Co-reporter:Chuang Li, Guangyue Xu, Xiaohao Liu, Ying Zhang, and Yao Fu
Industrial & Engineering Chemistry Research August 9, 2017 Volume 56(Issue 31) pp:8843-8843
Publication Date(Web):July 17, 2017
DOI:10.1021/acs.iecr.7b02046
Tetrahydrofurfuryl alcohol (THFAL), as a green industrial solvent, can be obtained directly from biomass-derived furfural with 100% conversion and 100% yield over a hydroxyapatite-supported Pd catalyst (Pd-HAP) under relatively mild conditions (40 °C, 1 MPa H2, and 3 h) in 2-propanol. At room temperature and reacting for 8 h, the yield of THFAL was more than 99%. By capturing the intermediates, two pathways were proposed as follows: (1) Furfural was partially hydrogenated to furfuryl alcohol, and then, furfuryl alcohol was further hydrogenated to THFAL. (2) Furfural and 2-propanol first formed 2-(isopropoxymethyl)furan (2-IPMF) via etherification, and then, 2-IPMF was ultimately converted to THFAL. The Pd-HAP catalyst was characterized by various techniques including XRD, SEM, TEM, HAADF-STEM, XPS, and ICP-AAS. The results revealed that the outstanding catalytic performance of Pd-HAP was attributed to the quasicoordination effect between Pd and HAP, which not only contributed to highly dispersed and stable Pd nanoclusters but also led to better activation of hydrogen. The recyclability of the Pd-HAP catalyst was also investigated and proved its stability in the conversion of furfural and high selectivity toward THFAL.
Co-reporter:Yongxiang Zhai;Chuang Li;Guangyue Xu;Yanfu Ma;Xiaohao Liu
Green Chemistry (1999-Present) 2017 vol. 19(Issue 8) pp:1895-1903
Publication Date(Web):2017/04/20
DOI:10.1039/C7GC00149E
Lignin primarily composed of methoxylated phenylpropanoid subunits is an abundant biomass that can be used to produce aromatics. Herein, a series of non-precious bimetallic Ni–Fe/AC catalysts were prepared for efficiently depolymerizing lignin. When organosolv birch lignin was used to determine the efficiency of the catalysts in methanol solvent, the Ni1–Fe1/AC (the ratio of Ni and Fe was 1 : 1) achieved the highest total yield of monomers (23.2 wt%, mainly propylguaiacol and propylsyringol) at 225 °C under 2 MPa H2 for 6 h. From GPC analysis, it is also proved that lignin was efficiently depolymerized. The Ni–Fe alloy structure was formed according to XRD, HRTEM, H2-TPR and XPS characterization. Based on the model compounds’ tests, the Ni1–Fe1/AC catalyst showed high efficiency in ether bond cleavage without hydrogenation of aromatic rings which could be attributed to the synergistic effect of Ni and Fe on the alloy structure. The total yield of monomers by using the Ni1–Fe1/AC catalyst reached 39.5 wt% (88% selectivity to PG and PS) when birch wood sawdust was used as the substrate.
Co-reporter:Qian Yao, Lujiang Xu, Chaofang Guo, Ziguo Yuan, Ying Zhang, Yao Fu
Journal of Analytical and Applied Pyrolysis 2017 Volume 124(Volume 124) pp:
Publication Date(Web):1 March 2017
DOI:10.1016/j.jaap.2017.03.004
•Cellulose was selectively converted into pyrroles via CFP process in NH3.•Different factors on the product distribution were investigated systematically.•9.7% yield of N-containing chemicals was achieved over γ-Al2O3 catalyst at 400 °C.•The selectivity of pyrroles in N-containing chemicals reached at 89.5%.•The possible conversion pathway from cellulose to pyrroles was proposed.In this study, cellulose was selectively converted into pyrroles via catalytic fast pyrolysis under ammonia atmosphere over the γ-Al2O3 catalyst. Both in situ and ex situ lab-scale fast pyrolysis sets were designed and used for investigation, and more pyrroles were produced via in situ CFP process. In addition, the effects of catalyst, reaction temperature and catalyst-to-cellulose ratio on the product distribution were investigated systematically. All these factors played important roles in the production of pyrroles. Under the optimized in situ CFP condition, at 400 °C and catalyst-to-cellulose ratio at 2, the carbon yield of N-containing chemicals from cellulose under ammonia atmosphere reached 9.7%. The selectivity of pyrroles in N-containing chemicals was 89.5%. The possible conversion pathway from cellulose to pyrroles was also proposed, that is, cellulose was firstly converted into anhydrosugars through thermal decomposition, then anhydrosugars underwent dehydration and rearrangement reactions to form furans. Thereafter, the furans were transformed into pyrroles by reacting with ammonia.Download high-res image (121KB)Download full-size image
Co-reporter:Chuang Li, Guangyue Xu, Yongxiang Zhai, Xiaohao Liu, Yanfu Ma, Ying Zhang
Fuel 2017 Volume 203(Volume 203) pp:
Publication Date(Web):1 September 2017
DOI:10.1016/j.fuel.2017.04.082
•Bimetallic Ni-Fe/AC catalysts with different Fe/Ni ratios are prepared.•Ni-Fe/AC catalysts are efficient for catalyzing EL to GVL under mild conditions.•The catalysts are characterized by XRD, TEM, HRTEM, EDX, XPS, H2-TPR and NH3-TPD.•Ni-Fe alloy and co-presented FeOx contribute to the high catalytic activity.•The Ni-Fe/AC catalysts can be easily separated due to their strong magnet.Gamma-valerolactone (GVL) has been identified as a sustainable high-value platform molecular for the production of fuels and carbon-based chemicals. In this work, a series of activated carbon supported low-cost bimetallic Ni-Fe catalysts (Ni-Fe/AC) with different molar content of Fe species were prepared by using co-precipitation method for the liquid phase hydrogenation of ethyl levulinate (EL) to produce γ-valerolactone. The Ni-Fe0.5/AC exhibited the highest activity among the bimetallic or monometallic catalysts under mild reaction conditions (100 °C, 4 MPa H2, 6 h) and achieved 99.3% conversion of EL and 99.0% yield of GVL. Under more mild conditions (60 °C, 2 MPa H2) and prolonging the reaction time to 24 h, EL could be converted completely and the obtained GVL yield was more than 98%. The catalysts were characterized by various techniques including XRD, TEM, HRTEM, EDX, XPS, H2-TPR and NH3-TPD. Based on the structure and activity relationship study, the formation of highly dispersed Ni-Fe alloy structure and the co-presented FeOx nanoparticles could be responsible for the high catalytic hydrogenation activity.Download high-res image (166KB)Download full-size image
Co-reporter:Xiaohao Liu, Lujiang Xu, Guangyue Xu, Wenda Jia, Yanfu Ma, and Ying Zhang
ACS Catalysis 2016 Volume 6(Issue 11) pp:7611
Publication Date(Web):October 3, 2016
DOI:10.1021/acscatal.6b01785
The hydrodeoxygenation (HDO) of lignin-derived phenols is important to produce the renewable biofuels. Herein, we reported a simple method to prepare magnetic nitrogen-doped carbon supported cobalt nitride catalysts (CoNx@NC) by copyrolysis of cellulose and cobalt nitrate under ammonia atmosphere. The catalysts were prepared at different temperatures and characterized by elemental analysis, atomic absorption spectroscopy (AAS), Brunauer–Emmett–Teller (BET) surface area analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and temperature-programmed reduction (TPR). The CoNx@NC-650 (pyrolyzed at 650 °C) exhibited the best HDO activity for eugenol conversion among a series of Co-based catalysts. The yield of propylcyclohexanol from eugenol was >99.9% under 2 MPa H2 at 200 °C for 2 h. Moreover, a high yield of propylcyclohexane (99.1%) could be achieved when the solid acid HZSM-5 was added to the reaction system. Other lignin-derived phenolic compounds were also investigated and the yield of alkanes was >90%. Based on the mechanism investigation, the catalyst demonstrated a high selectivity to cleave the Caryl–OR bond under mild conditions.Keywords: biomass; cobalt nitrides; hydrodeoxygenation; nitrogen-doped carbon; phenols conversion
Co-reporter:Lujiang Xu, Qian Yao, Zheng Han, Ying Zhang, and Yao Fu
ACS Sustainable Chemistry & Engineering 2016 Volume 4(Issue 3) pp:1115
Publication Date(Web):December 24, 2015
DOI:10.1021/acssuschemeng.5b01178
In this study, polylactic acid served as raw material to produce fine chemicals (pyridines) via a thermocatalytic conversion and ammonization (TCC-A) process. Ammonia was employed as not only carrier gas but also a reactant in this process. The thermal decomposition behavior of PLA under N2 or NH3 atmosphere was investigated. Different catalysts, including MCM-41, β-zeolite, ZSM-5 (Si/Al = 50) and HZSM-5 with different Si/Al ratios (Si/Al = 25, 50, 80) were also screened. Reaction temperature and residence time, which may affect the pyridines production, were investigated systematically. It was verified that all the investigated factors, including catalyst structure, catalyst acid amounts, reaction temperature, and residence time, influenced the PLA conversion and the pyridines production. The highest pyridines yield, 24.8%, was achieved by using HZSM-5 (Si/Al = 25) at around 500 °C. The catalyst regeneration tests were carried out. It demonstrated that the catalyst was stable after five regenerations and the catalytic activity did not change significantly. A possible reaction pathway from PLA to pyridines was also proposed. PLA initially thermally decomposed to form lactic acid and some byproducts such as acetaldehyde, acetone, etc., and then lactic acid, the mixture of acetaldehyde and acetone, or other byproducts reacted with ammonia to form imines and finally underwent complicated reactions to form pyridines.Keywords: Ammonia; Polylactic acid; Pyridines; Thermocatalytic conversion and ammonization; Zeolites
Co-reporter:Qian Yao, Lujiang Xu, Ying Zhang, Yao Fu
Journal of Analytical and Applied Pyrolysis 2016 Volume 121() pp:258-266
Publication Date(Web):September 2016
DOI:10.1016/j.jaap.2016.08.005
•The effect of diluted NH3 on TCC-A of furfural was investigated.•The carbon yield of indoles increased by 203.96% compared with that in pure NH3.•The production of N-containing chemicals was enhanced by diluted NH3 from furans.•The side reaction pathway to form coke was inhibited by the dilution of NH3.•The catalyst in diluted NH3 was more stable in pure NH3.Thermo-catalytic conversion and ammonization (TCC-A) is a novel and promising thermochemical conversion process for the direct production of N-heterocycles under NH3 atmosphere, which is similar to the pyrolysis technology through introducing exogenous nitrogen. Since NH3 served as the carrier gas and reactant, it played an important part in the process. The introduction of N2 into NH3 significantly enhanced the indoles production and catalyst stability in the TCC-A process of bio-derived furans. Under the optimized TCC-A conditions of furfural, NH3 being diluted by 25% N2 at 600 °C with WHSV as 1.5 h−1 and gas flow rate at 40 ml/min, the carbon yields of N-containing chemicals and indoles reached 46.51% and 33.04%, respectively, which increased by 90.54% and 203.96% compared with those in pure NH3. Using furan derivatives as the feedstock, diluted NH3 also showed positive effect on the production of N-containing chemicals. Functional groups in the furan derivatives strongly affect the product distribution. It was found that the increase of indoles production from furfural was because the generation of 2-furonitrile via the side reaction pathway to form coke was inhibited by the dilution of NH3. The catalysts were tested via five reaction/regeneration cycles in pure and diluted NH3 atmosphere and characterized by N2 adsorption/desorption, XRD, XRF, NH3-TPD analyses and SEM. Compared in pure NH3, the catalysts in N2 diluted NH3 was more stable, which could be due to the lower degree of dealumination, structure damage, and acid site loss.The N2 diluted NH3 showed a positive effect on the production of indole from furfural through TCC-A process.
Co-reporter:Jian-hua Guo, Guang-yue Xu, Fei Shen, Yao Fu, Ying Zhang and Qing-xiang Guo
Green Chemistry 2015 vol. 17(Issue 5) pp:2888-2895
Publication Date(Web):03 Mar 2015
DOI:10.1039/C4GC02406K
The long-chain alkanes obtained from the hydrodeoxygenation of plant oils are ideal substitutes for diesel. In this work, a new efficient catalytic system was established for the conversion of plant oil to long-chain alkanes under mild conditions with a bi-functional Ru/La(OH)3 catalyst. The hydrodeoxygenation of stearic acid was performed in an autoclave with Ru-based catalysts with different supports (HZSM-5, ZSM-5, SiO2–Al2O3, SiO2, ZrO2, Mg(OH)2, La(OH)3, and La2O3). Among these catalysts, Ru supported on basic La(OH)3 showed a remarkable catalytic performance for the reaction. Over 98% of long-chain alkanes were obtained with 100% conversion of stearic acid at 200 °C and 4 MPa H2. When crude Jatropha oil was hydrogenated, about 80.7 wt% of long chain alkanes were obtained under the optimized conditions (200 °C, 4 MPa H2, 8 h). The high efficiency of the Ru/La(OH)3 catalyst could be due to a co-effect of the high hydrogenation activity of Ru and the basic La(OH)3 support which can attract the acidic raw material. Additionally, the Ru/La(OH)3 catalyst was recycled four times and maintained a good activity and stability. The reaction pathway was also explored by using stearic acid as a model compound. Hydrogenation–decarbonylation could be the main pathway to produce n-heptadecane, which has one carbon atom less than stearic acid.
Co-reporter:Lujiang Xu, Yuanye Jiang, Qian Yao, Zheng Han, Ying Zhang, Yao Fu, Qingxiang Guo and George W. Huber
Green Chemistry 2015 vol. 17(Issue 2) pp:1281-1290
Publication Date(Web):24 Nov 2014
DOI:10.1039/C4GC02250E
In this study we demonstrate that indoles can be directly produced by thermo-catalytic conversion of bio-derived furans with ammonia over zeolite catalysts. MCM-41, β-zeolite, ZSM-5 (Si/Al = 50) and HZSM-5 catalysts with different Si/Al ratios (Si/Al = 25, 50, 63, 80) were screened and HZSM-5 with an Si/Al ratio of 25 showed the best reactivity for indole production due to the desired pore structure and acidity. Temperature displayed a significant effect on the product distribution. The maximum yield of indoles was obtained at moderate temperatures around 500 °C. The weight hourly space velocity (WHSV) of furan to catalyst investigation indicated that a lower WHSV could cause the overreaction of furan over the catalyst to produce more aniline and pyridines, while a higher WHSV would cause the incomplete reaction of furan. Because ammonia served as both a reactant and a carrier gas, to supply sufficient reactants and keep the desired reaction time, an appropriate ammonia to furan molar ratio was important for furan conversion to indoles. Under optimized conditions, the highest total carbon yield of indoles and their selectivity in the N-containing chemicals were 32% and 75%, respectively. 2-Methylfuran and the mixture of furan and 2-methylfuran were also studied, which demonstrated that more alkyl indoles could be selectively obtained via the coupling reaction of different bio-derived furans. Ring opening of the furan is a more favorable mechanism compared to the Diels–Alder mechanism, and the pyrrole reacting with furan is the more favorable pathway compared to pyrrole reacting with pyrrole based on our experimental and theoretical calculations.
Co-reporter:Lujiang Xu, Zheng Han, Qian Yao, Jin Deng, Ying Zhang, Yao Fu and Qingxiang Guo
Green Chemistry 2015 vol. 17(Issue 4) pp:2426-2435
Publication Date(Web):29 Jan 2015
DOI:10.1039/C4GC02235A
In this study, renewable pyridines could be directly produced from glycerol and ammonia via a thermo-catalytic conversion process with zeolites. The major factors, including catalyst, temperature, weight hourly space velocity (WHSV) of glycerol to catalyst, and the molar ratio of ammonia to glycerol, which may affect the pyridine production, were investigated systematically. The optimal conditions for producing pyridines from glycerol were achieved with HZSM-5 (Si/Al = 25) at 550 °C with a WHSV of glycerol to catalyst of 1 h−1 and an ammonia to glycerol molar ratio of 12:1. The carbon yield of pyridines was up to 35.6%. The addition of water to the feed decreased the pyridine yield, because water competed with glycerol on the acid sites of the catalyst and therefore impacted the acidity of the catalyst. After five reaction/regeneration cycles, a slight deactivation of the catalyst was observed. The catalysts were investigated by N2 adsorption/desorption, XRD, XRF and NH3-TPD and the results indicated that the deactivation could be due to the structure changes and the acid site loss of the catalyst. The reaction pathway from glycerol to pyridines was studied and the main pathway should be that glycerol was initially dehydrated to form acrolein and some by-products such as acetaldehyde, acetol, acetone, etc., and then acrolein, a mixture of acrolein and acetaldehyde, or other by-products reacted with ammonia to form imines and finally pyridines.
Co-reporter:Lujiang Xu, Qian Yao, Jin Deng, Zheng Han, Ying Zhang, Yao Fu, George W. Huber, and Qingxiang Guo
ACS Sustainable Chemistry & Engineering 2015 Volume 3(Issue 11) pp:2890
Publication Date(Web):October 7, 2015
DOI:10.1021/acssuschemeng.5b00841
Chemical conversion of biomass to value-added products provides a sustainable alternative to the current chemical industry that is predominantly dependent on fossil fuels. N-Heterocycles, including pyrroles, pyridines, and indoles, etc., are the most abundant and important classes of heterocycles in nature and widely applied as pharmaceuticals, agrochemicals, dyes, and other functional materials. However, all starting materials for the synthesis of N-heterocycles currently are derived from crude oil through complex multistep-processes and sometimes result in environmental problems. In this study, we show that N-heterocycles can be directly produced from biomass (including cellulose, lignocelluloses, sugars, starch, and chitosan) over commercial zeolites via a thermocatalytic conversion and ammonization process (TCC-A). All desired reactions occur in one single-step reactor within seconds. The production of pyrroles, pyridines, or indoles can be simply tuned by changing the reaction conditions. Meanwhile, N-containing biochar can be obtained as a valuable coproduct. We also outline the chemistry for the conversion of biomass into heterocycle molecules by the addition of ammonia into pyrolysis reactors demonstrating how industrial chemicals could be produced from renewable biomass resources. Only minimal biomass pretreatment is required for the TCC-A approach.Keywords: Biomass; N-Heterocycles; Reaction pathway; Thermocatalytic conversion and ammonization; Zeolites;
Co-reporter:Guangyue Xu;Jianhua Guo; Ying Zhang; Yao Fu;Jinzhu Chen;Longlong Ma; Qingxiang Guo
ChemCatChem 2015 Volume 7( Issue 16) pp:2485-2492
Publication Date(Web):
DOI:10.1002/cctc.201500442
Abstract
The production of pure cyclohexanone under mild conditions over catalysts with high reactivity, selectivity, compatibility, stability, and low cost is still a great challenge. Here we report a hydroxyapatite-bound palladium catalyst (Pd–HAP) to demonstrate its excellent performance on phenol hydrogenation to cyclohexanone. Based on catalyst characterization, the Pd nanoclusters (≈0.9 nm) are highly dispersed and bound to phosphate in HAP. Only basic active sites on HAP surface are detected. At 25 °C and ambient H2 pressure in water, phenol can be 100 % converted into cyclohexanone with 100 % selectivity. This system shows a universal applicability to temperature, pH, solvent, low H2 purity, and pressure. The catalyst reveals high stability to be recycled without deactivation or morphology change; and Pd nano-clusters barely aggregate even at 400 °C. During the reaction, HAP adsorbs phenol, and Pd nanoclusters activate and spillover H2. The mechanism is also investigated, proposed, and verified.
Co-reporter:Jianhua Guo, Guangyue Xu, Zheng Han, Ying Zhang, Yao Fu, and Qingxiang Guo
ACS Sustainable Chemistry & Engineering 2014 Volume 2(Issue 10) pp:2259
Publication Date(Web):August 27, 2014
DOI:10.1021/sc5003566
A new catalytic system was developed for the selective conversion of biomass-derived furfural to cyclopentanone in aqueous solution. CuZnAl catalysts with different Cu/Zn molar ratios (0.5, 1, 2, and 3) and calcination temperatures (350, 500, and 700 °C) were investigated, and the CuZnAl-500–0.5 catalyst (Cu/Zn = 0.5, calcined at 500 °C) showed a remarkable catalytic performance in the reaction. A 62% yield of cyclopentanone was obtained at the optimized conditions (150 °C, 4 MPa H2, 6 h), and the TOF was 9.4 h–1. The catalysts were characterized by nitrogen adsorption, XRD, TEM, N2O titration, ICP, XPS, and a carbon–sulfur analyzer. The factors that influenced the activity of catalysts were also investigated. Additionally, the CuZnAl-500–0.5 was recycled five times and maintained good activity and stability. Hence, the current work presents a new and efficient catalytic system for the conversion of furfural to cyclopentanone. The low-cost nature of the CuZnAl makes it a potential catalyst for the production of cyclopentanone in industry.Keywords: CuZnAl catalyst; Cyclopentanol; Cyclopentanone; Furfural; Hydrogenation
Co-reporter:Yan-Chao Qu, Xin-Lai Wei, Yong Zuo, Qing Xu, Shi-Zhi Yan, Ying Zhang, Yao Fu
International Journal of Hydrogen Energy 2014 Volume 39(Issue 25) pp:13136-13140
Publication Date(Web):22 August 2014
DOI:10.1016/j.ijhydene.2014.06.145
•Carboxylates and H2 were produced under mild conditions without using any catalyst.•The purity of hydrogen was up to 99.8%.•No CO or CO2 was detected in the gas products.•The mechanism was proposed and verified.In this study, we presented an unexpected environmentally benign and easy-to-implement reaction for producing highly pure hydrogen (99.8%) and value-added carboxylate from primary alcohols under basic conditions. No catalyst was required, and no environmentally harmful gas, such as CO and CO2, was produced. The reaction conditions, different reactants and the water tolerance of the reaction were examined. It was found that as long as the temperature is higher than 500 K, no matter what the pressure is, hydrogen and carboxylate can be produced from primary alcohols. Strong alkalinity and high solubility of the base is necessary for the reaction. It was confirmed that ethanol-water mixtures, which could be produced from biomass fermentation, can be used as feedstock in this process, making it more meaningful in terms of sustainability. The mechanism of the reaction was also investigated in detail.
Co-reporter:Yong Zuo; Ying Zhang;Dr. Yao Fu
ChemCatChem 2014 Volume 6( Issue 3) pp:753-757
Publication Date(Web):
DOI:10.1002/cctc.201300956
Abstract
A novel solid acid catalyst, sulfonated chloromethyl polystyrene (CP) resin (CP-SO3H-1.69), was synthesized by partially substituting chlorine groups (Cl) of CP resin with sulfonic group(SO3H). This new type solid acid contains not only acid sites, but also cellulose-binding sites (Cl). A high yield of levulinic acid up to 65.5 % was obtained by converting microcrystalline cellulose over CP-SO3H-1.69. The high catalytic activity of CP-SO3H-1.69 was attributed to high amount of sulfonic group and chlorine on the catalyst, which is essential to keep the catalyst with great affinity to substrate.
Co-reporter:Yan-Chao Qu, Zhi Wang, Qiang Lu, and Ying Zhang
Industrial & Engineering Chemistry Research 2013 Volume 52(Issue 36) pp:12771-12776
Publication Date(Web):2017-2-22
DOI:10.1021/ie401626d
4-Vinylphenol is an important chemical that can be used as the monomer for the production of poly(4-vinylphenol) (PVPh). Currently, 4-vinylphenol was prepared by the dehydrogenation of 4-ethylphenol over chromia/alumina catalyst at 600 °C. In this study, a low-cost process involving low-temperature fast pyrolysis of biomass without any catalyst was developed to selectively produce 4-vinylphenol. Pyrolysis gas chromatography/mass spectrometry (Py–GC/MS) was used for the fast pyrolysis of bagasse, cornstalk, bamboo, rice husk, rice straw, cotton straw, and poplar wood to investigate the effects of different materials on the selectivity of 4-vinylphenol. It was found that some of the herbaceous materials, such as bagasse, cornstalk, and bamboo, were suitable for the production of 4-vinylphenol, whereas woody materials were not applicable. The effects of temperature on 4-vinylphenol production were also investigated. 4-Vinylphenol contents of up to 7 and 20 wt % were achieved at 300 °C from bagasse and bagasse EMAL, respectively. For the first time, 4-vinylphenol was separated from the pyrolysis oil obtained by the fast pyrolysis of bagasse using a benchtop unit, and its structure was confirmed by various methods. Additionally, it was verified that 4-vinylphenol could be produced from compounds with a β-5 linkage, and a possible mechanism for the generation of 4-vinylphenol from a lignin model compound with a β-5 linkage is proposed.
Co-reporter:Xinlai Wei, Qiang Lu, Xianwei Sui, Zhi Wang, Ying Zhang
Journal of Analytical and Applied Pyrolysis 2012 Volume 97() pp:49-54
Publication Date(Web):September 2012
DOI:10.1016/j.jaap.2012.07.002
Water-insoluble pyrolytic cellulose with similar appearance to pyrolytic lignin was found in cellulose fast pyrolysis oil. The influence of pyrolysis temperature on pyrolytic cellulose was studied in a temperature range of 300–600 °C. The yield of the pyrolytic cellulose increased with temperature rising. The pyrolytic cellulose was characterized by various methods. The molecular weight distribution of pyrolytic cellulose was analyzed by gel permeation chromatography (GPC). Four molecular weight ranges were observed, and the Mw of the pyrolytic cellulose varied from 3.4 × 103 to 1.93 × 105 g/mol. According to the elemental analysis (EA), the pyrolytic cellulose possessed higher carbon content and lower oxygen content than cellulose. Thermogravimetric analysis (TGA) indicated that the pyrolytic cellulose underwent thermo-degradation at 127–800 °C and three mass loss peaks were observed. Detected by the pyrolysis gas chromatography–mass spectrometry (Py-GC/MS), the main pyrolysis products of the pyrolytic cellulose included saccharides, ketones, acids, furans and others. Fourier transforms infrared spectroscopy (FTIR) also demonstrated that the pyrolytic cellulose had peaks assigned to CO stretching and glycosidic bond, which agreed well with the Py-GC/MS results. The pyrolytic cellulose could be a mixture of saccharides, ketones, and their derivatives.Highlights► Water-insoluble pyrolytic cellulose was isolated from cellulose fast pyrolysis oil by water precipitation. ► The pyrolysis temperature effect on the pyrolytic cellulose production was investigated. ► The pyrolytic cellulose was characterized by GPC, EA, TGA, Py-GC/MS and FTIR. ► The pyrolytic cellulose underwent thermo-degradation at 127–800 °C and three mass loss peaks were observed. ► The structures of polysaccharide and ketones were detected in the pyrolytic cellulose.
Co-reporter:Jianhua Guo, Renxiang Ruan, and Ying Zhang
Industrial & Engineering Chemistry Research 2012 Volume 51(Issue 19) pp:6599-6604
Publication Date(Web):April 25, 2012
DOI:10.1021/ie300106r
Phenolic compounds in bio-oil are not stable and difficult to be upgraded to ideal fuels. In this study, simulated bio-oil as well as phenolic compounds separated from bio-oil by glycerol-assisted distillation were hydrotreated by Ru/SBA-15 catalyst and completely converted into C3 to C10 alcohols at mild conditions, which could be a feasible way to transfer the phenolic compounds in bio-oil or other real systems from lignin decomposition into high heating-value liquid fuel or fuel additives. The stability of the Ru/SBA-15 catalyst was also investigated. It was found that Ru/SBA-15 was stable with phenolic compounds in the simulated bio-oil but not in a real one.
Co-reporter:Zhi Wang;Dr. Qiang Lu; Xi-Feng Zhu; Ying Zhang
ChemSusChem 2011 Volume 4( Issue 1) pp:79-84
Publication Date(Web):
DOI:10.1002/cssc.201000210
Abstract
Sulfated zirconia was employed as catalyst for fast pyrolysis of cellulose to prepare levoglucosenone (LGO), a very important anhydrosugar for organic synthesis. The yield and the selectivity of LGO were studied in a fixed-bed reactor at different temperatures and cellulose/catalyst mass ratios. The experiments of catalyst recycling were also carried out. The results displayed that from 290 to 400 °C, the liquid and solid accounted for more than 95 wt % of products, and the higher temperature led to more liquid and less solid products. The introduction of SO42−/ZrO2 could promote cellulose conversion and LGO production. The temperature had a similar effect on the yield and selectivity of LGO at different cellulose/catalyst mass ratios. The maximum yield was obtained at 335 °C. Although the structure of the parent ZrO2 was retained after recycles, which was confirmed by X-ray diffraction and N2 adsorption–desorption measurements, the activity of SO42−/ZrO2 could only be partially recovered by simply calcination. The catalytic activity decrease could be mainly attributed to SO42− leaching, and the activity could be restored by further impregnation of H2SO4.
Co-reporter:Qiang Lu, Zhe Tang, Ying Zhang and Xi-feng Zhu
Industrial & Engineering Chemistry Research 2010 Volume 49(Issue 6) pp:2573-2580
Publication Date(Web):February 8, 2010
DOI:10.1021/ie901198s
Palladium supported on SBA-15 catalysts were developed and employed for catalytic cracking of biomass fast pyrolysis vapors using analytical pyrolysis−gas chromatography/mass spectrometry (Py-GC/MS). The Pd/SBA-15 catalysts displayed prominent capabilities to crack the lignin-derived oligomers to monomeric phenolic compounds and further convert them to phenols without the carbonyl group and unsaturated C−C bond on the side chain. Moreover, the catalysts almost completely eliminated the anhydrosugar products and decarbonylated the furan compounds. They also significantly decreased the linear aldehydes and dehydroxylated the linear ketones. In addition, the catalysts slightly decreased the acids, while methanol and hydrocarbons were increased. The above catalytic capabilities of the Pd/SBA-15 catalyst were enhanced with the increase of Pd content from 0.79 wt % to 3.01 wt %.
Co-reporter:Zhe Tang, Ying Zhang and Qingxiang Guo
Industrial & Engineering Chemistry Research 2010 Volume 49(Issue 5) pp:2040-2046
Publication Date(Web):February 2, 2010
DOI:10.1021/ie9015842
Pyrolytic lignins (PLs) are the major components in fast pyrolysis bio-oils and have detrimental effects on bio-oil properties. The existence of PLs also makes bio-oil upgrading rather difficult due to their nonvolatility and thermal instability. In this study, PL produced from rice husk was hydrocracked at 260 °C in supercritical ethanol under a hydrogen atmosphere by the use of Ru/ZrO2/SBA-15 or Ru/SO42−/ZrO2/SBA-15 catalyst. Trace amount of tar or coke was produced after the hydrocracking process, and most of the PL was converted into liquid fuel consisting of stable organic compounds with a heating value as high as 34.94 MJ/kg. The liquid product distribution was investigated by gas chromatography/mass spectrometry (GC-MS). The results demonstrated that, under supercritical ethanol conditions, Ru/ZrO2/SBA-15 and Ru/SO42−/ZrO2/SBA-15 were effective catalysts to convert PL to stable organic compounds such as phenols, guaiacols, anisoles, esters, light ketones, alcohols, long-chain alkanes, etc.
Co-reporter:Zhe Tang, Qiang Lu, Ying Zhang, Xifeng Zhu and Qingxiang Guo
Industrial & Engineering Chemistry Research 2009 Volume 48(Issue 15) pp:6923-6929
Publication Date(Web):July 8, 2009
DOI:10.1021/ie900108d
The crude bio-oil was upgraded in supercritical ethanol under hydrogen atmosphere by using Pd/SO42−/ZrO2/SBA-15 catalyst. This is a novel way to upgrade bio-oil with the combination of hydrotreatment, esterification, and cracking under supercritical conditions. The results indicated that the upgrading process performed effectively and the properties of the upgraded bio-oil were improved significantly. After the upgrading process, a trace amount of tar or coke was produced and most of the organic components were kept in the upgraded bio-oil. No phase separation was observed. The amount of aldehydes and ketones decreased evidently. In particular, aldehydes were almost completely removed. Most acids were converted into corresponding esters, and at the same time many new types of esters were produced. The results of TGA and DTA indicated that macromolecular compounds were decomposed and much more volatile compounds were produced after the upgrading process. The pH value and heating value of the upgraded bio-oil increased; meanwhile, the kinematical viscosity and density decreased compared to those of the crude bio-oil.
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