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GreenEnergyAnd
EnvironmentalProtection
LiminChen(陈礼敏)
Tel:**********
E-mail:******@
Office:B4-505:.
MainContents
• Pollutionfromtraditionalenergy
Petroleum processing and utilization
                 Coal utilization
• Biomass
Energy plants
               Thermochemical conversion
                Biological conversion
• Solarenergy
Photovoltaic conversion  
                 Photothermal conversion 
                 Photochemical conversion
• Othergreenenergy:hydro energy, wind, nuclear,geothermal            
energy, ocean energy, natural gas hydrate
•  Hydrogen
Production
                Storage & Utilization
•  Fuelcells:DMFC, lithium ion battery                 :.
Reference
EvaluationMethod
Attendancepoints:10 points credit will be possible for perfect attendance.
Presentation:40 points 
FinalExam:Points earned on the final exam will be prorated to a maximum of 
    “50" before assigning final :.
PollutionfromPetroleum
Utilization:.
WorldEnergyConsumptionTrendsbySource:.
WorldEnergyconsumptionbySource:.
COemission from different energy source
2 
:Global_Car
:.
Running out of oil ??
    The concern about "running out of oil" arises from misunderstanding the 
 significance of a petroleum industry measure called the Reserves/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 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 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 investment in 
exploration is also linked to the R/P ratio, and the world crude oil R/Pratio
typicallymovesbetween20-40 years, however specific national incentives to 
discover oil can extend that range upward. :.
Running out of oil ??
CrudeOilProvedReservesR/PRatio
USA-
CoalProvedReservesR/PRatio
TotalWorld1,
NaturalGasProvedReservesR/PRatio
USA-
.
Onebillion==1x1012.
3
OnebarrelofArabianLightcrudeoil=
USGS::.
ChemicalConstitutionofPetroleum
Organic
Compounds
Heteroatom
Hydrocarbons
Compounds
(C,H)
(S,N,O)
Crude
Oil
InorganicOrganic
CompoundsCompounds
+2+-
(Na,Ca,Cl)(Ni,V,Fe)
Metals:.
CrudeOil
•CrudeOilisamixtureofhydrocarbonscontainingamixtureof
100,000to1,000,000differentcompounds
o
•Boilingrangewellover1,000F
–Atthelowerendarethegaseoushydrocarbons
–methane(CH)andethane(CH)
426
–andinorganicgasessuchashydrogensulfide(HS)and
2
carbondioxide.
–Attheupperend,thematerialbecomesnon-volatileatabout
1100°F(atmosphericequivalentboilingpoint)
–resinsandasphaltenes
–containvaryingdegreessulfur,nitrogen,oxygen,and
heavymetalssuchasvanadiumandnickel.
:.
Hydrocarbons
•Essentialcomponentsofpetroleum
-C,HcompoundsbasedonquadrivalencyofcarbonatomsC
-Linkedbyasinglebond(alkanes)CC
-Linkedbydoublebond
CC
-Alkenes
-Linkedbyconjugateddoublebondsinringstructures
-Aromatics
•SaturatedAliphaticHC(n-alkanesorn-paraffins)
-StraightchainsofCatomseachwith2,3Hatoms(exceptCH4)
•generalformula:CnH2n+2
•CH3-(CH2)n-CH3:Ex)n-pentane:CH3-CH2-CH2-CH2-CH3:.
Alkanes
-Boilingpointanddensityincreasewithincreasing#ofCatoms
-EffectismuchmorepronouncedatlowC#’s
CC
•BranchedAlkanes(iso-alkanes)
CCCCC
-Branchinginthecarbonchain
C
--alkanes>-alkaneswiththesame#ofC
>
-duetomolecularinteractionsanddispersionforces
Isomers:compoundsthathavethesamechemicalformula,but
differentstructuresdifferentchemicalandphysicalproperties:.
IsomersofAlkanes
Thisistheprincipalreasonforthe
#CAtoms:5
#Isomers:3molecularcomplexityofpetroleum-
especiallyinthehigherboilingregion.
#CAtoms:8
Alkylgroups:
#Isomers:18
Alkaneminusahydrogenatom=
#CAtoms:18
Alkylradical(R•)
#Isomers:60,523
Ex)CH4CH3•:methylradicalgroup
#CAtoms:40
C2H6C2H5•:ethylradicalgroup
#Isomers:6,200,000,000,000
CC
-Iso-octane(anisomerofn-octane)
12345
-2,2,4-trimethylpentaneCCCCC
C
**i-alkaneshavehighoctane#:.,Octane#of2,2,4-TMP=100
n-alkaneshavelowoctane#:.,Octane#ofn-heptane=0:.
SaturatedCyclicHC(cycloparaffinsornaphthenes)
-Cyclicstructures(orrings)inallorpartofskeleton
-
-Generalformulaforsingle
Misleading2-DActuallynon-
ringcompounds:
representationplanarstructures
CH
n2n
Boilingpointsanddensitiesofcycloalkanes>boilingpointsof
n-alkanesforthesame#ofC
•UnsaturatedAliphaticHC(alkenesorolefins)
-Littleornoolefinsincrudeoils
-producedbyrefineryoperations
Forexample:ethylene(HC=CH)andpropylene(HC=CH-CH);
2223
petrochemicalfeedstocks:.
AromaticHydrocarbons
•Cyclicandpolyunsaturatedhydrocarbons
-Conjugateddoublebonds
Alkylaromatics
Benzene
CH3
CH3CH
3
para
TolueneXylene(meta)ortho
BTX:Importantpetrochemicalfeedstocks
•Aromaticcompoundshavehighoctanenumbers,butcontentin
gasolineislimitedbyenvironmentalregulations--healtheffectsdue
tohightoxicity:.
PolyaromaticHydrocarbons(PAH)or
PolynuclearAromatics(PNA)
•Aromatichydrocarbonscontainingmorethanonering,commonly
containingmorethantworings
NaphthaleneAnthracene
PhenanthrenePyrene
•associatedwithenvironmentalandhealthproblems-toxic
compounds
•deactivatecatalystsviacokingreactions
Hydroaromaticsofnaphtenoaromatics
-PartiallysaturatedPAH;
(tetrahydronaphthalene)-strongHdonors:.
HeteroatomCompounds
SulfurCompounds–mostproblematic
+H
2
+HS
2
S
S
CHCHSulfidesR-S-R
33
R-S-S-R(disulfides)
*canbereadilyremoved
shieldingpreventsremoval
ofSulfur:.
HeteroatomCompounds
NitrogenCompounds–twokinds
1)Neutral
carbazole
N
H
2)Basic
quinoline
N
*neutralizesacidicsites,therebydestroyingcatalyticactivity:.
HeteroatomCompounds
OxygenCompounds
O
OH
C
OH
Phenolic
Carboxylic
*Bothcouldcausecorrosionproblems
MetalCompounds
Porphyrins–mostcommonorganometalliccompounds
--metalatoms(Ni,V,Fe)atthecenterofcage
structures
--useHtosaturatestructureandbreakbondsto
releasemetalatoms:.
PropertiesofCrudeOil
  of Crude Oil
A.  ˚API
B.   Distillation
C.  Pour Point
D.  Flash  and 
E.  Vapor PressureEnvironmental Regulations
F.  Carbon Residue
G.  Salt  Number
H.  Metals
I.   Sediment and Water
J.   Acidity
K.  Sulfur:.
PhysicalProperties
(ASTM D-287)
60°F
SG     API 
Because of this inverse relationship between API and SG
 (specific gravity) there is a desire for high API crude oil 
for high distillate yield (.,  gasoline, diesel, and jet fuel).
API = 10
H2O
Crude Oils-     API ~ 10-50
* most commonly 20-45
ASTM:AmericanSocietyforTestingandMaterials:.
PhysicalProperties
Viscosity – ASTM D-2983
• flow properties, resistance to flow
Pour Point (PP) – ASTM D-97
•  temperature at which oil ceases to flow
-  PP ~ waxiness of oil (n-paraffin)
PP         n-paraffins
Flash Point (°F) –ASTM D-93
• temperature above which the oil will spontaneously ignite
Vapor Pressure (°F) – ASTM D-323
•  also known as (Reid – RVP)
•  True vapor pressure usually 5-9% > RVP:.
OtherPropertiesofOils
Carbon Residue - solid residue (% wt) remaining after heating to coking 
temperatures
Two tests:1) ASTM D-524 Ramsbottom Carbon
2) ASTM D-189 Conradson Carbon
Conradson Carbon Residue (CCR)
•  fouling
•  catalyst deactivation – coking propensity
CCR        Asphaltene 
Salt content – ASTM D-3230
•  lb NaCl/1000 bbl
•  desalting is necessary because NaCl content > 
10 lbs/1000 bbl leads to corrosion!:.
OtherPropertiesofOils
Metals – EPA method 3040
•  Ni, V, Ag, Hg, Na, Ca
•  catalyst deactivation
•  V > 2 ppm in fuel oils  corrosion problems
Sediment & Water – ASTM D-96
•  inorganic particles  operational problems
Acidity – ASTM D-664
•  titration w/ KOH
Sulfur – ASTM D-129,  1266, 1552, 2622
•  sour crudes   S >  wt %
•  sweet crudes  S <  wt %:.
SpecificationofCrudeOil
- API gravity
- Sulfur, wt %
- Pour Point, F
- Acid Number, mg KOH/g
- Viscosity at 100°F, cst
- Characterization factor K, K
UOPW:.
TrueBoilingPointDistillation(TBP)
Reported as TBP  yields, vol %
Butanes and lighter
Light gasoline 55-175F
Light naphtha175-300F
Heavy naptha300-400F
Kerosene400-500F
Atmosphere Gas Oil500-650F
Lt. Vacuum Gas Oil650-800F
Hvy. Vacuum Gas Oil800-1000F
Vacuum Residue>1000F:.
SpecificationsandEnvironmentalRegulations
Gasoline -  octane number -resistance to ignition by compression
87 – Regular         CR: 9
89 – Plus
93 – Super      CR: 12
Spark
Ignition
Engine Knock- Spontaneous ignition of fuel
 (higher octane gas reduces
 engine knock)
Compression
Diesel – cetane number (ASTM D-613)ratio
•ease of ignition when compressed with air.
Compression
Ignition:.
OctaneNumber
Octane Number:  R + M
         2
R:   Research Octane  (ASTM  2699)
M:  Motor Octane (ASTM-2700)
•  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 an . of ~ 40
Control . with additives such as:  1) TEL (tetraethyl lead)
- leaded gasoline (phased out)
2) Oxygenates :.
Products
DesiredProductsandImportantProperties:
1)Fuel–heatingvalue
2)Gasoline–octanenumber(87-93)increasecompressionratiowh