焙烧温度对Ni/La(Ⅲ)催化剂氢解山梨醇制备低碳二元醇性能的影响

曹晓峰; 张琦; 姜东; 刘琪英; 马隆龙; 王铁军; 李德宝

焙烧温度对Ni/La(Ⅲ)催化剂氢解山梨醇制备低碳二元醇性能的影响

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001;
2.
中国科学院大学, 北京 100049;
3.
中国科学院广州能源研究所中科院可再生能源重点实验室, 广东广州 510640

基金项目: 国家自然科学基金(51376185);国家重点基础研究发展规划(973计划,2012CB215304);国家高技术研究发展计划(863计划,2012AA101806);广东省自然科学基金(S2013010011612)。

详细信息

通讯作者:
姜东,副研究员,E-mail:jdred@sxicc.ac.cn;刘琪英,副研究员,,E-mail:liuqy@ms.giec.ac.cn。

中图分类号: O643.32
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出版历程
- 收稿日期: 2015-01-26
- 修回日期: 2015-03-23
- 刊出日期: 2015-08-30

Influence of calcination temperature on the performance of Ni/La(III) catalyst in the hydrogenolysis of sorbitol to low-carbon glycols

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China;
3.
CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

摘要

摘要: 采用水热法合成了纳米棒状La(OH)₃载体,通过湿式浸渍方法制备了10%Ni/La(Ⅲ)负载型催化剂,考察了500~800℃不同焙烧温度对于催化剂氢解山梨醇制备低碳二元醇的影响,结合XRD、SEM/EDS、BET、H₂-TPR-MS、CO/CO₂-TPD-MS、TG和ICP-AES等表征手段对Ni/La(Ⅲ)催化剂的构效关系进行了分析。结果表明,Ni/La(Ⅲ)催化剂表现出高的氢解反应活性,在较低的焙烧温度下(500℃)催化剂主要以NiO/La₂O₂CO₃结构形式存在。随着焙烧温度的升高,NiO/La₂O₂CO₃逐渐向La₂NiO₄-La₂O₃进行转变。碱性是影响不同催化剂活性的决定因素,高的焙烧温度促进了催化剂中强碱性位的生成,显著提高了氢解反应活性,但对液体产物的选择性无明显影响,在220℃、4MPa H₂、1.5h的条件下,山梨醇完全转化,低碳二元醇的产率可达到53%。低的焙烧温度则增加了催化剂的水热稳定性。催化剂的失活主要归结于活性金属粒子在水相反应中从载体表面脱落而发生团聚,降低氢解反应活性。
- 山梨醇 /
- 氢解 /
- 低碳二元醇 /
- 焙烧温度 /
- La₂O₂CO₃
Abstract: Nanorod-shaped La(OH)₃ support was prepared by hydrothermal method, over which the supported Ni/La(III) catalysts were obtained through wet impregnation method; the influence of calcination temperature on the performance of Ni/La(III) catalyst in the hydrogenolysis of sorbitol to low-carbon glycols was then investigated by means of XRD, SEM/EDS, BET, H₂-TPR-MS, CO/CO₂-TPD-MS, ICP-AES and TG. The results revealed that the Ni/La(III) catalysts are highly active for sorbitol hydrogenolysis; the yield of low-carbon glycols reaches 53% after reaction at 220℃ and 4 MPa H₂ for 1.5 h. The catalyst calcined at low temperature (500℃) is mainly in the form of NiO/La₂O₂CO₃, which may transform into La₂NiO₄-La₂O₃ with the increase of calcination temperature. The basicity is a crucial factor for the hydrogenolysis activity; high calcionation temperature may enhance the basicity of the catalysts and then improve their hydrogenolysis activity, whereas the calcination temperature has little effect on the products selectivity. However, NiO/La₂O₂CO₃ exhibits better hydrothermal stability than La₂NiO₄-La₂O₃ for sorbitol hydrogenolysis. The deactivation of catalysts can be attributed to the separation of active Ni particles from the support and the agglomeration of the active species, which may reduce the amount of the active metal sites and destroy the catalyst structure.
- sorbitol /
- hydrogenolysis /
- low-carbon glycols /
- calcination temperature /
- La₂O₂CO₃

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参考文献(31)

HUBER G W, IBORRA S, CORMA A. Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering[J]. Chem Rev, 2006, 106(9): 4044-4098.

The Pacific Northwest National Laboratory (PNNL), the National Renewable Energy Laboratory (NREL). Top value added chemicals from biomass[Z]. 2004.

CORMA A, IBORRA S, VELTY A. Chemical routes for the transformation of biomass into chemicals[J]. Chem Rev, 2007, 107(6): 2411-2502.

KOBAYASHI H, HOSAKA Y, HARA K, FENG B, HIROSAKI Y, FUKUOKA A. Control of selectivity, activity and durability of simple supported nickel catalysts for hydrolytic hydrogenation of cellulose[J]. Green Chem, 2014, 16(2): 637-644.

JIN X, JESSICA L, BALA S, REN S Q, RAGHUNATH V C. Lattice-matched bimetallic CuPd-graphene nanocatalysts for facile conversion of biomass-derived polyols to chemicals[J]. ACS Nano, 2012, 7(2): 1309-1316.

AGNIESZKA M R, KAMIL W, REGINA P. Hydrogenolysis goes bio: From carbohydrates and sugar alcohols to platform chemicals[J]. Angew Chem, 2012, 51(11): 2564-2601.

马继平, 于维强, 王敏, 贾秀全, 路芳, 徐杰. 催化选择转化多羟基化合物制备商附加值化学品研究进展[J]. 催化学报, 2013, 34(3): 492-507. (MA Ji-ping, YU Wei-qing, WANG Min, JIA Xiu-quan, LU Fang, XU Jie. Advances in selective catalytic transformation of ployols to value-added chemicals[J]. Chin J Catal, 2013, 34(3): 492-507.)

刘琪英, 廖玉河, 石宁, 王铁军, 马隆龙, 张琦. 生物质多元醇选择性催化氢解制小分子二元醇研究进展[J]. 化工进展, 2013, 32(5): 1035-1042. (LIU Qi-ying, LIAO Yu-he, SHI Ning, WANG Tie-jun, MA Long-long, ZHANG Qi. A review on small molecular diols production by catalytic hydrogenolysis of biomass derived polyols[J]. Chem Ind Eng Prog, 2013, 32(5): 1035-1042.)

KEYI W, MARTIN C H, TODD D F. Mechanism study of sugar and sugar alcohol hydrogenolysis using 1,3-diol model compounds[J]. Ind Eng Chem Res, 1995, 34(11): 3766-3771.

SOHOUNLOUE D K, MONTASSIER C, BARBIER J. Catalytic hydrogenolysis of sorbitol[J]. React Kinet Catal Lett, 1983, 22(3/4): 391-397.

BANU M, SIVASANKER S, SANKARANARAYANAN T M, VENUVANALINGAM P. Hydrogenolysis of sorbitol over Ni and Pt loaded on NaY[J]. Catal Commun, 2011, 12(7): 673-677.

BANU M, VENUVANALINGAM P, SHANMUGAM R, VISWANATHAN B, SIVASANKER S. Sorbitol hydrogenolysis over Ni, Pt and Ru supported on NaY[J]. Top Catal, 2012, 5511/13): 897-907.

ZHAO L, ZHOU J H, SUI Z J, ZHOU X G. Hydrogenolysis of sorbitol to glycols over carbon nanofiber supported ruthenium catalyst[J]. Chem Eng Sci, 2010, 65(1): 30-35.

ZHAO L, ZHOU J H, CHEN H, ZHANG M G, SUI Z J, ZHOU X G. Carbon nanofibers supported Ru catalyst for sorbitol hydrogenolysis to glycols: Effect of calcination[J]. Korean J Chem Eng, 2010, 27(5): 1412-1418.

ZHOU J H, ZHANG M G, ZHAO L, ZHOU J H. Carbon nanofiber/graphite-felt composite supported Ru catalysts for hydrogenolysis of sorbitol[J]. Catal Today, 2009, 147(S): 225-229.

CHEN X G, WANG X C, YAO S X, MU X D. Hydrogenolysis of biomass-derived sorbitol to glycols and glycerol over Ni-MgO catalysts [J]. Catal Commun, 2013, 39(5): 86-89.

HUANG Z W, CHEN J, JIA Y Q, LIU H L, XIA C G, LIU H C. Selective hydrogenolysis of xylitol to ethylene glycol and propylene glycol over copper catalysts[J]. Appl Catal B: Environ, 2014, 147: 377-386.

SUN J Y, LIU H C. Selective hydrogenolysis of biomass-derived xylitol to ethylene glycol and propylene glycol on Ni/C and basic oxide-promoted Ni/C catalysts[J]. Catal Today, 2014, 234: 75-82.

LIU H L, HUANG Z W, XIA C G, JIA Y Q, CHEN J, LIU H C. Selective hydrogenolysis of xylitol to ethylene glycol and propylene glycol over silica dispersed copper catalysts prepared by a precipitation-gel method[J]. ChemCatChem, 2014, 10(6): 2918-2928.

SUN H, DING Y Q, DUAN J Z, ZHANG Q J, WANG Z Y, LOU H, ZHENG X M Transesterification of sunflower oil to biodiesel on ZrO₂ supported La₂O₃ catalyst[J]. Bioresour Technol, 2010, 101(3): 953-958.

YANG G X, YU H, HUANG X Y, PENG F, WANG H J. Effect of calcium dopant on catalysis of Ir/La₂O₃ for hydrogen production by oxidative steam reforming of glycerol[J]. Appl Catal B: Environ, 2012, 127: 89-98.

ROELOFS J C A A, LENSVELD D J, DILLEN A J, JONG K P. On the structure of activated hydrotalcites as solid base catalysts for liquid-phase aldol condensation[J]. J Catal, 2001, 203(1): 184-191.

GAO J, HOU Z Y, GUO J Z, ZHU Y H, ZHENG X M. Catalytic conversion of methane and CO₂ to synthesis gas over a La₂O₃-modified SiO₂ supported Ni catalyst in fluidized-bed reactor[J]. Catal Today, 2008, 131(1/4): 278-284.

COSTA C N, ANASTASIADOU T, EFSTATHIOU A M. The selective catalytic reduction of nitric oxide with methane over La₂O₃-CaO systems: Synergistic effects and surface reactivity studies of NO, CH₄, O₂, and CO₂ by transient techniques[J]. J Catal, 2000, 194(2): 250-265.

MUHAMMAD B I C, MOHAMMAD M. H, PAUL A C. Effect of supercritical water gasification treatment on Ni/La₂O₃-Al₂O₃-based catalysts[J]. Appl Catal A: Gen, 2011, 405: 84-92.

MU Q T, WANG Y D. Synthesis, characterization, shape-preserved transformation, and optical properties of La(OH)₃, La₂O₂CO₃, and La₂O₃ nanorods[J]. J Alloy Comp, 2011, 509(2): 396-401.

WANG F, SHI R J, LIU Z Q, SHANG P J, PANG X Y, SHEN S, FENG Z C, LI C, SHEN W J. Highly efficient dehydrogenation of primary aliphatic alcohols catalyzed by Cu nanoparticles dispersed on rod-shaped La₂O₂CO₃[J]. ACS Catal, 2013, 3(5): 890-894.

ZHANG X H, WANG T J, MA L L, ZHANG Q, YU Y X, LIU Q Y. Characterization and catalytic properties of Ni and NiCu catalysts supported on ZrO₂-SiO₂ for guaiacol hydrodeoxygenation[J]. Catal Commun, 2012, 33: 15-19.

RACHA A, TOMOO M, TAKATO M, KOICHIRO J, KIYOTOMY K. Highly selective hydrogenolysis of glycerol to 1, 3-propanediol over a boehmite-supported platinum/tungsten catalyst[J]. ChemSusChem, 2013, 6(8): 1345-1347.

SUN C W, XIAO G L, LI H, CHEN L Q. Mesoscale organization of flower-Like La₂O₂CO₃ and La₂O₃ microspheres[J]. J Am Cera Soc, 2007, 90(8): 2573-2581.

SUN R Y, WANG T T, ZHENG M Y, DENG W Q, PANG J F, WANG A Q, WANG X D, ZHANG T. Versatile nickel-lanthanum(III) catalyst for direct conversion of cellulose to glycols[J]. ACS Catal, 2015, 5: 874-883.

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