Review of recent development of green chemical technologies

doi:10.16085/j.issn.1000-6613.2016.06.001

Abstract

Abstract: At present,China's chemical industry is facing big challenges of resources and environment,while green chemical technologies could provide ways to promote the sustainable development of China's chemical industry. This article proposed that the degree of green chemical technologies can be measured by atomic economy,energy consumption and low carbon of full life cycle. Then,it summarizes three basic ways to realize green chemistry,including low carbonization,clean processes and energy conservation. Moreover,this article reviews the development and application of green chemical technologies in China,involving in the chemical transformation of renewable biomass resources,green chemical process,high efficient reactor or separation equipment,green solvents,homogeneous catalysis used at low reaction temperature,green hydrogen production and utilization of carbon dioxide,etc. Finally,outlook is given,and it is suggested that the green carbon science concept should always be committed,and special attentions could be paid on direct conversion technologies,energy management in the input and intermediate process,and output CO₂ intensive transformation,etc.

Key words: green chemical technology, the sustainable development, biomass, carbon dioxide, outlook

摘要： 当前,我国化学工业面临资源和环境等方面的重大挑战,绿色化工技术对于环境的保护和经济的发展具有至关重要的作用,是化工行业可持续发展的必然选择。本文指出绿色化程度需用原子经济性、综合能耗以及全生命周期低碳等指标进行衡量,总结了实现绿色化的3个基本途径:低碳化、清洁化和节能化,并从生物质低碳可再生资源的化工利用、绿色反应工艺、高效反应与分离设备、绿色溶剂、低温均相催化、绿色制氢以及CO₂利用技术等方面,综述了近年来我国绿色化工技术创新上的主要进展。最后,对我国绿色化工技术发展的未来进行了展望,建议以绿色碳科学理念为基础,应重视直接转化技术、输入端和过程中能量的管理以及输出端CO₂的集中转化技术等方面的研究开发。

关键词: 绿色化工技术, 可持续发展, 生物质, 二氧化碳, 展望

CLC Number:

TQ021

YANG Heqin, LIU Zhicheng, XIE Zaiku. Review of recent development of green chemical technologies[J]. Chemical Industry and Engineering Progree, 2016, 35(06): 1575-1586.

杨贺勤, 刘志成, 谢在库. 绿色化工技术研究新进展[J]. 化工进展, 2016, 35(06): 1575-1586.

References

[1] FUJII H. Decomposition analysis of green chemical technology inventions from 1971 to 2010 in Japan[J]. Journal of Cleaner Production,2016,112:4835-4843.
[2] 何鸣元,孙予罕. 绿色碳科学——化石能源增效减排的科学基础[J]. 中国科学(化学),2011,41:925-932.
[3] HE M Y,SUN Y H,HAN B X. Green carbon science: scientific basis for integrating carbon resource processing,utilization,and recycling[J]. Angew. Chem. Int. Ed.,2013,52:9620-9633.
[4] HALLETT J P,WELTON T. Room-temperature ionic liquids:solvents for synthesis and catalysis[J]. Chem. Rev.,2011,111:3508-3576.
[5] 徐兆瑜. 离子液体在化学反应中的应用新进展[J]. 乙醛醋酸化工,2015,178(6):20-28.
[6] 李红宝. 化工节能技术及节能设备发展前景[J]. 山西化工,2010,30(6): 56-59.
[7] 孙宏伟,陈建峰. 我国化工过程强化技术理论与应用研究进展[J]. 化工进展,2011,30(1):1-15.
[8] 吴创之,周肇秋,阴秀丽,等. 我国生物质能源发展现状与思考[J]. 农业机械学报,2009,40(1):91-99.
[9] 闵恩泽,张利雄. 生物质炼油化工产业分析报告[M]. 北京:科学出版社,2013.
[10] 杜泽学,刘晓欣,江雨生,等. 近/超临界甲醇醇解油脂生产生物柴油工艺的中试[J]. 石油化工,2014,11(11):1296-1304.
[11] 国产首例地沟油所炼,生物航油成功试飞[EB/OL] http://it.sohu.com/20130424/n373883243.shtml.
[12] STUMBORG M,WONG A ,HOGAN E. Hydroprocessed vegetable oils for diesel fuel improvement[J]. Bioresource Technology,1996 ,56 (1):13-18.
[13] 亓荣彬,王玉军,朴香兰. 一种集成加氢制备生物柴油的方法:101029245[P] . 2007-09-05.
[14] 姚志龙. 脂肪酸甲酯超临界加氢制备脂肪醇新工艺研究[D]. 北京:中国石化石油化工科学研究院,2008.
[15] ZHOU J X. Development and future of full green chemical industry[J]. Chemical Engineering Design,2010,20(1):3-7.
[16] OWENS G S,ABU-OMAR M M. A tetraazaporphyrin with an intense,broad near-IR band[J].Chemistry Communication,2001(2):165-166.
[17] MADEIRA L R,VAN R F,SEDDON K R. Lipase-catalyzed reactions in ionic liquids[J].Organic Letter,2000,2:4189-4191.
[18] FARRELL A E,PLEVIN R J,TURNER B T,et al. Ethanol can contribute to energy and environmental goals[J]. Science,2006,311:506-508.
[19] HUBER GEORGE W, CHENG Y T. Catalytic pyrolysis of solid biomass and related biofuels,aromatic,and olefin compounds:US20090227823[P] . 2009-09-10.
[20] Virent succeds in producing PX from 100% plant-based sugars[N]. Petro Chemical News,2011-06-18:1.
[21] JI N,ZHANG T,ZHENG M Y,et al. Direct Catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts[J]. Angew. Chem. Int. Ed.,2008 ,47(44):8510-8513.
[22] WANG A Q ,ZHANG T. One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts[J]. Acc. Chem. Res.,2013,46(7):1377-1386.
[23] LUO C,WANG S,LIU H C. Cellulose conversion to polyols catalyzed by reversibly-formed acids and supported ruthenium clusters in hot water[J]. Angew. Chem. Int. Ed.,2007,46:7636-7639.
[24] YAN N,ZHAO C,LUO C,et al. One step conversion of cellobiose to C6-alcohols using a ruthenium nanocluster catalyst[J]. J. Am. Chem. Soc.,2006,128:8714-8715.
[25] WANG Y,WANG B,DENG W,et al. Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water[J]. Nature Comm.,2013,4: 2141-2141.
[26] DENG Y H,FENG X J,ZHOU M S,et al. Investigation of aggregation and assembly of alkali lignin using iodine as a probe[J]. Biomacromolecules,2011,12:1116-1125.
[27] OUYANG X P, DENG Y H, QIAN Y, et al. Adsorption characteristics of lignosulfonates in salt-free and salt-added aqueous solutions[J]. Biomacromolecules,2011,12(9):3313-3320.
[28] QIU X Q,ZHOU M S,YANG D J,et al. Evaluation of sulphonated acetone-formaldehyde (SAF) used in coal water slurries prepared from different coals[J]. Fuel,2007,86:1439-1445.
[29] XIA Q N ,CUAN Q,LIU X H,et al. Pd/NbOPO₄multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans[J]. Angew. Chem. Int. Ed.,2014,53(37):9755–9760.
[30] 孙斌,程时标,孟祥堃,等.己内酰胺绿色生产技术[J]. 中国科学(化学),2014,44(1):40-45.
[31] 金国杰,高焕新,杨洪云,等. 后合成Ti/HMS催化剂的表征及对丙烯的催化环氧化性能研究[J]. 分子催化,2010,24(1):6-11.
[32] 李军,高爽,奚祖威. 反应控制相转移催化研究的进展[J]. 催化学报,2010,31:895-911.
[33] 李奕川,沈本贤,肖卫国,等.千吨级丙烯直接环氧化制环氧丙烷工业试验[J]. 石油炼制与化工,2013,44:8-12.
[34] 姜杰. HPPO法环氧丙烷工业试验装置HAZOP分析项目通过专家审查[J]. 安全、健康和环境,2013,13(8):12
[35] Milorad P. Dudukovic,Frontiers in reactor engineering[J]. Science,2009,325:698-701
[36] Hung C P,Liu Z C,Xu C M,et al. Effects of additives on the p roperties of chloroalum inate ionic liquids catalyst for alkylation of isobutane and butene [J]. Appl. Catal. A,2004,277(122):41243.
[37] Cui J,With J D,Klusener P A A,et al. Identification of acidic species in chloroaluminate ionic liquid catalysts[J]. J. Catal.,2014,320:26–32.
[38] 綦振元,李岐东.烷基化工艺的技术特点及发展状况[J]. 化工设计,2015,25(1):6-9.
[39] 贾燕子,杨清河,孙淑玲,等. 渣油加氢处理过程中Mo-V/Al₂O₃的催化性能及协同效应[J]. 催化学报,2012,33(9):1546-1551.
[40] HILDEBRANDT D,GLASSER D,HAUSBERGER B,et al. Producing transportation fuels with less work[J]. Science,2009,323:1680-1681.
[41] ZHAO S,LIU X W,HUO C F,et al. Surface morphology of Hägg iron carbide (χ-Fe₅C₂) from ab initio atomistic thermodynamics[J]. J. Catal.,2012,294:47-53.
[42] HUO C F,WU B S,GAO P,et al. The mechanism of potassium promoter:enhancing the stability of active surfaces[J]. Angew. Chem. Int. Ed.,2011,50:7403-7406.
[43] DENG L J,HUO C F,LI Y W,et al. Density functional theory study on surface C_xH_y formation from CO activation on Fe₃C(100) [J]. J. Phys. Chem. C,2010,114:21585-21592.
[44] HUO C F,LI Y W,WANG J,et al. Insight into CH₄ formation in iron-catalyzed Fischer-Tropsch synthesis[J].J. Am. Chem. Soc., 2009,131:14713-14721.
[45] KANG J,ZHANG S,ZHANG Q,et al. Ruthenium nanoparticles supported on carbon nanotubes as efficient catalysts for selective conversion of syngas to diesel fuel[J]. Angew. Chem. Int. Ed.,2009,48:2565-2568.
[46] KANG J,CHENG K,ZHANG L,et al. Mesoporous zeolite-supported ruthenium nanoparticles ashighly selective Fischer-Tropsch catalysts for the production of C5—C11 isoparaffins[J]. Angew. Chem. Int. Ed.,2011,50: 5200-5203.
[47] HUANG Y Y,GUO Y L,WANG Y B. Ethylene glycol electrooxidation on coreeshell PdCuBi nanoparticles fabricated via substitution and self-adsorption processes[J]. Journal of Power Sources,2014,249:9-12.
[48] LIN L,PAN P B,ZHOU Z F,et al. Cu/SiO₂ catalysts prepared by the sol-gel method for hydrogenation of dimethyl oxalate to ethylene glycol[J]. Chin. J. Catal.,2011,32: 957-969.
[49] 江镇海. 国内外合成气制乙二醇技术进展[J]. 合成技术及应用,2010,25(44):27-30.
[50] 李涛. 国内合成气制乙二醇技术开发现状及思考[J]. 精细化工原料及中间体,2012,12:40-43.
[51] GUO X G ,FANG G Z ,LI G,et al. Direct,nonoxidative conversion of methane to ethylene,aromatics,and hydrogen[J]. Science,2014,344(2):616–619.
[52] 贾广斌,程广慧,蒋明敬,等. 空气预热器技术在齐鲁乙烯装置裂解炉的应用[J]. 齐鲁石油化工,2007,35(3):210-212.
[53] 陈亮,肖剑,谢在库,等.对二甲苯结晶分离技术进展[J].现代化工,2009,29(2):10-11.
[54] BP Corporation North America Inc. Energy efficient process for producing high purity paraxylene:US 6565653[P],2003-05-20.
[55] 洪周,张春,吴再娟,等. 原位法制备MFI型分子筛膜及其渗透性能[J]. 南京工业大学学报,2012,34(6):22-26.
[56] 徐南平,邢卫红. 一种膜过滤精制盐水的方法:200610038868.6[P]. 2009-02-11.
[57] ZHONG Z X,XING W H,LIU X,et al. Fouling and regeneration of ceramic membranes used in recovering titanium silicalite-1 catalysts[J]. Journal of Membrane Science,2007,301:67-75.
[58] LI W X,ZHANG X J,XING W H,et al. Hydrolysis of ethyl lactate coupled by vapor permeation using PDMS/ceramic compositemembrane [J]. Industrial & Engineering Chemistry Research,2010,49(22):11244-11249.
[59] 王迪勇,王金渠,杨建华,等. 蒸气相法ZSM-5 分子筛的合成及其负载的 Mo 催化剂在甲烷芳构化中的应用[J]. Chin. J. Catal.,2012,33:1383-1388.
[60] CAO Z W, JIANG H Q,LUO H X,et al. Natural gas to fuels and chemicals:improved methane aromatization in an oxygen-permeable membrane reactor[J]. Angew. Chem.Int. Ed.,2013,52:13794-13797.
[61] JIN Z H,LIU S,QIN L,et al. Methane dehydroaromatization by Mo-supported MFI-type zeolite with core-shell structure[J]. Appl. Catal. A: Gen.,2013,453:295-301.
[62] ZHAO H,SHAO L,CHEN J F. High-gravity process intensification technology and application[J]. Chemical Engineering Journal,2010,156:588-593.
[63] WEBB C,KANG H K,MOFFAT G,et al. Magnetically stabilized fluidized bed bioreactor:a tool for improved mass transfer in immobilized enzyme systems[J]. Chemical Engineering Journal and Biochemical Engineering Journal,1996,61(3):241-246.
[64] 慕旭宏,闵恩泽,宗保宁. 气液固三相磁稳定流化床的操作状态对反应结果的影响[J]. 化学反应工程与工艺,1997,13(2):198-202.
[65] 孟祥堃,慕旭宏,江雨生,等. 液固磁稳定床流体力学特性[J]. 化工学报,2004,55(1):l34-l37.
[66] 尧超群,乐军,赵玉潮,等. 微通道内气-液弹状流动及传质特性研究进展[J]. 化工学报,2015,66(8):2759-2766.
[67] 骆广生,兰文杰,李少伟,等. 微流控技术制备功能材料的研究进展[J]. 石油化工,2010,39(1):1-6.
[68] 陈光文. 微化工技术研究进展[J]. 现代化工,2007,27(10):8-13.
[69] 陈自力.甲烷液相催化氧化制甲醇的工艺研究[D].西安:西北大学,2008.
[70] 晏丽红.膜催化技术用于甲烷转化反应的研究进展[J].天津化工,2004,18(3):1-4.
[71] 陈希慧,李树本,王永忠,等.MoO₃/TiO₂和WO₃/TiO₂光催化分子氧氧化甲烷的活性[J].分子催化,2000,14(4):245-246.
[72] NOCETI R P,TAYLOR C E. Method for the photocatalytic conversion of methane:US5720858[P].,1998-02-24.
[73] CHEN L,ZHANG X W,HUANG L,et al.Post-plasma catalysis for methane partial oxidation to methanol:role of copper-promoted iron oxide catalyst[J].Chemical Engineering&Technology,2010,33(12):2073-2081.
[74] INDARTO A,YANG D R,PALGUNADI J,et al.Partial oxidation of methane with Cu-Zn-Al catalyst in adielectric barrier discharge[J].Chemical Engineering and Processing:Process Intensification,2008,47(5):780-786.
[75] CHEN L,ZHANG X W,HUANG L,et al.Partial oxidation of methane with air for methanol production in a post-plasma[J]. Chemical Engineering and Processing:Process Intensification,2009,48(8):1333-1340.
[76] CHEN L,ZHANG X W,HUANG L,et al.Application of inplasma catalysis and post-plasma catalysis for methane partial oxidation to methanol over a Fe₂O₃-CuO/γ-Al₂O₃ catalyst[J].Journal of Natural Gas Chemistry,2010,19(6):628-637.
[77] JI N,ZHANG T,ZHENG M Y,et al. Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts[J]. Angew. Chem.Int. Ed.,2008,47:8510-8513.
[78] LIU Y,LUO C,LIU H C. Tungsten trioxide promoted selective conversion of cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst [J]. Angew. Chem. Int. Ed. ,2012,51:3249-3253.
[79] AN D L,YE A H,DENG W P ,et al. Selective conversions of cellobiose and cellulose into gluconic acid in water medium in the presence of oxygen catalyzed by polyoxometalate-supported gold nanoparticles[J]. Chem. Eur.,J,2012,18: 2938-2947.
[80] ALIREZA Rahimi,ARNE Ulbrich,JOSHUA J Coon,et al. Ormic-acid-induced depolymerization of oxidized lignin to aromatics[J]. Nature,2014,515,249-252.
[81] DENG T S,CUI X J,QI Y Q ,et al. Conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by ZnCl₂ in water[J]. Chem Commun,2012,48:5494-5496.
[82] VINIT Choudhary,SAMIR H. Mushrif,CHRISTOPHER Ho,et al. Insights into the interplay of lewis and brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media[J].J. Am. Chem. Soc., 2013,135:3997-4006.
[83] HU J Y,MA J,ZHU Q G,et al. Transformation of atmospheric CO₂ catalyzed by protic ionic liquids:efficient synthesis of 2-oxazolidinones[J].Angew. Chem. Int. Ed.,2015,54:5399-5403.
[84] 史敬华,宋金良,张斌斌,等. 离子液体中CO₂与炔醇在温和条件下高效合成-亚甲基环状碳酸酯[J]. 中国科学(化学),2014,44(1):146-152.
[85] MATTHIAS W Haenel,STEPHAN Oevers,KLAUS Angermund,et al. Hall thermally stable homogeneous catalysts for alkane dehydrogenation[J]. Angew. Chem. Int. Ed.,2001,40: 3596-3600.
[86] YAO W,ZHANG X,JIA X,et al. Selective catalytic transfer dehydrogenation of alkanes and heterocycles by an iridium pincer complex[J].Angew. Chem. Int. Ed.,2014,53:1390-1394.
[87] HAN Z,RONG L,WU J,et al. Catalytic hydrogenation of cyclic carbonates:a practical approach from CO₂ and epoxides to methanol and diols[J]. Angew. Chem. Int. Ed.,2012,51:13041-13045.
[88] ZHANG L,HAN Z B ,ZHAO X Y ,et al. highly efficient ruthenium-catalyzed N-formylation of amines with H₂ and CO₂[J]. Angew. Chem. Int. Ed., 2015,54:6186-6189.
[89] NAVARRO P M,PENA M A,FIERRO J L G. Hydrogen production reactions from carbon feedstocks: fossil fuels and biomass[J]. Chem. Rev.,2007,107:3952-3991.
[90] 谢在库,金中豪,王仰东. 基于绿色氢科学理念构筑从低碳制氢到高效储氢的氢能体系[J]. 中国科学(化学),2013,43(1):1-9.
[91] FAN L S,ZENG L,LUO S W. Chemical-looping technology platform[J]. AIChE Journal,2015,61:2-22.
[92] U.S. Department of Energy. A prospectus for biological H₂ production.[EB/OL] http://www1.eere.energy.gov / hydrogenand fuelcells / production/pdfs/photobiological.pdf.
[93] 温福宇,杨金辉,宗旭,等. 太阳能光催化制氢研究进展[J].化学进展,2009,21:2285-2302.
[94] MAEDA K,DOMEN K. Photocatalytic water splitting:recent progress and future challenges[J]. J. Phys. Chem. Lett.,2010,1: 2655-2661.
[95] SUN N N,WEN X,WANG F,et al. Catalytic performance and characterization of Ni-CaO-ZrO₂ catalysts for dry reforming of methane[J]. Applied Surface Science,2011,257: 9169-9176.
[96] LIU Z C,ZHOU J,CAO K,et al.Highly dispersed nickel loaded on mesoporous silica: one-spot synthesis strategy and high performance as catalysts for methane reforming with carbon dioxide[J]. Applied Catalysis B: Environmental ,2012,125:324-330.
[97] YANG J,WANG D,LI C,et al. Roles of cocatalysts in photocatalysis and photoelectrocatalysis[J]. Acc. Chem. Res.,2013,46: 1900-1909.