MoS_2基催化剂上生物质基合成气制乙醇
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摘要
生物质作为重要的可再生绿色能源,由于资源丰富,分布广泛,S、N含量低,CO_2零排放等优点,必将为实现可持续发展起到举足轻重的作用。乙醇作为一种最具潜能的汽油添加剂及化石燃料替代品,具有辛烷值高,无污染等优点。因此,催化生物质基合成气制乙醇作为可再生能源开发的途径之一,极具研究价值及工业价值。综述MoS_2基催化剂上生物质基合成气制乙醇的重要研究进展,指出利用合成气催化制乙醇的效率还有待进一步提高,尚未达到实际应用要求。改性MoS_2基催化剂对乙醇选择性较高,但烃类及CO_2副产物较多。为了促进乙醇的生成,今后合成气催化制乙醇应深入系统的研究碱金属和过渡金属共同促进的MoS_2基催化剂,并借助科学技术发展运用新方法和新思路,制备高效、稳定的催化剂。
As clean and renewable non-fossil energy sources,biomass will play an important role in the sustainable development of energy because of widely distributed huge reserves,low contents of nitrogen and sulfur,and CO_2 neutrality.As the most potential gasoline additive and alternative fuel for the replacement of fossil fuels,ethanol has the advantages of high octane number and no environmental pollution.Thus,heterogeneous catalytic synthesis of ethanol from biomass-derived syngas is a promising way for the development of renewable energy sources and of great research and commercial values.This paper briefly reviews the progresses and advances in the field of catalytic conversion of syngas to ethanol and points out that the efficiency of the catalytic conversion of syngas to ethanol is far from industrial application and needs to be further improved.Modified MoS_2-based catalyst could enhance selectivity of ethanol,but also promote formation of hydrocarbons and CO_2.In order to facilitate the production of ethanol,stable and efficient MoS_2 based catalyst promoted by alkalis and transition metal should be studied systematically via new techniques and methods.
As clean and renewable non-fossil energy sources,biomass will play an important role in the sustainable development of energy because of widely distributed huge reserves,low contents of nitrogen and sulfur,and CO_2 neutrality.As the most potential gasoline additive and alternative fuel for the replacement of fossil fuels,ethanol has the advantages of high octane number and no environmental pollution.Thus,heterogeneous catalytic synthesis of ethanol from biomass-derived syngas is a promising way for the development of renewable energy sources and of great research and commercial values.This paper briefly reviews the progresses and advances in the field of catalytic conversion of syngas to ethanol and points out that the efficiency of the catalytic conversion of syngas to ethanol is far from industrial application and needs to be further improved.Modified MoS_2-based catalyst could enhance selectivity of ethanol,but also promote formation of hydrocarbons and CO_2.In order to facilitate the production of ethanol,stable and efficient MoS_2 based catalyst promoted by alkalis and transition metal should be studied systematically via new techniques and methods.
引文
[1]BP Energy.https://www.bp.com/content/dam/bp-country/zh_cn/Publications/StatsReview 2017/2017.pdf.
[2]查湘义.生物质能源化利用技术综述[J].甘肃农业,2014,(1):30-31.
[3]冯小芹.生物质利用技术的研究进展[J].安徽农业科学,2011,39(15):9207-9209.Feng Xiaoqing.Research advances of biomass utilization technology[J].Journalof Anhui Agricultural Sciences,2011,39(15):9207-9209.
[4]蒋剑春.生物质能源应用研究现状与发展前景[J].林产化学与工业,2002,22(2):75-80.JiangJianchun.Prospect on research and development of biomass energy utilization[J].Chemistry and Industry of Forest Products,2002,22(2):75-80.
[5]孙孝仁.21世纪世界能源发展前景[J].中国能源,2001,(2):19-20.SongXiaoren.Prospect of world energy development in 21 century[J].Energy of China,2001,(2):19-20.
[6]能源基金会.世界主要国家生物液体燃料政策研究报告[EB/OL].2014-05-01. http://www.efchina.org/Reports-zh/reports-20140501-zh.
[7]Zhou N,Huo M,Wu H,et al.Low temperature spray combustion of acetone-butanol-ethanol (ABE) and diesel blends[J].Applied Energy,2014,117:104-115.
[8]Ni Y,SunZ.Recent progress on industrial fermentative production of acetone-butanol-ethanol by Clostridium acetobutylicum in China[J].Applied Microbiology and Biotechnology,2009,83:415-424.
[9]Sun Y,Cheng J.Hydrolysis of lignocellulosic materials for ethanol production:a review[J].Bioresource Technology,2002,83:1-11.
[10]Moser W R,Connolly K E.Synthesis and characterization of copper-modified zinc chromites by the high temperature aerosol decomposition process for higher alcohol synthesis[J].Chemical Engineering Journal,1996,64:239-246.
[11]Mahdavi V,Peyrovi M H.Synthesis of C1-C6 alcohols over copper/cobalt catalysts:Investigation of the influence of preparative procedures on the activity and selectivity of Cu-Co2O3/ZnO,Al2O3 catalyst[J].Catalysis Communication,2006,7:542-549.
[12]Ng T K,Busche R M,Mcdonald C C,et al.Production of feedstock chemicals[J].Science,1983,219:733-740.
[13]Herman R G.Advances in catalytic synthesis and utilization of higher alcohols[J].Catalysis Today,2000,55:233-245.
[14]Deluga D A,Salge J R,Schmidt L D,et al.Renewable hydrogen from ethanol by autothermal reforming[J].Science,2004,303:993-997.
[15]Ferreira-Aparicio P,Benito M J,Sanz J L.New trends in reforming technologies:from hydrogen industrial plants to multifuel microreformers[J].Catalysis Reviews-Science and Engineering,2005,47:491-588.
[16]Fougret C M,Holderich W F.Ethylene hydration over metal phosphates impregnated with phosphoric acid[J].Applied Catalysis A:General,2001,207:295-301.
[17]Rostrup-Nielseu J R.Making fuels from biomass[J].Science,2005,308:1421-1422.
[18]Gray K A,Zhao L,Emptage M.Currentopinion in chemical biology[J].Current Opinion in Chemical Biology,2006,10:141-146.
[19]Zhang B W,Sheng T,Wang Y X,et al.Platinum-cobalt bimetallic nanoparticles with Pt skin for electro-oxidation of ethanol[J].ACS Catalysis,2017,7:892-895.
[20]Huber G W,Iborra S,Corma A.Synthesis of transportation fuels from biomass:chemistry, catalysts,and engineering[J].Chemical Reviews,2006,106:4044-4098.
[21]Bridgwater A V.Renewable fuels and chemicals by thermal processing of biomass[J]. Chemical Engineering Journal,2003,91:87-102.
[22]Andries J,Buhre B J P.Small-scale,distributed generation of electricity and heat using integrated biomass gasification-gas turbine-fuel cell systems[B].DGMK Tagungsber,2000,115-125.
[23]Jackson G R, Mahajan D.Method for production of mixed alcohols from synthesis gas:US,6248796[P].2001-06-19.
[24]Stevens R R.Process for producing alcohols from synthesis gas:US,4882360[P]1989-11-21.
[25]Kinkade N E.Tantalum-containing catalyst useful for producing alcohols from synthesis gas:US,4994498[P].1991-02-19.
[26]Li D,Yang C,Li W,et al.Ni/ADM:a high activity and selectivity to C2+OH catalyst for catalytic conversion of synthesis gas to C1-C5 mixed alcohols[J].Topics in Catalysis,2005,32:233-239.
[27]Upton B H,Chen C C,Rodriguez N M,et al.In situ electron microscopy studies of the interaction of iron,cobalt,and nickel with molybdenum disulfide single crystals in hydrogen[J].Journal of Catalysis,1993,141:171-190.
[28]Liu Z,Li X,Close M R.Screeningof alkali-promoted vapor-phase-synthesized molybdenum sulfide catalysts for the production of alcohols from synthesis gas[J].Industrial & Engineering Chemistry Research,1997,36(8):3085-3093.
[29]Muramatsu A,Tatsumi T,Tominaga H.Mixed alcohol synthesis from CO-H2 by use of KCl-promoted Mo/SiO2catalysts[J].Bulletin of the Chemical Society of Japan,1987,60:3157-3161.
[30]Woo H C,Park T Y,Kim Y G,et al.Alkali-promoted MoS2catalysts for alcohol synthesis:the effect of alkali promotiom and preparation condition on activity and selectivity[J].Studies in Surface Science and Catalysis,1993,75:2749-2752.
[31]Iranmahboob J,Toghiani H,Hill D O.Dispersion of alkali on the surface of Co-MoS2/clay catalyst:a comparison of K and Cs as a promoter for synthesis of alcohol[J].Applied Catalysis A:General,2003,247:207-218.
[32]Iranmahboob J,Hill D O.Alcohol synthesis from syngas over K2CO3/CoS/MoS2 on activated carbon[J].Catalysis Letters,2002,78:49-55.
[33]Smith K J,Herman R G,Klier K.Kinetic modelling of higher alcohol synthesis over alkali-promoted Cu/ZnO and MoS2 catalysts[J].Chemical Engineering Science,1990,45:2639-2646.
[34]Qi H J,Li D B,Yang C,et al.Nickel and manganese co-modified K/MoS2catalyst:high performance for higher alcohols synthesis from CO hydrogenation[J].Catalysis Communications,2003,4:339-342.
[35]Sehested J,Dahl S,Jacobsen J,et al.Methanation of CO over nickel:mechanism and kinetics at high H2/CO ratios[J].Journal of Physical Chemistry B,2005,109:2432-2438.
[36]Li D,Yang C,Qi H,et al.Higher alcohol synthesis over a La promoted Ni/K2CO3/MoS2 catalyst[J].Catalysis Communications,2004,5:605-609.
[37]Li Z,Fu Y,Jiang M.Structures and performance of Rh-Mo-K/Al2O3 catalysts used for mixed alcohol synthesis from synthesis gas[J].Applied Catalysis A:General,1999,187:187-198.
[38]Li Z R,Fu Y L,Jiang M,et al.Active carbon supported Mo-K catalysts used for alcohol synthesis[J].Journal of Catalysis,2001,199(2):155-161.
[39]Surisetty V R,Tavasoli A,Dalai A K.Synthesis of higher alcohols from syngas over alkali promoted MoS2 catalysts supported on multi-walled carbon nanotubes[J].Applied Catalysis A:General,2009,365:243-251.
[40]Tatsumi T,Muramatsu A,Tominaga H O.Supported molybdenum catalysts for alcohol synthesis from CO-H2[J].Applied Catalysis,1987,34(1-2):77-88.
[41]Surisetty V R,Dalai A K,Kozinski J.Synthesis of higher alcohols from synthesis gas over Co-promoted alkali-modified MoS2 catalysts supported on MWCNTs[J].Applied Catalysis A:General,2010,385:153-162.
[42]Storm D A.The production of higher alcohols from syngas using potassium promoted Co/Mo/Al2O3 and Rh/Co/Mo/Al2O3[J].Topics in Catalysis,1995,2:91-101.
[43]Bian G Z,Fu Y L,Ma Y S.Structure of Co-K-Mo/γ-Al2O3 catalysts and their catalytic activity for mixed alcohols synthesis[J].Catalysis Today,1999,51:187-193.
[44]Li Z G,Fu Y L,Bao J,et al.Effect of cobalt promoter on Co-Mo-K/C catalysts used for mixed alcohol synthesis[J].Applied Catalysis A:General,2001,220:21-30.
[45]Fu Y L,Fujimoto K,Lin P Y,et al.Effect of calcination conditions of the oxidized precursor on the structure of a sulfided K-Mo/γ-Al2O3, catalyst for mixed alcohol synthesis[J].Applied Catalysis A:General,1995,126(2):273-285.
[46]Tavasoli A,Abbaslou R M M,Trepanier M,et al.Fischer-Tropsch synthesis over cobalt catalyst supported on carbon nanotubes in a slurry reactor[J].Applied Catalysis A:General,2008,345:134-142.
[47]Ma X M,Lin G D,Zhang H B.Co-decorated carbon nanotube-supported Co-Mo-K sulfide catalyst for higher[J].Catalysis Lettters,2006,111(3-4):141-151.
[48]Tatsumi T,Muramatsu A,Tominaga H.Importance of sequence of impregnation in the activity development of alkali-promoted Mo catalysts for alcohol synthesis from CO + H2[J].Journal of Catalysis,1986,101:553-556.
[49]Lu G,Zhang C F,Gang Y Q,et al.Synthesis of mixed alcohols from CO2 contained syngas on supported molybdenum sulfide catalysts[J].Applied Catalysis A:General,1997,150:243-252.
[50]Fang K G,Li D B,Lin M G,et al.A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas[J].Catalysis Today,2009,147:133-138.
[2]查湘义.生物质能源化利用技术综述[J].甘肃农业,2014,(1):30-31.
[3]冯小芹.生物质利用技术的研究进展[J].安徽农业科学,2011,39(15):9207-9209.Feng Xiaoqing.Research advances of biomass utilization technology[J].Journalof Anhui Agricultural Sciences,2011,39(15):9207-9209.
[4]蒋剑春.生物质能源应用研究现状与发展前景[J].林产化学与工业,2002,22(2):75-80.JiangJianchun.Prospect on research and development of biomass energy utilization[J].Chemistry and Industry of Forest Products,2002,22(2):75-80.
[5]孙孝仁.21世纪世界能源发展前景[J].中国能源,2001,(2):19-20.SongXiaoren.Prospect of world energy development in 21 century[J].Energy of China,2001,(2):19-20.
[6]能源基金会.世界主要国家生物液体燃料政策研究报告[EB/OL].2014-05-01. http://www.efchina.org/Reports-zh/reports-20140501-zh.
[7]Zhou N,Huo M,Wu H,et al.Low temperature spray combustion of acetone-butanol-ethanol (ABE) and diesel blends[J].Applied Energy,2014,117:104-115.
[8]Ni Y,SunZ.Recent progress on industrial fermentative production of acetone-butanol-ethanol by Clostridium acetobutylicum in China[J].Applied Microbiology and Biotechnology,2009,83:415-424.
[9]Sun Y,Cheng J.Hydrolysis of lignocellulosic materials for ethanol production:a review[J].Bioresource Technology,2002,83:1-11.
[10]Moser W R,Connolly K E.Synthesis and characterization of copper-modified zinc chromites by the high temperature aerosol decomposition process for higher alcohol synthesis[J].Chemical Engineering Journal,1996,64:239-246.
[11]Mahdavi V,Peyrovi M H.Synthesis of C1-C6 alcohols over copper/cobalt catalysts:Investigation of the influence of preparative procedures on the activity and selectivity of Cu-Co2O3/ZnO,Al2O3 catalyst[J].Catalysis Communication,2006,7:542-549.
[12]Ng T K,Busche R M,Mcdonald C C,et al.Production of feedstock chemicals[J].Science,1983,219:733-740.
[13]Herman R G.Advances in catalytic synthesis and utilization of higher alcohols[J].Catalysis Today,2000,55:233-245.
[14]Deluga D A,Salge J R,Schmidt L D,et al.Renewable hydrogen from ethanol by autothermal reforming[J].Science,2004,303:993-997.
[15]Ferreira-Aparicio P,Benito M J,Sanz J L.New trends in reforming technologies:from hydrogen industrial plants to multifuel microreformers[J].Catalysis Reviews-Science and Engineering,2005,47:491-588.
[16]Fougret C M,Holderich W F.Ethylene hydration over metal phosphates impregnated with phosphoric acid[J].Applied Catalysis A:General,2001,207:295-301.
[17]Rostrup-Nielseu J R.Making fuels from biomass[J].Science,2005,308:1421-1422.
[18]Gray K A,Zhao L,Emptage M.Currentopinion in chemical biology[J].Current Opinion in Chemical Biology,2006,10:141-146.
[19]Zhang B W,Sheng T,Wang Y X,et al.Platinum-cobalt bimetallic nanoparticles with Pt skin for electro-oxidation of ethanol[J].ACS Catalysis,2017,7:892-895.
[20]Huber G W,Iborra S,Corma A.Synthesis of transportation fuels from biomass:chemistry, catalysts,and engineering[J].Chemical Reviews,2006,106:4044-4098.
[21]Bridgwater A V.Renewable fuels and chemicals by thermal processing of biomass[J]. Chemical Engineering Journal,2003,91:87-102.
[22]Andries J,Buhre B J P.Small-scale,distributed generation of electricity and heat using integrated biomass gasification-gas turbine-fuel cell systems[B].DGMK Tagungsber,2000,115-125.
[23]Jackson G R, Mahajan D.Method for production of mixed alcohols from synthesis gas:US,6248796[P].2001-06-19.
[24]Stevens R R.Process for producing alcohols from synthesis gas:US,4882360[P]1989-11-21.
[25]Kinkade N E.Tantalum-containing catalyst useful for producing alcohols from synthesis gas:US,4994498[P].1991-02-19.
[26]Li D,Yang C,Li W,et al.Ni/ADM:a high activity and selectivity to C2+OH catalyst for catalytic conversion of synthesis gas to C1-C5 mixed alcohols[J].Topics in Catalysis,2005,32:233-239.
[27]Upton B H,Chen C C,Rodriguez N M,et al.In situ electron microscopy studies of the interaction of iron,cobalt,and nickel with molybdenum disulfide single crystals in hydrogen[J].Journal of Catalysis,1993,141:171-190.
[28]Liu Z,Li X,Close M R.Screeningof alkali-promoted vapor-phase-synthesized molybdenum sulfide catalysts for the production of alcohols from synthesis gas[J].Industrial & Engineering Chemistry Research,1997,36(8):3085-3093.
[29]Muramatsu A,Tatsumi T,Tominaga H.Mixed alcohol synthesis from CO-H2 by use of KCl-promoted Mo/SiO2catalysts[J].Bulletin of the Chemical Society of Japan,1987,60:3157-3161.
[30]Woo H C,Park T Y,Kim Y G,et al.Alkali-promoted MoS2catalysts for alcohol synthesis:the effect of alkali promotiom and preparation condition on activity and selectivity[J].Studies in Surface Science and Catalysis,1993,75:2749-2752.
[31]Iranmahboob J,Toghiani H,Hill D O.Dispersion of alkali on the surface of Co-MoS2/clay catalyst:a comparison of K and Cs as a promoter for synthesis of alcohol[J].Applied Catalysis A:General,2003,247:207-218.
[32]Iranmahboob J,Hill D O.Alcohol synthesis from syngas over K2CO3/CoS/MoS2 on activated carbon[J].Catalysis Letters,2002,78:49-55.
[33]Smith K J,Herman R G,Klier K.Kinetic modelling of higher alcohol synthesis over alkali-promoted Cu/ZnO and MoS2 catalysts[J].Chemical Engineering Science,1990,45:2639-2646.
[34]Qi H J,Li D B,Yang C,et al.Nickel and manganese co-modified K/MoS2catalyst:high performance for higher alcohols synthesis from CO hydrogenation[J].Catalysis Communications,2003,4:339-342.
[35]Sehested J,Dahl S,Jacobsen J,et al.Methanation of CO over nickel:mechanism and kinetics at high H2/CO ratios[J].Journal of Physical Chemistry B,2005,109:2432-2438.
[36]Li D,Yang C,Qi H,et al.Higher alcohol synthesis over a La promoted Ni/K2CO3/MoS2 catalyst[J].Catalysis Communications,2004,5:605-609.
[37]Li Z,Fu Y,Jiang M.Structures and performance of Rh-Mo-K/Al2O3 catalysts used for mixed alcohol synthesis from synthesis gas[J].Applied Catalysis A:General,1999,187:187-198.
[38]Li Z R,Fu Y L,Jiang M,et al.Active carbon supported Mo-K catalysts used for alcohol synthesis[J].Journal of Catalysis,2001,199(2):155-161.
[39]Surisetty V R,Tavasoli A,Dalai A K.Synthesis of higher alcohols from syngas over alkali promoted MoS2 catalysts supported on multi-walled carbon nanotubes[J].Applied Catalysis A:General,2009,365:243-251.
[40]Tatsumi T,Muramatsu A,Tominaga H O.Supported molybdenum catalysts for alcohol synthesis from CO-H2[J].Applied Catalysis,1987,34(1-2):77-88.
[41]Surisetty V R,Dalai A K,Kozinski J.Synthesis of higher alcohols from synthesis gas over Co-promoted alkali-modified MoS2 catalysts supported on MWCNTs[J].Applied Catalysis A:General,2010,385:153-162.
[42]Storm D A.The production of higher alcohols from syngas using potassium promoted Co/Mo/Al2O3 and Rh/Co/Mo/Al2O3[J].Topics in Catalysis,1995,2:91-101.
[43]Bian G Z,Fu Y L,Ma Y S.Structure of Co-K-Mo/γ-Al2O3 catalysts and their catalytic activity for mixed alcohols synthesis[J].Catalysis Today,1999,51:187-193.
[44]Li Z G,Fu Y L,Bao J,et al.Effect of cobalt promoter on Co-Mo-K/C catalysts used for mixed alcohol synthesis[J].Applied Catalysis A:General,2001,220:21-30.
[45]Fu Y L,Fujimoto K,Lin P Y,et al.Effect of calcination conditions of the oxidized precursor on the structure of a sulfided K-Mo/γ-Al2O3, catalyst for mixed alcohol synthesis[J].Applied Catalysis A:General,1995,126(2):273-285.
[46]Tavasoli A,Abbaslou R M M,Trepanier M,et al.Fischer-Tropsch synthesis over cobalt catalyst supported on carbon nanotubes in a slurry reactor[J].Applied Catalysis A:General,2008,345:134-142.
[47]Ma X M,Lin G D,Zhang H B.Co-decorated carbon nanotube-supported Co-Mo-K sulfide catalyst for higher[J].Catalysis Lettters,2006,111(3-4):141-151.
[48]Tatsumi T,Muramatsu A,Tominaga H.Importance of sequence of impregnation in the activity development of alkali-promoted Mo catalysts for alcohol synthesis from CO + H2[J].Journal of Catalysis,1986,101:553-556.
[49]Lu G,Zhang C F,Gang Y Q,et al.Synthesis of mixed alcohols from CO2 contained syngas on supported molybdenum sulfide catalysts[J].Applied Catalysis A:General,1997,150:243-252.
[50]Fang K G,Li D B,Lin M G,et al.A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas[J].Catalysis Today,2009,147:133-138.