conversion of biomass-derived FFA over a hydrophilic mL of cyclohexane and both organic phase and aqueous phase Pd/NbOPO 4 catalyst. were analyzed by GC (Agilent 7890) equipped with an HP-5 column and an FID detector using internal standard method. The yields of products were calculated by using the equation: Experimental section yield [%] = (mol of carbon in product)/(mol of carbon in Chemicals reactant)×100%. Pt(NO 3)2·xH 2O and Pd(NO 3)2·xH 2O were purchased from Heraeus Materials Technology Shanghai Ltd. (Shanghai, Results and discussion China). RuCl 3·3H 2O was purchased from Aladdin Reagent Co., Reaction pathway and practicability study Ltd. (Shanghai, China). γ-Al 2O3 and H-Beta were purchased from Nankai University Catalyst Co., Ltd. (Tianjin, China). All We have investigated the reaction pathway of one-pot other chemicals were purchased from Sinopharm Chemical conversion of FFA to n-octane in cyclohexane over Reagent Co., Ltd. (Shanghai, China). All purchased chemicals multifunctional Pd/NbOPO 4 catalyst, and found 1-octanol had were of analytical grade and used without further purification.