Co-reporter:Qiying Liu, Tao Zhang, Yuhe Liao, Chiliu Cai, Jin Tan, Tiejun Wang, Songbai Qiu, Minghong He, and Longlong Ma
ACS Sustainable Chemistry & Engineering July 3, 2017 Volume 5(Issue 7) pp:5940-5940
Publication Date(Web):May 26, 2017
DOI:10.1021/acssuschemeng.7b00702
Producing chemicals from lignocellulosic biomass is important in view of the huge availability of biomass and positive environmental significance by reducing carbon emission due to fast carbon cycle during biomass growth and applications. Here, we prepared zirconium based solid acids for hydrolytic hydrogenation of raw lignocelluloses to coproduce C5/C6 sugar alcohols (the important platform for downstream chemicals and fuel production) as combined with commercial Ru/C. Among these solid acids, the amorphous zirconium phosphate (ZrP) presented the largest acidic sites, with medium and strong acidity as the majority, showing the highest goal sugar alcohols yield of 70% at optimal reaction conditions. During pennisetum transformation, this combined catalyst was reusable despite the activity of the second run being lower than the initial one, and the activity could be recovered by recalcination of spent ZrP. The primary structure of surviving lignin remained after cellulose and hemicellulose were converted, showing the significance for fractional biomass applications if considering the further transformation of lignin.Keywords: Biomass; Hydrolytic hydrogenation; Solid combined catalyst; Sugar alcohol;
Co-reporter:Jin Tan, Qiying Liu, Lungang Chen, Tiejun Wang, ... Guanyi Chen
Journal of Energy Chemistry 2017 Volume 26, Issue 1(Volume 26, Issue 1) pp:
Publication Date(Web):1 January 2017
DOI:10.1016/j.jechem.2016.08.004
One-pot achievement of ethyl levulinate from cassava was conducted in ethanol–water system over several simple sulfate salt catalysts. Al2(SO4)3 catalyst had the best performance in synthesizing ethyl levulinate comparing with those of a series of sulfate salts. The highest yields of ethyl levulinate was up to 39.27% as well as 7.78% levulinate acid when cassava was catalyzed in ethanol medium by adding 10 wt% water. 13C and 1H NMR spectroscopic investigations confirmed that isomerization of glucose to fructose over Al2(SO4)3 catalyst is an important step in producing ethyl levulinate and levulinate acid. Due to aggregations of Al3+ under hydrothermal conditions, tiny amount of Al3+ were detected in filtrate at the percentage of 0.32% even if in absolute water. Brønsted and Lewis acids could improve the yield of ethyl levulinate and levulinate acid by synergistic effect. All results suggested that Al2(SO4)3 was a simple and efficient catalyst for ethyl levulinate and levulinate acid production.Download high-res image (105KB)Download full-size imageEthyllevulinate (yield of 39.27%) and levulinate acid (yield of 7.78%) could be achieved efficiently from cassava over simple and single Al2(SO4)3 catalyst in ethanol–water system by one step.
Co-reporter:Shengxin An;Wenzhi Li;Qiyu Liu;Minghao Li;Qiaozhi Ma;Hou-min Chang
RSC Advances (2011-Present) 2017 vol. 7(Issue 52) pp:32452-32460
Publication Date(Web):2017/06/23
DOI:10.1039/C7RA05280D
A two-stage pretreatment method was developed to improve sugar recovery in this study. Firstly, the corn stover was pretreated with acidic dioxane to remove lignin, then the residue was subjected to dilute hydrochloric acid to eliminate the negative effects of hemicelluloses on enzymatic hydrolysis as well as increasing xylose yield. The optimal condition was 90 °C, 20 min, and 9/1 (v/v) dioxane–water including 1.0 wt% HCl solution in the first stage followed by 120 °C and 40 min for 1.0 wt% dilute hydrochloric acid in the second stage. The total yields of glucose and xylose were 91.5% and 79.7%, respectively, with a low cellulase dosage of 3 FPU g−1 of substrate. This two-stage pretreatment was effective due to the removal of lignin in the first stage and the hydrolysis of hemicelluloses in the second stage, resulting in a very high sugar recovery with a low enzyme loading.
Co-reporter:Yue Yang;Qiying Liu;Dan Li;Jin Tan;Qi Zhang;Chenguang Wang
RSC Advances (2011-Present) 2017 vol. 7(Issue 27) pp:16311-16318
Publication Date(Web):2017/03/14
DOI:10.1039/C7RA00605E
Selective hydrogenation of 5-hydroxymethylfurfural (HMF) has potential application in high quality biofuels. Herein, the catalytic hydrodeoxygenation (HDO) of HMF to 2,5-dimethylfuran (DMF) was investigated using bi-functional Ru–MoOx/C catalyst prepared by initial wetness impregnation. The high dispersion and electronic transfer between Ru and MoOx were demonstrated by a series of characterization techniques. During this HDO process, the synergy effect between metallic Ru and acidic MoOx species in the Ru–MoOx/C catalyst plays an essential role in obtaining maximized target product DMF (79.4%) via effective aldehyde group hydrogenation by Ru followed by dehydration over MoOx. This work also elucidated that DMF production proceeded through two distinct pathways: the 2,5-hydroxymethyl furan intermediate was preferable by the aldehyde group hydrogenation of HMF over the Ru–MoOx/C catalyst. Over MoOx/C catalyst, comparatively, 5-methyl furfural was the key intermediate by direct hydrogenolysis of the hydroxyl group in HMF. This kind of catalyst is stable for the first two runs by maintaining the target product yield. After the third run, the catalyst showed deactivation gradually but could be almost completely recovered after regeneration by H2 reduction.
Co-reporter:Qing Zhang, Jin Tan, Tiejun Wang, Qi Zhang, Longlong Ma, Songbai Qiu, Yujing Weng
Fuel 2016 Volume 165() pp:152-158
Publication Date(Web):1 February 2016
DOI:10.1016/j.fuel.2015.10.071
•100% of sorbitol conversion was achieved by using a fixed bed reactor.•Higher aromatics production occurred over the Ni/HZSM-5 catalyst.•Proper acidity of zeolite facilitates hydrogenation and aromatization of sorbitol.Aromatics including benzenes, olefins and naphthalenes derived from renewable biomass are of great importance on the potential substitution for diminishing fossil fuels. In this work, aromatics from biomass-derived sorbitol by hydrogenation and aromatization was investigated over the Ni/HZSM-5 and Ni/Hβ catalysts in a fixed-bed reactor. The testing results showed that all the catalysts revealed 100% of sorbitol conversion, while the formation of aromatics and carbon species were various during the catalytic processing of sorbitol. The selectivity of aromatics was found to be 53.2% and 17.1% over the Ni/HZSM-5(38) and Ni/Hβ catalyst, respectively. In addition, the catalysts were characterized by N2 physical adsorption, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), H2 temperature-programmed reduction (H2-TPR), and temperature-programmed desorption of ammonia (NH3-TPD) techniques. The characterization results revealed that the Ni/HZSM-5(38) catalyst contained the optimum acidic sites and the structural property, which favor the hydrogenation and aromatization of sorbitol in the reaction.Aromatics was achieved from catalytic processing of sorbitol over Ni/HZSM-5 and Ni/Hβ. Hydrogenation and aromatization of sorbitol was carried out in a fixed-bed reactor.
Co-reporter:Yong Liu, Lungang Chen, Tiejun Wang, Qi Zhang, Chenguang Wang, Jinyue Yan, and Longlong Ma
ACS Sustainable Chemistry & Engineering 2015 Volume 3(Issue 8) pp:1745
Publication Date(Web):June 23, 2015
DOI:10.1021/acssuschemeng.5b00256
Lignocellulosic biomass is a renewable feedstock that has the potential to replace the diminishing fossil fuels. Herein, we reported the simultaneous conversion of cellulose, hemicellulose and lignin from raw biomass into gasoline alkanes (hexanes and pentanes) and monophenols and related hydrocarbons over layered LiTaMoO6 and Ru/C in aqueous phosphoric acid medium. Specifically, gasoline alkanes were directly yielded from the carbohydrate components, based on hemicellulose and cellulose, and the total yield could be up to 82.4%. Notably, the lignin fraction could also be transformed into monophenols, related alcohols and hydrocarbons by the one-pot reaction. It suggested that the hydrocracking of monophenol fraction could be performed in this catalytic system. The total yield of volatile products was 53% based on the lignin fraction. In this paper, the influences of phosphoric acid concentration, substrate ash and the amino acids derived from the biogenic impurities were investigated and different raw biomass substrates were tested. Furthermore, the catalysts could be reused for several runs to convert raw biomass without pretreatment.Keywords: Catalytic conversion; Gasoline alkanes; Layered compounds; Lignocellulosic biomass; Phenols
Co-reporter:Yong Liu, Lungang Chen, Tiejun Wang, Xinghua Zhang, Jinxing Long, Qi Zhang and Longlong Ma
RSC Advances 2015 vol. 5(Issue 15) pp:11649-11657
Publication Date(Web):11 Dec 2014
DOI:10.1039/C4RA14304C
In aqueous phosphoric acid, cellulose was efficiently converted into hexanes using a Ru/C catalyst combined with layered compounds or silica–alumina materials. In this process, the direct production of hexanes from cellulose can be improved by suppressing the formation of isosorbide, which makes it difficult to yield hexanes by further hydrodeoxygenation. As the co-catalyst, layered compounds showed a significant inhibition effect on the formation of isosorbide from sorbitol due to the steric restrictions of sorbitol dehydration within the interlayers of layered compounds. Typically, layered LiNbMoO6 played a great role in promoting the production of hexanes directly from cellulose and a promising yield (72% carbon mol) of hexanes was obtained. In addition, the protonic acid, H3PO4, offered efficient catalysis for the hydrolysis of cellulose and the dehydration of the sorbitol hydroxyl moiety.
Co-reporter:Yuhe Liao, Qiying Liu, Tiejun Wang, Jinxing Long, Longlong Ma and Qi Zhang
Green Chemistry 2014 vol. 16(Issue 6) pp:3305-3312
Publication Date(Web):18 Mar 2014
DOI:10.1039/C3GC42444H
The selective transformation of cellulose to C6 alditols provides a feasible route towards the sustainable synthesis of chemicals and fuels. Herein, the catalytic performance of amorphous zirconium phosphate (ZPA) combined with 5 wt% Ru/C was evaluated in the direct conversion of cellulose to C6 alditols (sorbitol and mannitol) under hydrothermal conditions. The yield of C6 alditols reached 63.5% and 85.5% with microcrystalline cellulose and ball-milled cellulose as the feedstock, respectively. This hybrid catalyst was developed to convert concentrated cellulose to obtain C6 alditols with a high concentration of 68.8 mg mL−1 in the final products. The high yield of C6 alditols from cellulose was ascribed to the fact that ZPA favoured the adsorption of cellulose and promoted its depolymerization to cellobiose and glucose, which was hydrogenated immediately to C6 alditols over Ru/C. The weak adsorption of C6 alditols over ZPA inhibited the dehydration of C6 alditols to sorbitan. Furthermore, ZPA exhibited excellent hydrothermal stability and could be reused for several runs.
Co-reporter:Ning Shi, Qiying Liu, Tiejun Wang, Longlong Ma, Qi Zhang, and Qing Zhang
ACS Sustainable Chemistry & Engineering 2014 Volume 2(Issue 4) pp:637
Publication Date(Web):February 23, 2014
DOI:10.1021/sc400515x
Direct conversion of cellulose into furfural compounds (5-hydroxymethylfurfural and furfural) in hot compressed steam with the aid of phosphates was studied under temperatures of 250–330 °C and pressures of 0.5–3.5 MPa. The water in the steam could be adsorbed by cellulose to form water molecule layers, which could hydrolyze cellulose. Basic Na2HPO4 was found to be favorable for fragment product formation through hydrolysis of cellulose followed by retro-aldol condensation of saccharide, while the acidic dihydric phosphates (LiH2PO4, NaH2PO4, and Ca(H2PO4)2) were favorable for furfural compound formation through the hydrolysis–dehydration process. A total furfural compound yield of 34% was obtained under optimal conditions with the aid of NaH2PO4, accompanied by 16% solid residue formation. The solid residue containing dihydric phosphates could be used as phosphatic fertilizer.Keywords: 5-Hydroxymethylfurfural; Cellulose; Dihydric phosphate; Fuel; Hot compressed steam; Relative humidity;
Co-reporter:Bosong Li, Wei Lv, Qi Zhang, Tiejun Wang, Longlong Ma
Journal of Analytical and Applied Pyrolysis 2014 Volume 108() pp:295-300
Publication Date(Web):July 2014
DOI:10.1016/j.jaap.2014.04.002
•Sodium lignosulfonate was pyrolyzed under un-catalytic and catalytic conditions.•The main pyrolysis process of SL was separated into three stages.•HZSM-5 enhanced the mass loss and inhibited char formation.•HZSM-5 promoted cracking reactions of oxygenated products.•Aromatics, water, CO2 and CO are the main products.Industrial lignins are by-products of the pulp and paper industry and generally used as a low-grade fuel. In this study, pyrolysis and catalytic pyrolysis (using HZSM-5, an aluminosilicate zeolite) of sodium lignosulfonate (SL) were carried out in a coupling of thermogravimetric analysis and Fourier transform infrared spectroscopy (TG-FTIR) using nitrogen. The reaction temperature was increased from 30 to 650 °C, while the heating rates were varied from 10 to 40 °C/min. The pyrolysis process could be divided into three parts. Kissinger's method had been used to carry out dynamics calculation concerning pyrolysis of SL in main pyrolysis. The kinetic parameters and reaction orders in the three pyrolysis stage were gained. The generated products for SL pyrolysis were water, CO, CO2, aromatics, alkenes and alkyls. The catalytic effect of HZSM-5 is obvious. It inhibited char formation of SL pyrolysis, and promoted the degradation of high molecular weight compounds to low molecular weight compounds, promoted cracking reactions of oxygenated products.
Co-reporter:Yuhe Liao, Qiying Liu, Tiejun Wang, Jinxing Long, Qi Zhang, Longlong Ma, Yong Liu, and Yuping Li
Energy & Fuels 2014 Volume 28(Issue 9) pp:5778-5784
Publication Date(Web):August 5, 2014
DOI:10.1021/ef500717p
Enhancing the contact or interaction between cellulose and solid catalyst is a significant aspect in its efficient catalytic conversion. Herein, mixed ball milling of cellulose and solid catalyst was presented to achieve this goal, and the promotion effect was measured by hydrolytic hydrogenation of cellulose to sugar alcohols (the platform compounds for biogasoline) with solid acid and commercial 5 wt % Ru/C in water. The effects of ball-milling modes, time, and reaction parameters were studied. The properties of cellulose and solid acid catalyst before and after treatment were also analyzed. The yield of sugar alcohols reached 90.3% at 463 K with amorphous zirconium phosphate and Ru/C (mixed ball-milling time of 2 h). This high yield of sugar alcohols achieved in the mixed ball-milling time of 2 h was 12 times faster than that by the single ball milling of 24 h under the same reaction conditions. It is ascribed to the enhanced contact between cellulose and catalyst, resulting in promoting cellulose depolymerization. The high concentration of sugar alcohols up to 67 mg/mL was obtained by augmenting the mass ratio of cellulose/catalyst.
Co-reporter:Yong Liu, Lungang Chen, Tiejun Wang, Ying Xu, Qi Zhang, Longlong Ma, Yuhe Liao and Ning Shi
RSC Advances 2014 vol. 4(Issue 94) pp:52402-52409
Publication Date(Web):09 Oct 2014
DOI:10.1039/C4RA10834E
Non-edible cellulose has attracted considerable attention to be converted into valuable platform chemicals. Direct transformation of cellulose to C6 alditols (mannitol and sorbitol) provides a sustainable route. A productive approach is presented in this work using a Ru/C catalyst combined with H+-released boron phosphate in an aqueous phase. A yield of C6 alditols as high as 74.9% with a 91% conversion of cellulose is achieved. By adding silica–alumina materials, the yield of C6 alditols can be improved to 93.5% with complete conversion. The acid sites gradually released from boron phosphate under hydrothermal conditions could promote the hydrolysis of cellulose without significant degradation of glucose. Furthermore, the interaction of boric acid with C6 alditols may form borate–polyol complexes, which can enhance the stability of the C6 alditols to avoid further hydrogenolysis and dehydration of the C6 alditols formed. Due to the adsorption ability of the substrate, the addition of silica–alumina materials with a high content of silica leads to improved performance.
Co-reporter:Ning Shi, Qiying Liu, Longlong Ma, Tiejun Wang, Qi Zhang, Qing Zhang and Yuhe Liao
RSC Advances 2014 vol. 4(Issue 10) pp:4978-4984
Publication Date(Web):06 Nov 2013
DOI:10.1039/C3RA45813J
A novel method of direct degradation of cellulose into 5-hydroymethylfurfural (HMF) in hot compressed steam was introduced, with the inorganic acidic salts (NaHSO4, KHSO4, NaH2PO4 and KH2PO4) as catalysts. The water molecules in the steam were absorbed by the catalysts to form an acidic aqueous layer on the surface of the cellulose, where the cellulose was converted into HMF and spread into the gas phase. The relative humidity of steam could influence the reaction route by controlling the acidity of the aqueous layer. Low relative humidity of steam was favoured for the carbonization of cellulose, while high relative humidity was preferred for hydrolysis-dehydration of cellulose to form HMF. A moderate HMF yield of 30.4 mol% was obtained with NaH2PO4 as the catalyst. This novel methodology demonstrated an efficient and green HMF production from cellulose, without organic solvents and toxic transition metal cations.
Co-reporter:Xinghua Zhang, Jinxing Long, Wei Kong, Qi Zhang, Luangang Chen, Tiejun Wang, Longlong Ma, and Yuping Li
Energy & Fuels 2014 Volume 28(Issue 4) pp:2562
Publication Date(Web):March 27, 2014
DOI:10.1021/ef402421j
Ni-Based catalysts using mixed oxides of Al2O3–SiO2, Al2O3–TiO2, TiO2–SiO2, and TiO2–ZrO2 as supports were evaluated for hydrotreatments using guaiacol as the model compound and characterized by N2 physical adsorption, X-ray diffraction (XRD), temperature-programmed desorption of ammonia (NH3-TPD), and temperature-programmed reduction of hydrogen (H2-TPR) techniques. The influence of the support, solvent, reaction temperature, and pressure on guaiacol conversion and product distributions were determined. Guaiacol conversion of 100% with cyclohexane selectivity of 86.4% was obtained over the Ni/TiO2–ZrO2 catalyst at the conditions of 300 °C, 4.0 MPa H2 pressure, and decalin solvent. Furthermore, this system is also efficient for real bio-oil, where nearly 19.3% of the upgraded bio-oil yield was achieved under the optimal conditions determined for guaiacol. Gas chromatography–mass spectrometry (GC–MS) analysis showed that the principal components were phenolic compounds, while the content of acids and aldehydes was negligible. The pH of bio-oil increased from 2.38 to 4.21, and the high heating value drastically increased from 13.1 to 25.8 MJ/kg.
Co-reporter:Qi-Ying Liu, Yu-He Liao, Tie-Jun Wang, Chi-Liu Cai, Qi Zhang, Noritatsu Tsubaki, and Long-Long Ma
Industrial & Engineering Chemistry Research 2014 Volume 53(Issue 32) pp:12655-12664
Publication Date(Web):2017-2-22
DOI:10.1021/ie5016238
ZrP with large surface, mesoporous volume, and size was prepared. Its catalytic performance was evaluated in hydrolytic hydrogenation of cellulose to sorbitol/mannitol combined with commercial Ru/C. A significantly enhanced sorbitol/mannitol yield was obtained as compared with that of the water-soluble acidic phosphates and buffer solution of potassium acid phthalate combined with the same Ru/C. The enhanced yield was attributed to the Lewis and Brönsted acid on ZrP surface improving the surface’s absorption and activation for cellulose and accelerating the rate-determined hydrolysis step. The maximal sorbitol/mannitol yield of 63% and 81% could be obtained by using microcrystalline and ball milling cellulose as the feedstock, respectively. The ZrP combined with Ru/C was adaptable to the high concentrated cellulose and obtained 5.8 wt % of sorbitol/mannitol concentration. The remarkably enhanced cellulose hydrolysis by ZrP sharply decreased the use of Ru/C, which is significant for the essential application.
Co-reporter:Ning Shi, Qiying Liu, Qi Zhang, Tiejun Wang and Longlong Ma
Green Chemistry 2013 vol. 15(Issue 7) pp:1967-1974
Publication Date(Web):25 Apr 2013
DOI:10.1039/C3GC40667A
A high 5-hydroxymethylfurfural (HMF) yield of 53 mol% was obtained by direct degradation of cellulose in a biphasic system with concentrated NaHSO4 and ZnSO4 as co-catalysts, with 96% of cellulose conversion in 60 min. The high concentration of catalysts in the aqueous solution and the high volume ratio of organic phase to aqueous phase were responsible for the excellent performance. The depolymerization of cellulose is the rate-determine step, and the formed glucose could be efficiently converted by concentrated catalysts in the aqueous solution, leading to low concentration of glucose in the solution and thus suppressing the side reactions such as humin and char formation.
Co-reporter:Dr. Jinzhu Chen;Wei Zhang;Dr. Limin Chen;Dr. Longlong Ma;Dr. Hui Gao;Dr. Tiejun Wang
ChemPlusChem 2013 Volume 78( Issue 2) pp:142-148
Publication Date(Web):
DOI:10.1002/cplu.201200276
Abstract
Cyclohexanone is an industrially important intermediate in the synthesis of materials such as nylon and polyamides, but direct selective hydrogenation of phenol to cyclohexanone under green conditions is a challenge owing to the over-reduction of cyclohexanone to cyclohexanol. A catalyst made of palladium nanoparticles supported on polyaniline-functionalized carbon nanotubes, Pd–PANI/CNT, which was shown to be highly active towards the direct hydrogenation of phenol to cyclohexanone, is reported. Phenol conversion exceeding 99 % was achieved with a cyclohexanone selectivity of >99 % under atmospheric pressure of hydrogen in aqueous media. The generality of the catalyst for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance, again under green and mild conditions. It is suggested the Pd–N interactions and polymeric stabilization play a key role in the formation of stable and highly dispersed palladium nanoparticles on the conducting composite material PANI/CNT. The results also indicate that the phenol conversion is related presumably to the conductive property of PANI/CNT, whereas the cyclohexanone selectivity is attributed to the nitrogen-containing nature of PANI/CNT.
Co-reporter:Dr. Jinzhu Chen;Wei Zhang;Dr. Limin Chen;Dr. Longlong Ma;Dr. Hui Gao;Dr. Tiejun Wang
ChemPlusChem 2013 Volume 78( Issue 2) pp:
Publication Date(Web):
DOI:10.1002/cplu.201390006
Co-reporter:Dr. Jinzhu Chen;Jing Huang;Dr. Limin Chen;Dr. Longlong Ma;Dr. Tiejun Wang;Dr. Uzma I. Zakai
ChemCatChem 2013 Volume 5( Issue 6) pp:1598-1605
Publication Date(Web):
DOI:10.1002/cctc.201200582
Abstract
Using phenolic bio-oil as feedstock for sustainable production of alkane fuels is of great significance. Here, the hydrodeoxygenation of phenol and its derivatives has been systematically investigated in aqueous media with a dual-functional catalyst system consisting of water-soluble, ionic liquid-like copolymer A-stabilized nanocatalysts and the mineral acid H3PO4. The developed Ru/A-H3PO4 catalyst system achieved a complete phenol conversion with cyclohexane selectivity higher than 99 %, making it by far one of the most efficient systems for phenol hydrodeoxygenation. Mercury poisoning experiments revealed that the in situ generated Ru nanoparticles are true a heterogeneous catalyst for hydrogenation. The catalytic activity of metal site for phenol hydrodeoxygenation to cyclohexane decreased with the order of Ru>Rh>Pt≫Pd. Our findings also demonstrated the delicate balance between activity and stability of ionic liquid-like copolymer-stabilized nanocatalysts. The research highlights an efficient catalyst system of transforming phenols into alkanes.
Co-reporter:Hualiang Zuo, Qiying Liu, Tiejun Wang, Longlong Ma, Qi Zhang, and Qing Zhang
Energy & Fuels 2012 Volume 26(Issue 6) pp:3747-3755
Publication Date(Web):May 14, 2012
DOI:10.1021/ef300063b
Catalytic hydrodeoxygenation (HDO) of vegetable oils to renewable alkane-type biofuels has attracted more and more concern in recent years. However, the presently used catalysts were mainly focused on the sulfided CoMo and NiMo catalysts, which inevitably posed sulfur contamination in final products. Therefore, exploring nonsulfured catalyst for this processing is of fundamental importance, but it is still an open challenge. In this paper, we prepared the sulfur free Ni supported on SiO2, γ-Al2O3, SAPO-11, HZSM-5, and HY by incipient wetness impregnation and tested the catalytic performance in HDO of methyl palmitate. Alkanes with long carbon chains were mainly produced with two possibly parallel approaches: hydrogenation of hexadecanal to hexadecanol, followed by dehydration/hydrogenation to C16 alkane and decarbonylaton/decarboxylation of hexadecanoic acid to C15 alkane. The acidity of catalysts significantly influenced their catalytic performance, and the Ni/SAPO-11 catalysts with weak and medium acidity showed superior properties to the other catalysts due to the synergistic effect of metal Ni and acidic support. The maximum yield of 93% for C15+ alkanes was observed over 7 wt % Ni/SAPO-11 under the mild reaction conditions of 493 K and 2 MPa, indicating its promising application in this reaction.
Co-reporter:Dr. Qing Zhang;Dr. Ting Jiang;Dr. Bing Li; Tiejun Wang;Dr. Xinghua Zhang;Dr. Qi Zhang; Longlong Ma
ChemCatChem 2012 Volume 4( Issue 8) pp:1084-1087
Publication Date(Web):
DOI:10.1002/cctc.201100508
Co-reporter:Qing Zhang, Ke Qiu, Bing Li, Ting Jiang, Xinghua Zhang, Longlong Ma, Tiejun Wang
Fuel 2011 Volume 90(Issue 11) pp:3468-3472
Publication Date(Web):November 2011
DOI:10.1016/j.fuel.2011.06.046
Ni/HZSM-5 catalysts calcined at different temperatures were used in the isoparaffin production by aqueous phase processing of sorbitol and characterized by N2 physical adsorption, temperature-programmed reduction (H2-TPR), temperature-programmed desorption of ammonia (NH3-TPD) and Raman techniques. The effect of calcination temperature of the catalysts on the catalytic performance for the reaction was investigated. The activity test results indicated that the maximal i-C6H14 selectivity of 45.4% and the total i-C6H14 and i-C5H12 yield of 32.3% were obtained over the catalyst calcined at 500 °C, which exhibited the optimum surface area and pore structure with 100% of the reducibility of Ni species on the surface of HZSM-5. In addition, the amount and the strength distribution of acidic surface sites of the catalyst decreased with the increase of calcination temperature at 500 °C above. All these factors result in an increase in the formation of isoparaffin.Graphical abstractNi/HZSM-5 catalyst was developed with high catalytic activity for aqueous phase processing of sorbitol. The isoparaffin yield was affected distinctly by calcination temperature of the catalyst. The catalysts were characterized and such effect by calcination temperature was investigated in substance.Highlights► Development of an efficient Ni/HZSM-5 catalyst for sorbitol hydrogenation. ► Skillful integration of metal centers and acidic sites for isoparaffin production. ► Optimizing the interaction between Ni and the support by proper calcination.
Co-reporter:Xinghua Zhang, Tiejun Wang, Longlong Ma, Qi Zhang, Xiaoming Huang, Yuxiao Yu
Applied Energy (December 2013) Volume 112() pp:
Publication Date(Web):1 December 2013
DOI:10.1016/j.apenergy.2013.04.077
•ZrO2–SiO2 mixed oxides as catalyst supports.•ZrO2–SiO2 mixed oxides possess amphoteric character and excellent textural properties.•Phenol and guaiacol were completely converted over Ni/ZrO2–SiO2 catalyst.•The selectivity for the desired product cyclohexane was in excess of 90%.The main products of lignin degradation are phenolic compounds. It is meaningful to study the processes by which cyclohexane is produced from phenolic compounds via hydrodeoxygenation (HDO), because it could be used as fuel additives, chemical feedstock and solvent. In this work, support material ZrO2–SiO2 mixed oxides with different Si/Zr ratio were synthesized, and a series of Ni/SiO2–ZrO2 catalysts with different Ni loading were prepared by impregnation method. The exploration of HDO process was carried out using phenol and guaiacol as model compounds. Effects of Si/Zr ratio, Ni loading and reaction temperature on conversion of phenol and guaiacol as well as distribution of HDO products were systematically investigated. The results showed that almost all of phenol and guaiacol could be effectively converted into O-free products. And the selectivity of cyclohexane was in excess of 90%.
Co-reporter:Tiejun Wang, Yong Yang, Mingyue Ding, Qiying Liu, Longlong Ma
Applied Energy (December 2013) Volume 112() pp:
Publication Date(Web):1 December 2013
DOI:10.1016/j.apenergy.2013.05.054
•A novel reformer with porous ceramic tube circled by electric wire was designed.•The temperature uniformities along diameter and axial direction were measured.•The auto-thermal reforming of model and real biomass fuel gas was performed.•The hot electron promoted biomass fuel gas elimination mechanism was proposed.A novel reformer with porous ceramic oxygen distribution tube circled by electric wire for inspiring hot electron was designed for auto-thermal reforming of biomass raw fuel gas to produce syngas (H2 + CO). The temperature of auto-thermal reformer was nearly uniform due to the excellent performance of partial oxygenation reaction in the reformer with porous ceramic tube for oxygen partitioning. The hot-electron inspired by electric wire promoted the cracking of biomass tar to form radical species, which were converted effectively to syngas over nickel based catalyst. The hot-electron also played an essential role in decreasing coke deposition on the surface of nickel based catalyst, which prolonged the lifetime of the reforming catalyst.
Co-reporter:Lungang Chen, YuPing Li, Xinghua Zhang, Qi Zhang, Tiejun Wang, Longlong Ma
Applied Catalysis A: General (20 May 2014) Volume 478() pp:117-128
Publication Date(Web):20 May 2014
DOI:10.1016/j.apcata.2014.03.038
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