1,4-丁炔二醇加氢过程研究进展

doi:10.16085/j.issn.1000-6613.2017-0320

摘要/Abstract

摘要： 1，4-丁炔二醇（BYD）加氢产物1，4-丁二醇（BDO）是重要的有机化工原料，工业上该加氢过程存在反应压力高、设备投资大、催化剂易失活等问题。本文综述了1，4-丁炔二醇加氢反应过程的特点，对比了不同BYD加氢工艺并分析了各工艺特点和面临的问题，回顾了Ni基、Pt基、Pd基加氢催化剂的开发进展，简述了新型加氢反应器的特点与研究进展。基于催化剂表面氢浓度对BYD加氢反应过程影响显著的特点，提出通过强化反应过程气液、液固传质效率对BYD加氢过程进行改进，以期降低反应压力。通过加入金属助剂和改变载体性质开发加氢催化剂，提高催化剂活性和稳定性。最后总结展望了开发BYD低压加氢剂催化剂和低压加氢反应器的发展趋势，结合BYD加氢Ni基催化剂具有磁性的特点，提出磁场辅助流化床对BYD加氢过程的潜在应用前景。

关键词: 1, 4-丁炔二醇, 1, 4-丁二醇, 加氢, 过程强化, 催化剂, 反应器

Abstract: 1,4-butanediol(BDO),hydrogenation product of 1,4-butynediol(BYD),is an important organic chemical raw material. The main problems of industrial hydrogenation of BYD are high pressure,huge capital investment and catalyst deactivation. Characteristics of the hydrogenation process of BYD,characteristics and confronting problems of hydrogenation process,development of Ni-based,Pt-based and Pd-based catalysts for hydrogenation process and new types of reactors were reviewed. Based on the characteristics of great impact of hydrogen concentration of catalyst surface on the BYD hydrogenation reaction process,it was proposed to improve the hydrogenation process of BYD by enhancing the gas-liquid,liquid-solid mass transfer efficiency and to reduce the hydrogenation pressure. The activity and stability of the catalyst could be improved by adding supporting metals and change of the carriers. The development trends of low pressure 1,4-butynediol hydrogenation catalyst and reactor were discussed. Combining the magnetic properties of the Ni-based catalyst used in the hydrogenation process,the potential application of magnetically assisted fluidized bed reactor in BYD hydrogenation process was proposed.

Key words: 1,4-butynediol, 1,4-butanediol, hydrogenation, process intensification, catalyst, reactors

中图分类号:

TQ032.4

刘响, 廖启江, 张敏卿. 1,4-丁炔二醇加氢过程研究进展[J]. 化工进展, 2017, 36(08): 2787-2797.

LIU Xiang, LIAO Qijiang, ZHANG Minqing. Research progress of 1,4-butynediol hydrogenation process[J]. Chemical Industry and Engineering Progress, 2017, 36(08): 2787-2797.

参考文献

[1] 陈海红. 1,4-丁二醇生产工艺及其技术进展[J]. 精细石油化工进展,2014,15(1):46-49. CHEN H H. Production process and its technical progress of 1,4-butanediol[J]. Advances in Fine Petrochemicals,2014,15(1):46-49.
[2] 陈荣富,顾其威. 1,4-丁炔二醇用Raney镍加氢合成1,4-丁二醇的本征动力学研究[J]. 化学反应工程与工艺,1988,4(2):1-8. CHEN R F,GU Q W. A study on the intrinsic kinetics of catalytic hydrogenation of 1,4-butynediol to 1,4-butanediol by Raney nickel catalyst[J]. Chemical Reaction Engineering and Technology,1988,4(2):1-8.
[3] BECKER R,BROCKER FJ,KAIBEL G,et al. Process and catalysts for preparing 1,4-butanediol by the hydrogenation of 1,4-butynediol:WO9815513A1[P]. 1998-04-16.
[4] HILES A G,TUCK M W M. Process:WO1991001961 A1[P]. 1991-02-21.
[5] RUDOFF S,DETHOMAS W. Process and catalyst for preparing 1,4-butanediol:US3950441A[P]. 1976-04-13.
[6] SCHOEDEL N,HOFMANN K-H,WIESNER F,et al. Two-step process and catalysts for the hydrogenation of 1,4-butynediol to 1,4-butanediol:DE19625189C1[P]. 1997-10-23.
[7] SHARIF M,TURNER K. Butane-1,4-diol preparation:EP143634A2[P]. 1985-06-05.
[8] TAYLOR P D,VANDERSPURT T H. 1,4-Butanediol:US4083882A[P]. 1978-04-11.
[9] TANIELYAN S,SCHMIDT S,MARIN N,et al. Selective hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol over particulate Raney^® nickel catalysts[J]. Topics in Catalysis,2010,53(15-18):1145-1149.
[10] BERGUERAND C,YURANOV I,CARDENAS-LIZANA F,et al. Size-controlled pd nanoparticles in 2-butyne-1,4-diol hydrogenation:support effect and kinetics study[J]. The Journal of Physical Chemistry C,2014,118(23):12250-12259.
[11] 陈荣富,顾其威. 淤浆鼓泡床中Raney镍催化加氢反应的过程动力学[J]. 华东理工大学学报,1988,14(3):269-273. CHEN R F,GU Q W. Process kinetics of hydrogenation reaction with raney nickel catalyst in bubbling slurry bed[J]. Journal of East China University of Science and Technology,1988,14(3):269-273..
[12] 朱余民,顾春根,赵金玲,等. 丁炔二醇催化加氢的反应分析[J]. 化学反应工程与工艺,1985(4):2. ZHU Y M,GU C G,ZHAO J L,et al. Reaction analysis of catalytic hydrogenation of 1,4-butynediol[J]. Chemical Reaetion Engineering and Technology,1985(4):2.
[13] 华萱,王承学. 浆态反应器Pd催化剂丁炔二醇加氢制1,4-丁二醇的反应机理及动力学研究[J]. 吉林化工学院学报,1991(4):9. HUA X,WANG C X. Reaction and kinetic research of the hydrogenation of butynediol to 1,4-butanediol using pd catalyst in a slurry reactor[J]. Journal of Jilin Institute of Chemical Technology,1991(4):9.
[14] 华萱,王承学. 丁炔二醇加氢制1,4-丁二醇反应动力学研究[J]. 化工学报,1992,43(1):69-74. HUA X,WANG C X. Kinetics of hydrogenation of butynediol to 1,4-butanediol by using Pd catalyst in a slurry reactor[J]. CIESC Journal,1992,43(1):69-74.
[15] KIWI-MINSKER L,JOANNET E,RENKEN A. Loop reactor staged with structured fibrous catalytic layers for liquid-phase hydrogenations[J]. Chemical Engineering Science,2004,59(22/23):4919-4925.
[16] JOANNET E,HORNY C,KIWI-MINSKER L,et al. Palladium supported on filamentous active carbon as effective catalyst for liquid-phase hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol[J]. Chemical Engineering Science,2002,57(16):3453-3460.
[17] JOSEPH WOOD,BODENES L,BENNETT J,et al. Hydrogenation of 2-butyne-1,4-diol using novel bio-palladium catalysts.[J]. Ind. Eng. Chem. Res.,2010,49(3):980-988.
[18] 崔小明. 1,4-丁二醇生产技术进展及市场分析[J]. 甘肃石油和化工,2013(1):6-13. CUI X M. Development of 1,4-butanediol production technology and market analysis[J]. Gansu Shiyou He Huagong,2013,(1):6-13.
[19] 胡磊,赵攀. 炔醛法生产1,4-丁二醇的优势及工艺方案的探讨[C]//第九届宁夏青年科学家论坛石化专题论坛论,2013:473-477 HU L,ZHAO P. Advantages and technological process of 1,4-butanediol production by acetylene-formaldehyde method[C]//The Ninth Ningxia Young Scientist Forum,2013:473-477.
[20] 山秀丽. 1,4-丁二醇生产工艺技术评价[J]. 化学工程,2006,34(7):67-70. SHAN X L. Process technology assessment of 1,4-butanediol[J]. Chemical Engineering,2006,34(7):67-70.
[21] 徐志超,章小林,李耀会,等. 1,4-丁二醇制备工艺的现状及展望[J]. 化工设计通讯,2012,38(4):7-9. XU Z C,ZHANG X L,LI Y H,et al. Status and prospects of 1,4-butanediol preparation technology[J]. Chemical Engineering Design Communications,2012,38(4):7-9.
[22] 周树理. 1,4-丁二醇生产技术及市场前景分析[J]. 当代石油石化,2014(6):35-40. ZHOU S L. Technology and market prospects of 1,4-butanediol[J]. Petroleum & Petrochemical Today,2014(6):35-40.
[23] BREMER N J,MILBERGER E C,DOLHYJ S R. Maleic anhydride:DE2453677A1[P]. 1975-06-12.
[24] SHARIF M,TURNER K. Process for the production of butane-1,4-diol:US4584419[P]. 1986-04-22.
[25] TURNER K,SHARIF M,RATHMELL C,et al. Process for the production of butane-1,4-diol:US4751334[P].1988-06-14.
[26] OKUYAMA M. Process for preparing 1,4-butanediol:US5981810[P]. 1999-11-09.
[27] ZAJACEK J G,SHUM W P. Butanediol production:US6127584[P]. 2000-10-03.
[28] TAYLOR P D,VANDERSPURT T H. Production of 1,4-butanediol:US4083882[P]. 1978-04-11.
[29] 芦振江,胡磊. 雷珀(Reppe)法生产BDO中的雷尼镍催化剂活性本质的探讨[C]//第八届宁夏青年科学家论坛石化专题论坛论文集,2012:429-431. LU Z J,HU L. Discussion on reactivity of Raney nickel catalyst in BDO production by reppe method[C]//The 8th Ningxia Young Scientist Forum on Petrochemical,2012:429-431.
[30] REPPE W,STEINHOFER A,SPAENIG H,et al. Production of alkinols:US2300969[P]. 1942-11-03.
[31] REISS W,JOSCHEK H I,SCHNUR R,et al. Manufacture of butynediol:US4093668[P]. 1978-06-06.
[32] 菲利普·N·沃德. 改进的丁二醇制造方法:106232561A[P]. 2016-12-14. PHILIP N WARD. Improved butanediol manufacturing process:106232561A[P]. 2016-12-14.
[33] 李瑞香,范春芳,白淑梅. 1,4-丁二醇的生产及应用[J]. 山西化工,2009(3):50-52,59. LI R X,FAN C F,BAI S M. Production and application of 1,4-butanediol[J]. Shanxi Chemical Industry,2009(3):50-52,59.
[34] 任晓军,胡燕,章小林,等. Reppe两步法合成1,4-丁二醇工艺中二段加氢催化剂的研究进展[J]. 江汉大学学报(自然科学版),2014,42(2):61-63. REN X J,HU Y,ZHANG X L,et al. Research progress in second section of hydrogenation catalyst for reppe two-steps synthesis of 1,4-butanediol[J]. Journal of Jianghan University (Natural Science Edition),2014,42(2):61-63.
[35] RANEY M. Method of producing finely-divided nickel:US1628190 A[P]. 1927-05-27.
[36] HORT E V,Graham D E. Hydrogenation of 2-butyne-1,4-diol to 1,4-butanediol:US2967893[P]. 1961-01-10
[37] HADLEY R L. Hydrogenation catalyst:US2948687[P]. 1960-08-09.
[38] EUGENE V H,WALDO R D. Raney nickel catalyst:GB2104794A[P]. 1983.
[39] FISCHER Rolf,SIGWART Christoph. Preparation of 1,4-butanediol:US5977417A[P]. 1999-11-02
[40] R·贝克,F·J·布罗克,G·卡贝尔,等. 1,4-丁炔二醇催化氢化制备1,4-丁二醇的方法:1222902[P]. 1999-07-14. BECKER R,BROCKER F J,KAIBEL G,et al. Process for preparing 1,4-butanediol by catalytic hydrogenation of 1,4-butinediol:1222902[P]. 1999-07-14.
[41] DE THOMAS W R,HORT E V. Catalyst comprising Raney nickel with adsorbed molybdenum compound:US4153578A[P]. 1979-05-08
[42] 卡尔-海因茨·霍夫曼,妮科尔·肖德尔,彼得·马蒂亚斯·弗里兹,等. 丁炔二醇经两步催化加氢制备丁二醇的方法:1172792[P]. 1998-02-11. HOFMANN KARL-HEINZ,SCHODEL NICOLE,FRITZ PETER MATTHIAS,et al. Method for preparing butanediol from butydiol through two-step catalyzing hydrogenation:1172792[P]. 1998-02-11.
[43] 赵永祥,李海涛,杨学英,等. 丁炔二醇两步法加氢制丁二醇二段加氢催化剂的制备方法:101306368[P]. 2008-11-19. ZHAO Y X,LI H T,YANG X Y,et al. Preparation method of butanediol secondary hydrogenation catalyst by butynediol two-step hydrogenation:101306368[P]. 2008-11-19.
[44] 李海涛,徐亚琳,王永钊,等. Ni/Al₂O₃催化剂在粗1,4-丁二醇液相加氢中的失活研究[C]//第七届全国催化剂制备科学与技术研讨会,2009:234-236. LI H T,XU Y L,WANG Y Z,et al. Study of deactivation of Ni/Al₂O₃ catalyst in liquid hydrogenation of 1,4-butanediol[C]//The 7th National Conference on Catalyst Preparation Science and Technology,2009:234-236.
[45] 李海涛. 丁炔二醇加氢制1,4-丁二醇催化剂的失活机理与改性研究[D]. 太原:山西大学,2011. LI H T. Study of deactivation and promotion of catalyst employed in hydrogenation of butynediol to 1,4-butanediol[D]. Taiyuan:Shanxi University,2011.
[46] LI H,XU Y,GAO C,et al. Structural and textural evolution of Ni/γ-Al₂O₃ catalyst under hydrothermal conditions[J]. Catalysis Today,2010,158(3):475-480.
[47] LI H,ZHAO Y,GAO C,et al. Study on deactivation of Ni/Al₂O₃ catalyst for liquid phase hydrogenation of crude 1,4-butanediol aqueous solution[J]. Chemical Engineering Journal,2012,181:501-507.
[48] 徐亚琳,李海涛,张建平,等. 临氢水热处理对Ni/γ-Al₂O₃催化剂结构和性能的影响[J]. 分子催化,2010(2):112-116. XU Y L,LI H T,ZHANG J P,et al. Effect of hydrothermal treatment under H₂ atmosphere on the structure and performance of Ni/γ-Al₂O₃ catalyst[J]. Journal of Molecular Catalysis,2010(2):112-116.
[49] 孙自瑾,李海涛,徐亚琳,等. 助剂对Ni/γ-Al₂O₃催化剂活性和抗水合性能的影响[J]. 工业催化,2012,20(5):14-18. SUN Z J,LI H T,XU Y L,et al. Effects of the promoter on catalytic activity and hydrothermal stability of Ni/γ-Al₂O₃ catalysts[J]. Industrial Catalysis,2012,20(5):14-18.
[50] 赵永祥,徐亚琳,李海涛,等. 一种高水热稳定性氧化铝载体及其制备方法:101786024A[P]. 2010-07-28. ZHAO Y X,XU Y L,LI H T,et al. Alumina carrier with high hydrothermal stability and preparation method thereof:101786024A[P]. 2010-07-28.
[51] 赵永祥,梁旭,杨学英,等. 一种氧化铝载体及其制备方法:101322949[P]. 2008-12-10. ZHAO Y X,LIANG X,YANG X Y,et al. Alumina supporter and preparation method thereof:101322949[P]. 2008-12-10.
[52] 梁旭. Al₂O₃物性对Ni/Al₂O₃催化剂丁炔二醇二段加氢性能的影响[D]. 太原:山西大学,2009. LIANG X. Influence of physical properties of Al₂O₃ on catalytic performance of Ni/Al₂O₃ catalyst for secondary hydrogenation of butynediol[D]. Taiyuan:Shanxi University,2009.
[53] 李海涛,陈昊然,张因,等. 炭包覆氧化铝负载镍催化剂的制备和表征及其催化加氢性能[J].催化学报,2011,32(1):111-117. LI H T,CHEN H R,ZHANG Y,et al. Preparation and characterization of carbon-covered alumina supported Ni catalyst and its catalytic performance for hydrogenation[J]. Chinese Journal of Catalysis,2011,32(1):111-117.
[54] 郭江渊,李海涛,张智隆,等. 表面酸性对Ni/SiO₂-Al₂O₃催化剂催化1,4-丁炔二醇高压加氢性能的影响[J]. 分子催化,2016,30(1):37-45. GUO J Y,LI H T,ZHANG Z L,et al. Effect of surface acidity on Ni/SiO₂-Al₂O₃ catalyst performance for 1,4-butynediol hydrogenation[J]. Journal of Molecular Catalysis,2016,30(1):37-45.
[55] LI C,ZHANG M,DI X,et al. One-step synthesis of Pt@ZIF-8 catalyst for the selective hydrogenation of 1,4-butynediol to 1,4-butenediol[J]. Chinese Journal of Catalysis,2016,37(9):1555-1561.
[56] TELKAR M,RODE C,JAGANATHAN R,et al. Platinum catalyzed hydrogenation of 2-butyne-1,4-diol[J]. Journal of Molecular Catalysis A:Chemical,2002,187:181-193.
[57] RODE C V,TAYADE P R,NADGERI J M,et al. Continuous hydrogenation of 2-butyne-1,4-diol to 2-butene-and butane-1,4-diols[J]. Organic Process Research & Development,2006,10(2):278-284.
[58] 王承学,赵凤玉. 丁炔二醇加氢制丁二醇Pd/γ-Al₂O₃ 催化剂的制备与评价[J]. 工业催化,1995,3(2):23-27. WANG C X,ZHAO F Y. Preparation and evaluation of Pd/γ-Al₂O₃ catalyst for hydrogenation of butynediol tobutanediol[J]. Industrial Catalysis,1995,3(2):23-27.
[59] JOANNET E,HORNY C,KIWI-MINSKER L,et al. Palladium supported on filamentous active carbon as effective catalyst for liquid-phase hydrogenation of 2-butyne-1,4-diol to 2-butene-1,4-diol[J]. Chemical Engineering Science,2002,57(16):3453-3460.
[60] KIWI-MINSKER L,JOANNET E,RENKEN A. Solvent-free selective hydrogenation of 2-butyne-1,4-diol over structured palladium catalyst[J]. Industrial and Engineering Chemistry Research,2005,44(16):6148-6153.
[61] RODE C. Catalytic hydrogenation of 2-butyne-1,4-diol Activity,selectivity and kinetics studies[J]. Journal of the Japan Petroleum Institute,2008,51(3):119-133.
[62] 赵永祥,张因,孙自瑾,等. 一种适用于加氢放热反应的外循环反应装置:103566837A[P]. 2014-02-12. ZHAO Y X,ZHANG Y,SUN Z J,et al. External circular reaction device suitable for hydrogenation exothermic reaction:103566837A[P]. 2014-02-12.
[63] 胡小军,卢涛. 气液相逆流鼓泡固定床BDO加氢反应器:104801239A[P]. 2015-07-29. HU X J,LU T. BDO (1,4-butanediol) hydrogenation reactor adopting gas-liquid-phase countercurrent bubbling fixed bed:104801239A[P]. 2015-07-29.
[64] 胡小军. 1,4-丁二醇内换热式高压加氢反应器:203291831U[P]. 2013-11-20. HU X J. 1,4-butanediol internal heat exchange-type high-pressure hydrogenation reactor:203291831U[P]. 2013-11-20.
[65] NATIVIDAD R,KULKARNI R,NUITHITIKUL K,et al. Analysis of the performance of single capillary and multiple capillary (monolith)reactors for the multiphase Pd-catalyzed hydrogenation of 2-butyne-1,4-diol[J]. Chemical Engineering Science,2004,59(22/23):5431-5438.
[66] WINTERBOTTOM J M,MARWAN H,STITT E H,et al. The palladium catalysed hydrogenation of 2-butyne-1,4-diol in a monolith bubble column reactor[J]. Catalysis Today,2003,79/80:391-399.
[67] REHM T H,BERGUERAND C,EK S,et al. Continuously operated falling film microreactor for selective hydrogenation of carbon-carbon triple bonds[J]. Chemical Engineering Journal,2016,293(1):345-354.
[68] CHEN C M,LEU L P. Hydrodynamics and mass transfer in three-phase magnetic fluidized beds[J]. Powder Technology,2001,117:198-206.
[69] HRISTOV J. A hydrodynamic treatise on liquid-solid fluidized beds[J]. Reviews in Chemical Engineering,2006,22(4/5):195-375.
[70] HRISTOV J. Topics of gas-liquid-solid fluidization bed hydrodynamics[J]. Reviews in ChemicalEngineering,2007,23(6):373-526.
[71] HRISTOV J. Mass transfer chemical reactors basic studies and practical implementations thereof[J]. Reviews in Chemical Engineering,2009,25(1/2/3):1-254.
[72] WORDEN VS TARM. Phase holdup,liquid dispersion,and gas-to-liquid mass transfer measurements in a three-phase magnetofluidized bed[J]. Chemical Engineering Science,1997,52(2):279-295.
[73] ZHU Q,LI H,ZHU Q,et al. Hydrodynamic study on magnetized fluidized beds with Geldart-B magnetizable particles[J]. Powder Technology,2014,268:48-58.
[74] ZHOU L,DIAO R,ZHOU T,et al. Behavior of magnetic Fe₃O₄ nano-particles in magnetically assisted gas-fluidized beds[J]. Advanced Powder Technology,2011,22(3):427-432.
[75] LI W,ZONG B,LI X,et al. Interphase mass transfer in G-L-S magnetically stabilized bed with amorphous alloy SRNA-4 catalyst[J]. Chinese Journal of Chemical Engineering,2006,14(6):734-739.
[76] 张金利,卢立祥,孟祥堃,等. 气-液-固磁稳定床研究进展[J]. 现代化工,2003,23(s1):12-14. ZHANG J L,LU L X,MENG X K,et al. Research progress in gas-liquid-solid magnetically stabilized bed[J]. Modern Chemical Industry,2003,23(s1):12-14.
[77] ZONG B N,MU X H,ZHANG X X. Magnetically stabilized bed reactors[J]. Chinese Journal of Catalysis,2013,34:61-68.
[78] 曾平,周涛,陈冠群,等. 磁场流化床的研究与应用[J]. 化工进展,2006,25(4):371-377. ZENG P,ZHOU T,CHEN G Q,et al. Research and application of magnetic fluidized bed[J]. Chemical Industry and Engineering Progress,2006,25(4):371-377.
[79] 汪颖,江雨生,罗耀邦,等. 磁稳定床己内酰胺加氢精制新工艺[J]. 精细化工,2003,20(8):472-474. WANG Y,JIANG Y S,LUO Y B,et al. New process for purification of caprolactam in magnetically stabilized bed reactor[J]. Fine Chemicals,2003,20(8):472-474.
[80] 傅送保,朱泽华,罗耀邦,等. 磁稳定床反应器中己内酰胺加氢精制应用研究[J]. 石油化工,2004,33(4):364-367. FU S B,ZHU Z H,LUO Y B,et al. Study on purification of caprolactam in magnetically stabilized bed reactor[J]. Petrochemical Technology,2004,33(4):364-367.
[81] MENG X,MU X,ZONG B,et al. Purification of caprolactam in magnetically stabilized bed reactor[J]. Catalysis Today,2003,79/80:21-27.
[82] 谢文华,宗保宁. 磁性催化剂与磁稳定床反应器[J]. 化学进展,2009,21(11):2474-2482. XIE W H,ZONG B N. Magnetic catalysts and magnetically stabilized bed reactor[J]. Progress in Chemistry,2009,21(11):2474-2482.
[83] 孟祥堃,张晓昕,宗保宁,等. 磁稳定床反应器重整生成油后加氢过程研究[J]. 石油炼制与化工,2002,33(4):1-4. MENG X K,ZHANG X X,ZONG B N,et al. Study on process of selective hydrogenation of olefins in reformate using magnetically stabilized bed reactor[J]. Petroleum Processing and Petrochemicals,2002,33(4):1-4.
[84] PENG Y,DONG M,MENG X,et al. Light FCC gasoline olefin oligomerization over a magnetic NiSO₄/γ-Al₂O₃ catalyst in a magnetically stabilized bed[J]. AIChE Journal,2009,55(3):717-725.
[85] DONG M,PAN Z,PENG Y,et al. Selective acetylene hydrogenation over core-shell magnetic Pd-supported catalysts in a magnetically stabilized bed[J]. AIChE Journal,2008,54(5):1358-1364.
[86] YU L,WANG Q,LIU C,et al. Magnetically stabilized bed for selective hydrogenation of benzene[J]. Chemical Engineering & Technology,2014,37(3):392-397.