低温高活性高选择性苯选择加氢催化剂-郑州大学-刘寿长.ppt

,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,低温高活性,苯选择加氢催化剂,郑州大学,刘寿长,1.,引言,由苯选择加氢，经由环己烯制备尼龙,-6,和尼龙,-66,具有安全、原子经济性和环境友好等优点。,自由基反应，安全隐患，副反应多，环境污染,安全，碳原子利用率,100%,，环境友好,尼龙,-6,和尼龙,-66,热力学上对生成环己烯极为不利，研究方向集中在如何提高环己烯选择性和收率上。,催化剂研发是该技术的核心和难点。,1980,年，瑞典,Odembrand,等提出分步加氢机理；,1989,年,日本旭化成实现了苯选加氢催化技术工业化；,1992,年，荷兰,Strurijk,等提出催化剂亲水性的概念；,1999,年，复旦大学等开发了,Ru-B,非晶合金催化剂；,2004-2006,，中科院大连化物所，纳米非晶和金；,20082012,年，复旦大学，,华东理工大学等,用“双溶剂法”制备,了,Ru-M/SBA-15,催化剂。,2011-2013,，中科院化学所，碱性催化体系。,。,国内外研究进展,1998,年,-2007,年，开发了,Ru-M-B/ZrO,2,(M=La,、,Zn,和,Fe,等,),第一代负载型催化剂，完成了间歇中试和连续中试，申报了发明专利。实现了催化剂制备技术国产化。,本实验室研究进展：,2009-2011,年，开发了第二代非负载型,Ru-Zn,催化剂，并与设计单位联合开发了,10,万吨工艺包，实现了催化剂制备技术和催化工艺国产化。目前已有,6,套 工业化装置建成投产。,2012-2013,年，开发了第三代低温高活性催化剂，完成了催化剂制备技术工业化实验。,2.,低温高活性苯选择加氢催化剂,催化剂五个重要指标：,1,.,活性指数,：,用,40,、,50,或,60,表示，分别为苯转化,40%,、,50%,和,60%,时，每克催化剂每小时转化苯的克数；要求大于,100,；,2.,环己烯选择性,：,用,S,40,、,S,50,或,S,60,表示，分别为苯转化,40%,、,50%,和,60%,时环己烯选择性；要求大于,80%,；,3.,微晶粒径（,XRD,）,：要求小于,10nm,；,4.,活性组分含量,：,要求大,90%,；,5.,微量元素含量,：,小于,0.001%.,t/,min,T/,o,C,BZ/%,HA/%,HE/%,C,BZ,/mol%,S,HE,/mol%,Y,HE,/mol%,10,139.9,54.13,7.109,38.76,44.54,84.82,37.78,15,141.7,37.41,11.83,50.76,61.30,81.46,49.94,20,139.6,23.96,17.64,58.40,75.01,77.22,57.93,25,141.5,16.27,22.87,60.85,82.94,73.16,60.68,30,140.0,10.66,28.05,61.30,88.78,69.13,61.37,45,140.1,3.262,42.54,54.20,96.54,56.62,54.66,60,138.4,1.109,53.80,45.10,98.82,46.20,45.65,表,2.1,催化剂（,SJ101028,）在,140,o,C,下的活性与选择性,t/,min,T/,o,C,BZ/%,HA/%,HE/%,C,BZ,/mol%,S,HE,/mol%,Y,HE,/mol%,10,149.3,68.83,3.889,27.28,30.04,87.78,26.37,15,150.0,53.83,6.886,39.29,44.84,85.39,38.29,20,149.2,40.99,10.26,48.75,57.70,82.95,47.86,25,149.1,31.32,13.62,55.06,67.49,80.54,54.36,30,149.1,23.76,17.04,59.20,75.23,78.06,58.72,45,149.2,10.56,26.70,62.74,88.89,70.65,62.80,60,149.6,4.91,35.56,59.53,94.80,63.17,59.89,表,2.2,催化剂（,SJ101028,）在,150,o,C,下的活性与选择性,140,o,C,：,t,50,=12min,，,50,=157,，,S,50,=84%,；,低温性能好,t,60,=15min,，,60,=151,，,S,60,=82%.,高活性、高选择性,150,o,C,：,t,50,=17min,，,50,=111,，,S,50,=84%,；,t,60,=21min,，,60,=108,，,S,60,=82%.,注,：,t,50,、,t,60,分别为苯转化,50%,和,60%,的时间（,min,）；,50,、,60,分别为苯转化,50%,和,60%,时，每克催化剂每小时转化苯的克数；,S,50,、,S,60,分别为苯转化,50%,和,60%,时环己烯选择性,.,2.3,数据处理：,图,2.1,温度对苯转化率（,a,）和环己烯选择性（,b,）的影响,2.4,温度对苯转化率和环己烯选择性的影响,2.5,环己烯选择性和收率的极限值,催化剂编号,t,40,、,40,、,S,40,和,Y,40,20130301,10,t,40,=6min,；,40,=251,；,S,40,=84%,；,Y,40,=32%,20130525,9.5,t,40,=8min,；,40,=189,；,S,40,=84%,；,Y,40,=33%,20130528,10.5,t,40,=10min,；,40,=151,；,S,40,=86%,；,Y,40,=38%,20130322,10.63,t,40,=11min,；,40,=137,；,S,40,=85%,；,Y,40,=34%,20130615,11.5,t,40,=14min,；,40,=108,；,S,40,=87%,；,Y,40,=35%,20121208,12,t,40,=18min,；,40,=84,；,S,40,=86%,；,Y,40,=34%,2.5.1,苯转化,40%,时环己烯选择性和收率的极限值,催化剂编号,t,50,、,50,、,S,50,和,Y,50,20130301,10,t,50,=8min,；,50,=236,；,S,50,=82%,；,Y,50,=41%,20130525,9.5,t,50,=10min,；,50,=189,；,S,50,=82,%,；,Y,50,=41%,20130528,10.5,t,50,=13min,；,50,=145,；,S,50,=83,%,；,Y,50,=42%,20130322,10.63,t,50,=14min,；,50,=135,；,S,50,=84,%,；,Y,50,=42%,20130319,11,t,50,=17min,；,50,=111,；,S,50,=84,%,；,Y,50,=42%,20121208,12,t,50,=23min,；,50,=82,；,S,50,=84%,；,Y,50,=42%,2.5.2,苯转化,50%,时环己烯选择性和收率的极限值,催化剂编号,t,60,、,60,、,S,60,和,Y,60,20130301,10,t,60,=10min,；,60,=226,；,S,60,=80,%,；,Y,60,=48%,20130525,9.5,t,60,=12min,；,60,=189,；,S,60,=79,%,；,Y,60,=47%,20130528,10.5,t,60,=16min,；,60,=141,；,S,60,=80,%,；,Y,60,=48%,20130322,10.63,t,60,=18min,；,60,=126,；,S,60,=81%,；,Y,60,=49%,20130319,11,t,60,=21min,；,60,=108,；,S,60,=82,%,；,Y,60,=49%,20121208,12,t,60,=27min,；,60,=84,；,S,60,=81%,；,Y,60,=49%,2.5.3,苯转化,60%,时环己烯选择性和收率的极限值,结论,：,苯选择加氢是以降低,催化剂,活性来提高,环己烯,选择性的,。,确定了环己烯选择性和收率的极限值。低温高活性催化剂与活性中心的数目和催化剂的表面性质密切相关。,利用反应物和产物的物性特征和动力学因素，利用传质原理可以最大限度提高环己烯选择性。,t,/min,T,/,C,BZ,/%,S,HE,/%,Y,HE,/%,5,144,12.91,90.32,11.66,10,145,24.60,87.97,21.64,15,149,39.54,86.24,34.10,20,155,53.63,82.68,44.34,25,160,65.48,78.56,51.44,2.6.1,催化剂（,2013062211,）直接加氢活性与选择性,t,40,=15min,；,40,=101,；,S,40,=86%,；,Y,40,=34%,；,t,50,=19min,；,50,=99,；,S,50,=84%,；,Y,50,=42%,；,t,60,=23min,；,60,=98,；,S,60,=80%,；,Y,60,=48%.,t,/min,T,/,C,BZ,/%,S,HE,/%,Y,HE,/%,5,149,8.6,92.56,7.96,10,153,19.64,91.90,18.05,15,156,31.15,90.21,28.10,20,158,42.10,87.13,36.68,25,157,52.59,84.58,44.48,30,154,60.14,82.46,49.59,2.6.2,催化剂（,2013062211,）预处理,22h,活性与选择性,t,40,=20min,；,40,=75,；,S,40,=83%,；,Y,40,=50%,；,t,50,=24min,；,50,=79,；,S,50,=85%,；,Y,50,=51%,；,t,60,=30min,；,60,=75,；,S,60,=83%,；,Y,60,=50%.,2.6.3,低温高活性催化剂工业生产数据,第,1,批,t,40,=11min,；,40,=137,；,S,40,=87%,。,t,50,=14min,；,50,=135,；,S,50,=85%,。,t,60,=17min,；,60,=133,；,S,60,=82%,。,第,2,批,t,40,=10min,；,40,=151,；,S,40,=86%,。,t,50,=12min,；,50,=157,；,S,50,=84%,。,t,60,=14min,；,60,=162,；,S,60,=81%,。,第,3,批,t,40,=9min,；,40,=168,；,S,40,=83%,。,t,50,=11min,；,50,=171,；,S,50,=81%,。,t,60,=14min,；,60,=162,；,S,60,=79%,。,第,4,批,t,40,=8min,；,40,=189,；,S,40,=87%,。,t,50,=10min,；,50,=189,；,S,50,=85%,。,t,60,=13min,；,60,=174,；,S,60,=81%,。,Applied Catalysis A,2013,450,：,160-168(,研究论文,),3.1 Ru-Zn,催化剂上苯选择加氢制环己烯,3.,环己烯高选择性和收率多相催化机制,3.2,催化剂表征,图,3.1.Ru-Zn(,x,),催化剂和,Ru-Zn(,x,)AH,的,XRD,谱,催化剂中,Zn,可能以,ZnO,形式存在。,ZnO,与反应修饰剂,ZnSO,4,反应生成了,(Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,。,图,3.2 XPS Ru-Zn(8.6%),催化剂,Zn 2p,3/2,谱,与,ZnO,的,Zn 2p,3/2,的,电子结合能,(BE),接近。,图,3.3.AES Ru-Zn(8.6%),催化剂,Zn LMM,谱,与,Zn(),的俄歇电子,动能,(KE),接近，证实,Zn,助剂以,ZnO,存在。,图,3.4.Ru-Zn(8.6%),催化剂的,AES,深度剖析图,ZnO,在催化剂表面,富集，少部分,Ru,被,氧化为了,RuO,2,。,图,3.5.XPS Ru-Zn(8.6%)AH,的,Zn 2p,3/2,谱,电子结合能,升高了,0.7 eV,。,图,3.6.AES Ru-Zn(8.6%)AH,的,Zn LMM,谱,俄歇电子动能降低了,0.2 eV,，与,(Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,生成一致。,Zn(),将部分,电子转移给了,Ru,。,图,3.7 XPS Ru-Zn(8.6%)AH,的,Ru 3p,3/2,谱,大部分,Ru,以金属,Ru,存在，,一小部分活性最强的活性,中心被氧化为,RuO,2,。,(Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,的生成导致了,Ru,原子配位,环境的变化。,图,3.8.Ru-Zn(8.6%),催化剂和,Ru-Zn(8.6%)AH,的,TEM,照片,图,3.9.Ru-Zn(8.6%),催化剂和,Ru-Zn(8.6%)AH,的,TEM,照片,图,3.10.Ru-Zn(29.1%),催化剂和,Ru-Zn(29.1%)AH,的,TEM,照片,RuO,2,的分步还原峰,图,3.11.Ru-Zn(29.1%),催化剂和,Ru-Zn(29.1%)AH,的,H,2,-TPR,423 K,3.3,催化剂性能,Catalyst,Conversion,a,(%),Selectivity,a,(%),Yield,a,(%),Maximum,yield,b,(%),pH,value,c,Ru-Zn(0%),57.9,38.2,22.1,23.1,5.7,Ru-Zn(2.6%),68.1,47.2,32.1,32.1,5.8,Ru-Zn(5.2%),54.4,69.5,37.8,48.0,5.9,Ru-Zn(7.7%),50.5,71.1,35.9,47.4,5.9,Ru-Zn(8.6%),46.0,76.2,35.1,50.9,6.1,Ru-Zn(9.6%),26.4,84.1,22.2,50.4,5.9,Ru-Zn(12.4%),20.7,86.0,17.8,49.8,6.1,Ru-Zn(14.9%),13.1,87.5,11.5,34.2,5.8,Ru-Zn(29.1%),6.8,90.4,6.2,19.0,6.0,Ru-Zn(0,%),d,100,0,0,0,7.2,Ru-Zn(8.6,%),d,86.7,1.9,1.6,1.6,7.3,表,2.1 Ru-Zn(,x,),催化剂性能,3.4.1.(Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,的,Zn,2+,与,Ru,之间有电子相互作用。,3.4,量子化学研究,3.4.2 (Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,均匀分散在催化剂表面，可以占据一部活性强的,Ru,活性位。,H,H,H,H,3.4.3.(Zn(OH),2,),3,(ZnSO,4,)(H,2,O),5,含有丰富的结晶水，可以在催化剂表面形成稳定的滞水层。,1.ZnO,在催化剂表面富集，不能提高,Ru,催化剂的环己烯选择性。,2.ZnSO,4,难于化学吸附在,Ru,催化剂表面，只能在一定程度上提高,Ru,催化剂的环己烯选择性。,3.,表面的,ZnO,可以浆液中,ZnSO,4,反应生成一种新的物质，对提高,Ru,催化剂环己烯选择性的关键作用。,4.,催化体系系和化学环境对提高环己烯的选择性具有重要作用。,3.7,结论,4.,纳米,Ru-Mn/ZrO,2,催化剂上苯选择加氢制环己烯,催化学报，,2013,34:684-694(,封面文章,),5.,第四周期过渡金属对苯加氢,Ru,基催化剂性能的影响,Applied Catalysis A,2013,Accepted.,6.,助剂,La,在苯加氢,Ru,催化剂环己烯选择性中的作用,Journal of Molecular Catalysis A,2013,368-369:119-124.,7.Ce,修饰的,Ru,催化剂上苯选择加氢制环己烯,Journal of energy chemistry,2013,Accepted.,8.,醇类对苯选择加氢制环己烯,Ru-Zn,催化剂性能的影响,Chemical Engineering Journal,2013,218:415-424;,Thank You!,