绿色能源与环境保护Lecture1

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1、Limin Chen（陈礼敏）Tel:13710847179E-mail:Office:B4-505Green Energy And Green Energy And Environmental ProtectionEnvironmental Protection Pollution from traditional energy Petroleum processing and utilization Coal utilization Biomass Energy plants Thermochemical conversion Biological conversion Solar ene

2、rgy Photovoltaic conversion Photothermal conversion Photochemical conversion Other green energy:hydro energy,wind,nuclear,geothermal energy,ocean energy,natural gas hydrate Hydrogen Production Storage&Utilization Fuel cells:DMFC,lithium ion battery Main ContentsReferenceEvaluation MethodAttendance p

3、oints:10 points credit will be possible for perfect attendance.Presentation:40 points Final Exam:Points earned on the final exam will be prorated to a maximum of “50 before assigning final grades.Pollution from Petroleum Pollution from Petroleum UtilizationUtilizationWorld Energy Consumption Trends

4、by SourceWorld Energy consumption by SourceCO2 emission from different energy sourcehttp:/en.wikipedia.org/wiki/File:Global_Carbon_Emission_by_Type.pngRunning out of oil?The concern about running out of oil arises from misunderstanding the significance of a petroleum industry measure called the Rese

5、rves/Production ratio(R/P).This monitors the production and exploration interactions.The R/P is based on the concept of proved reserves of fossil fuels.Proved reserves are those quantities of fossil fuels that geological and engineering information indicate with reasonable certainty can be recovered

6、 in the future from known reservoirs under existing economic and operating conditions.The Reserves/Production ratio is the proved reserves quantity divided by the production in the last year,and the result will be the length of time that those remaining proved reserves would last if production were

7、to continue at the current level.It is important to note the economic and technology component of the definitions,as the price of oil increases(or new technology becomes available),marginal fields become proved reserves.We are unlikely to run out of oil,as more fields become economic.Note that inves

8、tment in exploration is also linked to the R/P ratio,and the world crude oil R/P ratio typically moves between 20-40 years,however specific national incentives to discover oil can extend that range upward.Running out of oil?Crude Oil Proved Reserves R/P RatioMiddle East 89.4 billion tonnes 93.4 year

9、USA 3.8 9.8 yearsUSA-1995 USGS data 10.9 33.0 yearsTotal World 137.3 43.0 yearsCoal Proved Reserves R/P RatioUSA 240.56 billion tonnes 247 yearsTotal World 1,043.864 235 yearsNatural Gas Proved Reserves R/P Ratio USA 4.6 trillion cubic metres 8.6 yearsUSA-1995 USGS data 9.1 17.0 yearsTotal World 141

10、.0 66.4 years.One billion=1 x 109.One trillion=1 x 1012.One barrel of Arabian Light crude oil=0.158987 m3 and 0.136 tonnes USGS:U.S.Geological SurveyChemical Constitution of PetroleumCrude OilOrganicCompoundsHydrocarbons(C,H)MetalsHeteroatomCompounds(S,N,O)InorganicCompounds(Na+,Ca2+,Cl-)OrganicComp

11、ounds(Ni,V,Fe)Crude Oil Crude Oil is a mixture of hydrocarbons containing a mixture of 100,000 to 1,000,000 different compounds Boiling range well over 1,000 oF At the lower end are the gaseous hydrocarbonsmethane(CH4)and ethane(C2H6)and inorganic gases such as hydrogen sulfide(H2S)and carbon dioxid

12、e.At the upper end,the material becomes non-volatile at about 1100F(atmospheric equivalent boiling point)resins and asphaltenes contain varying degrees sulfur,nitrogen,oxygen,and heavy metals such as vanadium and nickel.Hydrocarbons Essential components of petroleum-C,H compounds based on quadrivale

13、ncy of carbon atoms-Linked by a single bond(alkanes)-Linked by double bond-Alkenes-Linked by conjugated double bonds in ring structures-AromaticsCC Saturated Aliphatic HC(n-alkanes or n-paraffins)-Straight chains of C atoms each with 2,3 H atoms(except CH4)general formula:CnH2n+2 CH3-(CH2)n-CH3:Ex)n

14、-pentane:CH3-CH2-CH2-CH2-CH3CC CAlkanes-Boiling point and density increase with increasing#of C atoms-Effect is much more pronounced at low C#sBranched Alkanes(iso-alkanes)-Branching in the carbon chainCCCCCCCC-Boiling pt.of n-alkanes B pt.of iso-alkanes with the same#of CB.PB.P-due to molecular int

15、eractions and dispersion forcesIsomers:compounds that have the same chemical formula,but different structures different chemical and physical propertiesIsomers of AlkanesThis is the principal reason for the molecular complexity of petroleum-especially in the higher boiling region.Alkyl groups:Alkane

16、 minus a hydrogen atom=Alkyl radical(R)Ex)CH4CH3:methyl radical group C2H6C2H5:ethyl radical group#C Atoms:5#Isomers:3#C Atoms:8#Isomers:18#C Atoms:18#Isomers:60,523#C Atoms:40#Isomers:6,200,000,000,000-Iso-octane(an isomer of n-octane)-2,2,4-trimethylpentaneCCCCCCCC*i-alkanes have high octane#:e.g.

17、,Octane#of 2,2,4-TMP=100 n-alkanes have low octane#:e.g.,Octane#of n-heptane=012345Saturated Cyclic HC(cycloparaffins or naphthenes)-Cyclic structures(or rings)in all or part of skeleton-e.g.cyclohexaneMisleading 2-DrepresentationActually non-planar structures-General formula for single ring compoun

18、ds:CnH2nBoiling points and densities of cycloalkanes boiling points of n-alkanes for the same#of C Unsaturated Aliphatic HC(alkenes or olefins)-Little or no olefins in crude oils-produced by refinery operationsFor example:ethylene(H2C=CH2)and propylene(H2C=CH-CH3);petrochemical feedstocksAromatic Hy

19、drocarbons Cyclic and polyunsaturated hydrocarbons-Conjugated double bondsBenzeneAlkylaromaticsTolueneCH3CH3CH3Xylene(meta)orthoparaBTX:Important petrochemical feedstocks Aromatic compounds have high octane numbers,but content in gasoline is limited by environmental regulations-health effects due to

20、 high toxicityPolyaromatic Hydrocarbons(PAH)or Polynuclear Aromatics(PNA)Aromatic hydrocarbons containing more than one ring,commonly containing more than two ringsNaphthaleneAnthracenePhenanthrenePyrene associated with environmental and health problems-toxic compounds deactivate catalysts via cokin

21、g reactionsHydroaromatics of naphtenoaromatics-Partially saturated PAH;e.g.tetralin (tetrahydronaphthalene)-strong H donorsHeteroatom CompoundsSulfur Compounds most problematicS+H2SSCH3CH3shielding prevents removalof SulfurSulfides R-S-R R-S-S-R (disulfides)*can be readily removed+H2Heteroatom Compo

22、undsNitrogen Compounds two kinds1)NeutralNH2)BasicN quinoline*neutralizes acidic sites,thereby destroying catalytic activitycarbazoleHeteroatom CompoundsOxygen CompoundsCOHOCarboxylicOHPhenolic*Both could cause corrosion problemsMetal CompoundsPorphyrins most common organometallic compounds -metal a

23、toms(Ni,V,Fe)at the center of cage structures -use H to saturate structure and break bonds to release metal atomsProperties of Crude OilI.Physical PropertiesA.APIB.ViscosityC.Pour PointD.Flash PointE.Vapor PressureF.Carbon ResidueG.Salt ContentH.MetalsI.Sediment and WaterJ.AcidityK.SulfurII.Specific

24、ation of Crude OilIII.TBP DistillationIV.Specification and Environmental RegulationsV.Octane NumberPhysical PropertiesSG API APIH2O=10Crude Oils-API 10-50*most commonly 20-45Because of this inverse relationship between API and SG(specific gravity)there is a desire for high API crude oil for high dis

25、tillate yield(e.g.,gasoline,diesel,and jet fuel).(ASTM D-287)131.5 SG141.5 APIF15gravity60FASTM:American Society for Testing and MaterialsPhysical PropertiesViscosity ASTM D-2983 flow properties,resistance to flowPour Point(PP)ASTM D-97 temperature at which oil ceases to flow-PP waxiness of oil(n-pa

26、raffin)PP n-paraffinsFlash Point(F)ASTM D-93 temperature above which the oil will spontaneously igniteVapor Pressure(F)ASTM D-323 also known as(Reid RVP)True vapor pressure usually 5-9%RVP Other Properties of OilsCarbon Residue-solid residue(%wt)remaining after heating to coking temperaturesTwo test

27、s:1)ASTM D-524 Ramsbottom Carbon2)ASTM D-189 Conradson CarbonConradson Carbon Residue(CCR)fouling catalyst deactivation coking propensityCCR Asphaltene Salt content ASTM D-3230 lb NaCl/1000 bbl desalting is necessary because NaCl content 10 lbs/1000 bbl leads to corrosion!Other Properties of OilsMet

28、als EPA method 3040 Ni,V,Ag,Hg,Na,Ca catalyst deactivation V 2 ppm in fuel oils corrosion problemsSediment&Water ASTM D-96 inorganic particles operational problemsAcidity ASTM D-664 titration w/KOHSulfur ASTM D-129,1266,1552,2622 sour crudes S 0.5 wt%sweet crudes S 1000FTrue Boiling Point Distillati

29、on(TBP)Specifications and Environmental RegulationsGasoline-octane number-resistance to ignition by compression87 Regular CR:989 Plus93 Super CR:12Spark IgnitionEngine Knock-Spontaneous ignition of fuel(higher octane gas reduces engine knock)CompressionratioDiesel cetane number(ASTM D-613)ease of ig

30、nition when compressed with air.CompressionIgnitionOctane NumberR:Research Octane (ASTM 2699)M:Motor Octane(ASTM-2700)Octane Number:R+M 2 Octane measured by comparing performance of gasoline to binary mixture of:n-heptane (0)2,2,4-trimethylpentane (100)*Gasoline distilled straight from crude oil has

31、 an O.N.of 40Control O.N.with additives such as:1)TEL(tetraethyl lead)-leaded gasoline(phased out)2)Oxygenates ProductsDesired Products and Important Properties:1)Fuel heating value2)Gasoline octane number(87-93)increase compression ratio while preventing“knocking”-increases power.-aromatics(benzene

32、)-leaded fuel TEL(tetraethyl lead)*However,Pb poisons the catalyst in catalytic converter so lead was removed.Pb is toxic.Pb had been added to increase octane number.-sulfur -vapor pressure3)Solvents purity(boiling point)4)Diesel cetane(hexadecane C16H34)Cetane number determines ease of ignition und

33、er compression -sulfurProducts5)Heating/Fuel Oils heating value -viscosity -sulfur and nitrogen6)Lube Oil viscosity -thermal sensitivity -purity7)Asphalt asphaltene content -binding properties8)Heavy Fuel Oils heating value -sulfur and metals9)Cokea)Fuel volatile matter(ignitability)-S and metalsb)M

34、aterial crystallinity -S and metalsObjectives in RefiningCrude OilRefining ProcessProducts:1)Fuels2)Petrochemicals3)MaterialsChemical ConstitutionPhysicalProperties1)Separation2)Conversion3)Finishing4)SupportSpecificationsOverall Objective:Convert crude oil into desired products in an economicallyfe

35、asible and environmentally acceptable manner!RefineryEnvironmentalEconomicFuture ProspectsProductsDemand for gasoline&Diesel increasing*sulfur and metal content has been increasing with the heavier crude oils being collected in recent timesfuture prospects:-catalysts -new processes -modeling*20 mill

36、ion barrels is consumed in the U.S.per day(1 barrel=42 U.S.gal)*60%of oil is importedSimple Refinery FlowGasolineLPGJet Fuel&DieselAsphaltCokeFuel OilDistillationDewaxingDeasphaltingCatalyticCrackingAlkylationReformingDelayed CokingDesaltingHydrotreatmentCrude OilSulfur RecoveryHydrogen ProductionSe

37、parationFinishingConversionSupportLight EndsUnitHydrocrackingVisbreakingBlendingFuture Trends in Petroleum RefiningProduct slate:-gasoline/diesel Overall energy demand structureDemand for ProductsFeedstock SupplyEnvironmentalRegulationsTechnologyDevelopmentForces&FactorsGeopolitics°rading quality

38、 of crude oil Alternative feeds-oil sand-natural gas-coalMore strict regulations on-transportation fuels-refinery operationsNew refining technologies-processes-catalysts Other technol.-fuel cellNeed for More Flexible and Versatile Refinery Crude Trends in U.S.Source:F.Self,E.Ekholm,and K.Bowers,Refi

39、ning Overview-Petroleum,Processes and Products,AIChE,2000.(ROPPP)US EPA Tier 2 Regulations on Fuels U.S.EPAs Tier 2 gasoline sulfur rule and recently adopted diesel ruling will both have a dramatic effect on the U.S.refining industry.New gasoline sulfur regulations will require most refiners to meet

40、 a 30 ppm sulfur average with an 80 ppm cap for both conventional and reformulated gasoline by January 1,2006.The new on-road diesel regulation specifies a per-gallon sulfur cap of 15 ppm effective June 1,2006.New Processes for Low-Sulfur Fuels Process Design for Ultra-Low Sulfur Fuel New and more a

41、ctive and more selective catalysts for existing HDS processes.Novel processing scheme that does not depend on HDS.Examples of New Processing Approaches:Reactive adsorption of sulfur without high-pressure HDS(Phillips Petroleum)Selective adsorption of sulfur compounds,without hydrogen(Penn State Univ

42、ersity research)Liquid-phase oxidation followed by extraction.Bio-desulfurization that is not limited by steric restriction of 4,6-DMDBT(Energy Biosystems).Future RefineryIncreasingly heavier and more sour crude supplyDemand for cleaner and higher-performance transportation fuelsChallenges for Futur

43、e Refinery Heavy residue conversion Reduction of heterotaoms and aromatics in fuels diesel problem in U.S.Attainment of the required performance characteristics Octane number(conflict!)Cetane number Increasingly higher demand for hydrogenSources of Hydrogen Current Sources Catalytic reforming-capaci

44、ty will be reduced by limits on aromatics content of gasoline Natural gas-increasing demand for electricity generation Possible Future Sources Reforming Light ends(C1-C4)Reforming Heavy Ends(e.g.,heavy fuel oil,VDR)Gasification of Coke Pollution from Petroleum CxHy,Aromatics,SOx,NOx,CO,CO2.Additives.What about other pollution?How to resolve the pollution from petroleum?谢谢观看/欢迎下载BY FAITH I MEAN A VISION OF GOOD ONE CHERISHES AND THE ENTHUSIASM THAT PUSHES ONE TO SEEK ITS FULFILLMENT REGARDLESS OF OBSTACLES.BY FAITH I BY FAITH