催化简介新版.pptx

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,*,Advanced principles in catalysis,Chapter One：Catalysis and Catalysts,Yongdan Li,Department of Catalysis Science and Technology,Catalytic phenomenon,One of the most important natural phenomena,Life processes,Without catalysis,life is not possible,Natural Processes,Acid and base processes,Active application of catalysis,Fermentation,SO,2,+1/2O,2,SO,3,有奖竞猜,:,出处,?,有关人物,?,待月西厢下,迎风户半开,月移花影动,疑是玉人来,2023 CATTECH 5,2,Dfinition de la catalyse,Beaucoup de corps ont la proprit dexercer sur dautres corps une action trs diffrente de laffinit chimique.Par cette action,ils conduisent la dcomposition des corps et la formation de nouveaux composs,qui ont une composition dans laquelle ils nentrent pas.Cette nouvelle puissance,inconnue jusqualors,que lon trouve la fois dans la nature organique et inorganique,je lappellerai,puissance catalytique,.Jappellerai aussi,catalyse,la dcomposition des corps par cette force,Jns Jakob Berzelius(1836),Un catalyseur est une substance qui change la vitesse dune raction chimique sans que lui-mme apparaisse dans les produits,Wilhelm Ostwald(1895),A catalyst is,a substance,that,selectively transforms reactants into products,through,an uninterrupted,and repeated cycle of,elementary steps,in which,the catalyst participates,while being,regenerated in its original form at the end,of each cycle during the life of the catalyst.,M.Boudart,Perspectives in Catalysis,(J.M.Thomas and K.I.Zamaraev,Eds),Blackwell,Oxford,1992,p.183,Definition of Catalysis,W.Ostwald,P.Sabatier,R,P,I,R,P,*,R,P,1900,1900,1925,Intermdiaire instable,Site actif,W.Ostwald,P.Sabatier,H.S.Taylor,dlocalise,physique,localise,chimique,localise,chimique,Michel Che,Presented on the“Workshop for Building up the Core Courses in Industrial Catalysis”,Tianjin,August,2023,Definition of Catalysis,A catalyst is a,substance,that,increases,the,rate,at which a chemical reaction approaches,equilibrium,without itself becoming,permanently,involved in the reaction.,James T.Richardson,Principles of Catalyst Development,Plenum Press,New York and London,1989,一种催化剂是一种,物质，,它,增长,一种化学反应到达,平衡,旳,速率，,但它本身不,永久,旳牵涉在反应中。,Property,Actively involved in the reaction,It is a reactant,Contact action-No remote superpower,Follow all chemical laws,Increase the rate of approaching equilibrium,Can not change thermodynamic equilibrium,Not permanently involved,One site catalyze the reaction of many molecules in a sequential manner,Definition of Catalysis,N,2,3H,2,2NH,3,Activation energy for gas phase reaction as high as 57 kcal/mole,Catalytic pathway,H,2,2H,a,N,2,2N,a,N,a,+H,a,NH,a,NH,a,+H,a,(NH,2,),a,(NH,2,),a,+H,a,(NH,3,),a,(NH,3,),a,NH,3,Adsorption of nitrogen is rate limiting step with an activation energy of 12 kcal/mole。,At 500,o,C increase the rate of reaction by 10,13,times！,ExampleAmmonia synthesis,Operating conditions,:,-,T:as low as,78 K,and as high as,1500 K,-P:as low as 10,-9,and as high as 103 bar,-reactants in gas phase,-reactants in polar or non polar solvents,-with or without assistance of photons,radiation or electron transfer at electrodes,-with pure metals as unreactive as gold or as reactive as sodium,-with multicomponent and multiphase inorganic compounds and acidic organic polymers,-at site time yields as low as 10,-5,s,-1,(one turnover per day)and as high as 109 s,-1,(gas kinetic collision rate at 10 bar),Range of Catalytic Reactions,Michel Che,Presented on the“Workshop for Building up the Core Courses in Industrial Catalysis”,Tianjin,August,2023,Four key points of the definition,1,Chemical equilibrium cannot be changed,Chemical equilibrium depends only on the state of system,thermodynamic functions,G,r,H,r,and,K,r,depends only on the start and end state,Catalyst can only accelerate the reactions with,G,r,0,G,r,0,can be used to judge if a reaction happens or not,Table 1.Criteria for the feasibility of a reaction,G,r,0,Feasibility,1.10 kcal/mole,Non feasible,What is,G,?,What is,G,r,?,What is,G,r,0,?,Four key points of the definition,2 Catalyst accelerates forward and backward reactions in the same time and with same ratio,Chemical equilibrium constant is not changed,A good catalyst for the forward reaction is also a good catalyst for the backward reaction,Hydrogenation and dehydrogenation,Ammonia Synthesis,Catalyst is a species in the reaction system,thus contributes to the thermodynamic state of the system,3 A catalyst has selectivity,Normally a system has many possible reactions,A catalyst accelerates one specific reaction,A catalyst is a reactant,It interacts with other reactants by chemical reactions,Its activity depends on the chemical state of itself,Examples,HCOOH,H,2,O+CO Al,2,O,3,Catalyst,HCOOH H,2,+CO,2,Metal catalyst,CO+H,2,methane methanation,mixed hydrocarbons F-T synthesis,Methanol,Mixed alcohols,Mixed oxygenated compounds,Four key points of the definition,4 A catalyst has limited life,Not permanently involved,Highly active material,Lose activity for many reasons,Its a chemical substance,It undergoes natural involvement,Deactivation is a slow process,Compared to molecular reaction,Four key points of the definition,Property of catalyst,Activity,High reaction rate is desirable,Higher output,smaller reactor volume is preferred,Low reaction temperature and low pressure are favored,High yield,Easy operation,Slow deactivation,Better selectivity,Selectivity,High yield of purpose product,Control of deactivation,High output for industrial process,Deactivation and life,Time dependent yield,Decide operation mode and economical benefits,Important property of a catalyst,Catalysis,Catalytic phenomenon,A science covering catalysis and its technology,Industrial catalysis discipline,Catalysis science,commercial application of catalysis and related reaction engineering,Sub disciplines of industrial catalysis,Homogeneous catalysis,Mechanism:ligand exchange reaction,Homogeneous catalyst,Homogeneous catalysis,Several definitions,Heterogeneous catalysis,Heterogeneous system,Mechanism:surface adsorption and reaction,Interfacial processes are important,No need for catalyst separation with reactants,Widely used in industry,Suitable for large scale production,Heterogeneous catalyst,Several definitions,Enzymatic catalysis,Bioactive catalyst,Like homogeneous catalyst,Very high specific activity,Very high selectivity,Bioactive material,Enzyme catalyst,Enzyme catalysis,Contents of this course,Principles of heterogeneous catalysis,Principles of heterogeneous catalysts,Process need to heterogeneous catalysts,Several definitions,Process Technology,Shape,size,pores,mechanical property,Kinetics,selectivity,Mass,heat and,momentum transfer,Stability and life,Reaction engineering,optimization,mass and heat transfer,Synthetic chemistry,Engineering sciences,Catalysis,Transfer,Interface,Physics and Materials science,Particle,Reactor,Intrinsic process,Application,New process,Max yield,Min consumption,Easy operation,Material,structure,mechanism,microscopic dynamics,Active sites,Supporting knowledge,Multiscale and multidisciplinary nature of industrial catalysis,An example -power generation from coal,It is not just chemistry,You can not ignore the technology,Shapes of real catalysts,Phenomena in catalytic reactors,Contributions of catalytic science to human society,Key techs in 20 century,which changed the life of human,Ammonia synthesis,Petroleum processing,Polymerization,Environmental cleanup techs,Fuel cells,Key techs changing the life of human,Fuel cell technology,Hydrogen energy system,high performance fuel,Key techs awaiting breakthrough and will change the life,Photo stimulated decomposition of water,Liquefaction of coal,Natural gas upgrading,Environmental issues,Catalysis looks,to the future,National Academy Press,Washingon,D.C.,1992,2023:W.S.Knowles/H.Kagan,R.Noyori,K.B.Sharpless(Nobel/Wolf Prize 2023)for chirally catalysed hydrogenation/oxidation,.,Historical overview of catalytic technology,Table 1,History of development of catalytic processes,Year,Process,Catalyst,1750,H2SO4 lead chamber process,NO/NO2,1870,SO2 oxidation,Pt,1880,Deacon process(Cl2 from HCl),ZnCl2-CuCl2,1885,Claus process(H2S and SO2 to S),bauxite,1900,fat hydrogenation,Ni,methane from syngas,Ni,1910,coal Liquefaction,Fe,upgrading coal liquids,WS2,ammonia synthesis(Haber-Bosch),Fe/K,NH3 oxidation to nitric acid,Pt,1920,methanol synthesis(high pressure process),Zn,Cr oxide,Fischer-Tropsch synthesis,promoted Fe,Co,SO2 oxidation,V2O5,acetaldehyde from acetylene,Hg2+/H2SO4,1930,catalytic cracking(fixed bed,Houdry),clays,Ethane epoxidation,Ag,polyethylene chloride,peroxide,Polyethylene(low density,ICI),peroxide,oxidation of benzene to maleic anhydride,V,alkylation,HF/H2SO4,1940,hydroformylation,alkene to aldehyde,Co,catalytic reforming(gasoline),Pt,cyclohexane oxidation(nylon 66 production),Co,benzene hydrogenation to cyclohexane,Ni,Pt,Synthetic rubber,SBR,BNR,Butylrubber,Li,peroxide,peroxide,Al,1950,polyethylene(high density)Ziegler-Natta,Phillips,Ti,Cr,polypropene Ziegler-Natta,Ti,polybutadiene Ziegler-Natta,Ti,Co,Ni,hydrodesulfiding(HDS),Co,Mo sulfides,naphtalene oxidation to phthalic anhydride,V,Mo oxides,ethylene oxidation to acetaldehyde,Pd,Cu,p-xylene oxidation to terephtalic acide,Co,Mn,ethylene oligomerization,Al(Et)3,1960,butene oxidation to maleic anhydride,V,P oxides,acrylonitrile via ammoxidation of propene(Sohio),Bi,Mo oxides,propene oxidation to acrolein/acrylic acid,Bi,Mo oxides,xylenes hydroisomerisation,Pt,propene metathesis,W,Mo,Re,adiponitrile via butadiene hydrocyanization,Ni,improved reforming catalysts,Pt,Re/Al2O3,improved cracking catalysts,Zeolites,acetic acid from MeOH(carbonylation),Co,vinyl chloride via ethene oxyclorination,Cu chloride,ethene oxidation to vinyl acetate,Pd/Cu,o-xylene oxidation to phthalic anhydride,V,Ti oxides,propene oxidation to propene oxide,Mo,hydrocracking,Ni-W/Al2O3,HT water-gas shift process,Fe2O3/Cr2O3/MgO,LT water-gas shift process,CuO/ZnO/Al2O3,1970,methanol synthesis(low pressure,ICI),Cu-Zn-Al oxide,acetic acid from MeOH(carbonylation,low pressure process,Monsanto),Rh,improved process for xylene isomerization,zeolite,-alkenes via ethene oligomerization/isomerization/metathesis(SHOP),Ni,Mo,improved hydroformylation,Rh,auto exhaust gas catalysts,Pt/Rh,L-DOPA(Monsanto),Rh,cyclooctenamer(metathesis),W,hydroisomerization,Pt/zeolite,selective reduction of NO(with NH3),V2O5/TiO2,1980,gasoline from methanol process(Mobil),zeolite,vinyl acetate from ethane and acetic acid,Pd,methylacetate(carboxylation),Rh,methylacrylate via t-butanol oxidation,Mo oxides,improved coal liquefication,Co,Mo sulfides,diesel fuel from syngas,K,Na,1990,polyketon(from CO and ethene,Pd,主要参照书,TE624.4/G2,催化过程旳化学(美)盖茨(Gates,B.C.)等著 徐晓等译盖茨 B.C.著,O643.3/D64,催化作用原理导论 邓景发编著邓景发 编著,O643.3/S34,多相催化中旳传质(美)C.N.塞脱菲尔特著 陈诵英译萨特菲尔德(Satterfield,C.N.)著,TQ426/L94,工业催化原理 李玉敏编著李玉敏 编著,TQ032/W96-1,绿色催化过程与工艺 王延吉,赵新强编著王延吉 编著,O643.3 C357-1,Catalysis:principles and applications/editors,B.Viswanathan,S.Sivasanker,A.V.RamaswamyViswanathan,B.,O647 K81-1,Surface science:foundations of catalysis and nanoscience/Kurt W.KolasinskiKolasinski,Kurt.,XX(345755.2),Material concepts in surface reactivity and catalysis/Henry Wise,Jacques OudarWise,Henry,1919-,TQ032 H143,Industrial catalysis:a practical approach/Jens HagenHagen,Jens.,主要参照书,O64 K52 v.6,The Chemical physics of solid surfaces and heterogeneous catalysis,.v.6,Coadsorption,promoters and poisons/D.A.King,D.P.Woodruff,edKing,D.A.,TQ032.41 S253,Heterogeneous catalysis in industrial practice,/Charles N.SatterfieldSatterfield,Charles N.,O643.31 R523,Principles of catalyst development,/James T.RichardsonRichardson,James Thomas,1928-,主要参照书,O643.32 S774Heterogeneous catalytic science/author,R.D.SrivastavaSrivastava,R.D.,O643.3 B711=2Heterogeneous catalysis:principles and applications/G.C.BondBond,G.C.(Geoffrey Colin),TQ03 L478Heterogeneous reactor design/Hong H.LeeLee,Hong H.,O643.3 B756Kinetics of heterogeneous catalytic reactions/Michel Boudart and G.Dj鈋ga-MariadassouBoudart,Michel.,主要参照书,TQ032.42 S253Heterogeneous catalysis in practice/Charles N.SatterfieldSatterfield,Charles N.,TQ02 C263Chemical and catalytic reaction engineering/James J.CarberryCarberry,James J.,O643.3 D767The physical basis for heterogeneous catalysis:Battelle Institute Materials Science Colloquia,Gstaad,Switzerland,Sept.2-6,1974/Robert I.Jaffee,chairman;edited by Edmund Drauglis,Robert I.JaffeeBattelle Institute Materials Science Colloquia(9th:1974:Gstaad,Switzerland),O643.3 S253Mass transfer in heterogeneous catalysis by Charles N.SatterfieldSatterfield,Charles N.,主要参照书,