Organic ChemistryOrganic Chemistry

Carbon BasedCarbon Based Carbon forms Carbon forms

bonds with many bonds with many different elements.different elements.

Carbon wants to Carbon wants to bond 4 times.bond 4 times.

Bonding is the Bonding is the force that holds force that holds atoms in a atoms in a molecule together.molecule together.

BondingBonding

Covalent BondsCovalent Bonds Atoms in a Atoms in a

molecule share molecule share electrons.electrons.

Ionic BondsIonic Bonds One atom gives up One atom gives up

an electron to the an electron to the other.other.

Attracted by Attracted by charges.charges.

Making or Breaking Making or Breaking bonds.bonds. Each bond has a Each bond has a

specific Bond specific Bond energy.energy.

Energy, usually Energy, usually heat, will break heat, will break bonds.bonds.

Energy is giving off Energy is giving off when bonds from.when bonds from.

What is Process ChemistryWhat is Process Chemistry

Study of Hydrocarbons found in Crude Study of Hydrocarbons found in Crude oiloil ClassificationsClassifications Structure and Chemical symbolsStructure and Chemical symbols

Study of the Chemical and Physical Study of the Chemical and Physical changes taking place in a refinery.changes taking place in a refinery.

Study of equipment used in Study of equipment used in separating and chemically changing separating and chemically changing crude products.crude products.

Mixture of Mixture of Hydrocarbons and Hydrocarbons and ImpuritiesImpurities

CarbonCarbon - 84% - 84% HydrogenHydrogen - 14% - 14% SulfurSulfur - 1 to 3% - 1 to 3%

NitrogenNitrogen - less than - less than 1% 1%

OxygenOxygen - less than - less than 1% 1%

MetalsMetals - less than 1% - less than 1% SaltsSalts - less than 1% - less than 1% BS&WBS&W

A Little HistoryA Little History

"Drake's Folly" "Drake's Folly" In 1859, at Titusville, Penn., Col. Edwin Drake In 1859, at Titusville, Penn., Col. Edwin Drake

drilled the first successful well through rock and drilled the first successful well through rock and produced crude oil. produced crude oil.

Petroleum was prized mostly for its yield of Petroleum was prized mostly for its yield of kerosene until the turn of the century. kerosene until the turn of the century. Gasoline was burned offGasoline was burned off

By the 1920s, crude oil as an energy source By the 1920s, crude oil as an energy source - not just as a curiosity - came into its own- not just as a curiosity - came into its own

Remarkably varied Remarkably varied substancesubstance

It can be a straw-It can be a straw-colored liquid or colored liquid or tar-black tar-black

Red, green and Red, green and brown hues are not brown hues are not uncommonuncommon

Some flow about as Some flow about as well as cold peanut well as cold peanut butter. butter.

Basic Types of Crude oilsBasic Types of Crude oils

ParaffinicParaffinic Mostly ParaffinMostly Paraffin WaxyWaxy

NaphthenicNaphthenic Mostly cyclo-paraffinsMostly cyclo-paraffins

SweetSweet Little or no SulfurLittle or no Sulfur

SourSour Lots of SulfurLots of Sulfur

HydrocarbonsHydrocarbons

A group of Compounds in Organic A group of Compounds in Organic Chemistry.Chemistry. Referred to as “Oils” or Petroleum.Referred to as “Oils” or Petroleum. Compounds are mainly Compounds are mainly HydroHydrogen and gen and CarbonCarbon

Can contain other elements such as Sulfur, Can contain other elements such as Sulfur, Nitrogen, and Heavy Metals.Nitrogen, and Heavy Metals.

Closely related to vegetable oils, and Closely related to vegetable oils, and alcohols.alcohols.

Classifications of Classifications of HydrocarbonsHydrocarbons

AlkanesAlkanes ( (Paraffin’sParaffin’s) - Single Bonds) - Single Bonds Chains, Branched changes (Chains, Branched changes (IsomersIsomers), or ), or

rings (rings (CycloCyclo-)-) AlkenesAlkenes ( (Olefin’sOlefin’s) - Contain at least ) - Contain at least

one double bondone double bond AlkynesAlkynes – Triple bonds – Triple bonds Aromatics – Aromatics – Base is a Benzene ringBase is a Benzene ring NaphthalenesNaphthalenes – Cyclo-paraffins – Cyclo-paraffins

AlkanesAlkanes

Straight or Branched Straight or Branched Chains.Chains.

All Bonds are single All Bonds are single bonds. bonds.

Ending in – “ane”Ending in – “ane” Chemical SymbolsChemical Symbols

CCnnHH2n+22n+2

Referred to as normalReferred to as normal nbutane or nC4.nbutane or nC4.

Ranging from CRanging from C11 to Cto C5050++

Saturated Saturated HydrocarbonsHydrocarbons Meaning it has its Meaning it has its

full amount of full amount of HydrogenHydrogen

No double bonds.No double bonds. Paraffinic / WaxyParaffinic / Waxy Stable compoundsStable compounds

H

H

H

H

Hc

c

c

H

H

cHH

H

H

Hc

c

H

HH

H

Ethane C2H8

Top Ten Paraffin'sTop Ten Paraffin's

MethaneMethane CHCH44

EthaneEthane CC22HH66

PropanePropane CC33HH88

ButaneButane CC44HH1010

PentanePentane CC55HH1212

HexaneHexane CC66HH1414

Heptane Heptane CC77HH1616

OctaneOctane CC88HH1818

NonaneNonane CC99HH2020

Decane Decane CC1010HH2222

H

Hc

H

H

Methane CH4

H

H

HH

H

H

H

Hc

c

c

H

H

cH

Hc

cH

H

Hexane (n-Hexane) C6H14

H

H

H

H

H

H

HH

HHc

c

c

c

c

c

c

c

cH

HH

H

H

H

H

H

H

H

cHH

Decane (n-decane) C10H22

Isomer’sIsomer’s Included in the Alkanes and Alkenes.Included in the Alkanes and Alkenes. Branched ChainsBranched Chains Indicated byIndicated by

iso-Hexane, oriso-Hexane, or i-Hexanei-Hexane

Same Chemical formula different Same Chemical formula different molecular shape.molecular shape.

Different Properties.Different Properties. The Larger the Chain, the more isomers it The Larger the Chain, the more isomers it

can have.can have.

H

H

H

H

Hc

c

c

H

H

cHH

H

Butane (n-butane) C4H10

H

H

H

H

Hc

c

cH

H

cH

H

H

Iso-butane

NaphthenesNaphthenes Cyclo-paraffin’sCyclo-paraffin’s

Different Chemical Formula Different Chemical Formula from straight chained paraffin.from straight chained paraffin.

CCnnCC2n2n

Ringed Saturated hydrocarbonsRinged Saturated hydrocarbons May have one ring or several May have one ring or several

combined.combined. Different properties than Different properties than

straight chains or isomers of straight chains or isomers of the same Carbon content.the same Carbon content.

H

HH

H

Hc

cc

c c

H

H

H

H

H

cyclo-pentane

H

H

H

H

H

cc

c c

HccH

H

H

cyclo-hexane

H

H

H

AlkenesAlkenes Straight or Branched Straight or Branched

ChainsChains Double bonded Double bonded

hydrocarbons.hydrocarbons. Ending in –eneEnding in –ene Referred to OlefinsReferred to Olefins

Chemical symbolsChemical symbols CCnnHH2n2n. For 1 double . For 1 double

bondbond DiolefinsDiolefins

2 double bonds2 double bonds

Unsaturated Unsaturated HydrocarbonsHydrocarbons Are lacking some Are lacking some

hydrogen due to hydrogen due to double bonds.double bonds.

Formed in refinery in Formed in refinery in cracking without the cracking without the presence of presence of hydrogen.hydrogen.

Break down readily Break down readily in treating reactorsin treating reactors

H

H

Hcc

c

cH

H

H

HH

ButeneC4H8

HH

HH

c

c

cH

c

c

H

H

H

Pentadiene C5H8

AlkynesAlkynes

Triple bonded Triple bonded hydrocarbonshydrocarbons

Ending in –yneEnding in –yne Chemical symbols Chemical symbols

CCnnHH2n-2 2n-2 For 1 triple For 1 triple bond.bond.

Unsaturated Unsaturated hydrocarbonshydrocarbons Lacking hydrogen Lacking hydrogen

due to triple bondsdue to triple bonds Triple bond is Triple bond is

slightly stronger slightly stronger than double bondthan double bond

Formed in the same Formed in the same way as Alkenesway as Alkenes

Break down readily Break down readily in treating reactorsin treating reactors

H c c H

ethyne C2H2

H H

H

Hc c

c

c

c

H

H

H

Pentyne C5H8

H

AromaticsAromatics

Base is benzene ringBase is benzene ring Cyclo-alkeneCyclo-alkene

Can have sub Can have sub groupsgroups Methyl, EthylMethyl, Ethyl

Common namesCommon names BenzeneBenzene TolueneToluene XyleneXylene

PNA’sPNA’s Polynuclear Polynuclear

aromaticsaromatics Two or more Two or more

benzene ringsbenzene rings Environmentally Environmentally

un-friendlyun-friendly

H

H

H

cc

c c

Hcc

H

H

H

cc

c cH

polynucleararomaticPNA

H

H

cc

c c

Hcc

H

H

H

Benzene (aromatic)

ImpuritiesImpurities

SulfidesSulfides R-S-RR-S-R

Mercaptans (Thiols)Mercaptans (Thiols) R-SHR-SH Ethyl mercaptan Ethyl mercaptan

added to Natural gasadded to Natural gas Skunk odor.Skunk odor.

PhenolsPhenols Alcohol like Alcohol like

moleculesmolecules

PyrolesPyroles Nitrogen Nitrogen

compounds found compounds found in crude.in crude.

Bottom Sediment Bottom Sediment and Water.and Water. BS&WBS&W

H

H

H H

cc

c c

HN

pyrole

H

H

Hc

c

H

H

HMercaptan

S

SH

H

H

Hc

cH

cHH

H

Sulfides

HO

H

Water

From Crude to your car.From Crude to your car.

Separating the Separating the good from the good from the ugly.ugly. DistillationDistillation Removing Removing

impuritiesimpurities Catalytic processesCatalytic processes BlendingBlending

Refined ProductsRefined Products

Compounds in CrudeCompounds in Crude

Each Compound Each Compound has different has different physical properties.physical properties.

These properties These properties are used in the are used in the separation or separation or distillation process.distillation process.

Mainly based on Mainly based on boiling pointboiling point

Crude oil is Crude oil is separated into separated into other mixtures.other mixtures. LPGLPG GasolineGasoline Jet FuelJet Fuel DieselDiesel Gas oilsGas oils Resid and/or coke.Resid and/or coke.

ViscosityViscosity

Measurement of thickness of a liquid.Measurement of thickness of a liquid. How easily it pours or flowsHow easily it pours or flows The heavier the material the higher the The heavier the material the higher the

viscosity (usually)viscosity (usually) Test method for diesel, jet, and lube oils.Test method for diesel, jet, and lube oils.

Vapor Pressure and Flash Vapor Pressure and Flash pointpoint

Referred to as RVP (Reid Vapor Pressure)Referred to as RVP (Reid Vapor Pressure) Equilibrium of liquid and vapor in a closed Equilibrium of liquid and vapor in a closed

atmosphere.atmosphere. The lighter the material the higher the vapor The lighter the material the higher the vapor

pressure. More volatile.pressure. More volatile. Flash point – temperature which Flash point – temperature which

compound will ignite. compound will ignite. Volatility.Volatility.

HydrocarbonHydrocarbon BP °FBP °F Product Product RangeRange

HydrocarboHydrocarbonn

BP BP °F°F

Product Product RangeRange

Methane - CMethane - C -258-258 Natural GasNatural Gas Octane-COctane-C88 258258 GasolineGasoline

Ethane – CEthane – C22 -127-127 Natural GasNatural Gas Nonane-CNonane-C99 304304Gasoline/Gasoline/

DistillateDistillate

Propane – CPropane – C33 -43-43 LPGLPG Decane-CDecane-C1010 345345Gasoline/Gasoline/

DistillateDistillate

iso-Butane – Ciso-Butane – C44 1111 LPGLPGUndecane-Undecane-CC1111

385385Gasoline/Gasoline/

DistillateDistillate

n-Butane – Cn-Butane – C44 3131 LPG/ GasolineLPG/ GasolineDodecane-Dodecane-CC1212

421421 DistillateDistillate

Pentane – CPentane – C55 96.896.8 GasolineGasolineTridecane-Tridecane-CC1313

456456 DistillateDistillate

Hexane – CHexane – C66 155155 GasolineGasolineOctadecane-Octadecane-CC1818

601601 DistillateDistillate

Benzene – CBenzene – C66 176176 GasolineGasoline Eicosane-CEicosane-C2020 651651Distillate/Distillate/

Gas oilGas oil

Cyclohexane – Cyclohexane – CC66

177177 GasolineGasolineGas Oils-Gas Oils-CC2020++

650-1100 650-1100 °F°F

Heptane-CHeptane-C77 209209 GasolineGasoline

Boiling RangesBoiling Ranges

LUX HUX JFA JetHot Drum

Liquid1st Fract

OH Liquid2nd Fract OH Liquid

1st Fract Bottoms

RCO2nd Stg

LPS Bottoms

1st Stg LPS

Bottoms

IBP 39 154 241 7 -39 -36 272 418 97 973% 60 178 280 79 12 15 305 490 104 1025% 62 188 294 94 17 22 323 521 136 134

10% 64 194 312 157 36 76 357 575 202 18720% 68 202 325 200 90 95 404 637 294 24730% 76 212 335 220 146 143 460 678 394 30940% 80 219 360 244 185 170 536 714 513 37650% 120 237 393 260 201 194 615 746 620 45160% 126 252 413 277 219 201 678 782 692 56170% 136 266 478 291 242 217 728 824 753 66480% 147 281 478 318 266 238 778 872 819 73690% 163 308 530 337 289 252 848 931 898 81695% 169 333 568 351 318 263 900 974 949 879FBP 184 370 626 380 359 289 987 1070 1041 993

Boiling PointsBoiling Points

What is IBPWhat is IBP Initial boiling Initial boiling

pointpoint What is FBPWhat is FBP

Final boiling Final boiling pointpoint

S/R Naptha

Stove OilVDF

DieselVDF Gas

Oil

Vac Heavy

Gas Oil

Sim Dist IBP 55 206 344 480 5323 % (deg. F) 79 253 406 561 5975 % (deg. F) 85 268 426 588 62110% (deg. F) 98 293 455 630 65820% (deg. F) 144 324 491 675 70330% (deg. F) 162 351 518 698 73440% (deg. F) 191 379 540 716 76350% (deg. F) 204 405 559 732 78860% (deg. F) 217 430 577 747 81770% (deg. F) 232 455 595 763 84680% (deg. F) 257 482 615 783 88090% (deg. F) 278 514 640 810 93095% (deg. F) 292 538 662 835 96898% (deg. F) 309 563 685 867 1011Sim Dist FBP 333 587 717 917 1063

Crude Unit Basic products

DistillationDistillation

Physically separating compounds from a Physically separating compounds from a mixture based on boiling points.mixture based on boiling points.

Each compound in the mixture has a Each compound in the mixture has a different boiling point.different boiling point.

FractionationFractionation Simple distillation Simple distillation

fine tuned.fine tuned. The taller the tower The taller the tower

and more trays adds and more trays adds in separation.in separation.

DebutanizerDebutanizer Removes Butane and Removes Butane and

lighterlighter Dehexanizer/SplitterDehexanizer/Splitter

Removes Hexane Removes Hexane and lighter.and lighter.

Natural GasNatural Gas

Natural GasNatural Gas Contains mainly Contains mainly

Methane and Methane and EthaneEthane

Referred to asReferred to as CC11 Methane Methane CC2 2 EthaneEthane

Found with crude Found with crude oil but removed at oil but removed at the sight.the sight.

Low heat energyLow heat energy

LPGLPG

Liquefied Petroleum Liquefied Petroleum Gas.Gas. Propane (CPropane (C33)) Butane Butane (C(C44))

In crude oilIn crude oil Produced from Produced from

refinery processesrefinery processes Sold as productSold as product Butane can be used in Butane can be used in

gasoline blending.gasoline blending. Low heat energyLow heat energy

GasolineGasoline

Gasoline ContainsGasoline Contains PentanePentane (C5)(C5) HexaneHexane (C6)(C6) HeptaneHeptane (C7)(C7) OctaneOctane (C8)(C8) NonaneNonane (C9)(C9)

Gasoline boil in the Gasoline boil in the range of 55 to 400 range of 55 to 400 degrees Fahrenheit.degrees Fahrenheit.

More heat energy than More heat energy than LPGLPG

Jet Fuel and DieselJet Fuel and Diesel

Jet fuel and Diesel are Jet fuel and Diesel are group as Distillates group as Distillates

Jet fuel boil in the Jet fuel boil in the range of 200 to 550 range of 200 to 550 degreesdegrees Heat energy higher Heat energy higher

than gasolinethan gasoline Diesel, at about 300-Diesel, at about 300-

700 degrees. 700 degrees. Higher heat energyHigher heat energy

H

H

H

H

H

HH

HHc

c

c

c

c

c

c

c

cH

HH

H

H

H

H

H

H

H

H

H

H

H

H

H

H

HH

Hc

c

c

c

c

c

c

c

cH

HH

H

H

H

H

H

H

H

cHH

Gas oils and Resid.Gas oils and Resid.

Heavy oils - CHeavy oils - C14 14 and largerand larger Can be used asCan be used as

Bunker FuelBunker Fuel Feed Stocks to Cracking Feed Stocks to Cracking

units and Coker.units and Coker. AsphaultAsphault

Gas oils boil in the range Gas oils boil in the range of 600 –1100 degrees.of 600 –1100 degrees.

Greatest heat energyGreatest heat energy

Hydrogen PlantHydrogen Plant

Main producer of Hydrogen for the Main producer of Hydrogen for the Hydrocracker.Hydrocracker. High Purity Hydrogen.High Purity Hydrogen.

By-products are CO and COBy-products are CO and CO22

COCO22 Sold as product Sold as product

Steam Reforming ProcessSteam Reforming Process

HydrotreatingHydrotreating

Catalytically removes Catalytically removes impurities. impurities. Mostly Sulfur and Mostly Sulfur and

Nitrogen.Nitrogen. Consumes HydrogenConsumes Hydrogen Produces HProduces H22S and NHS and NH33

Fuel specifications and Fuel specifications and environmental environmental concerns.concerns.

Makes corrosive salts.Makes corrosive salts.

H

H

Hc

c

H

H

HMercaptan

S HS

H

H

H

H H

cc

c c

HN

pyrole

Ammonia

HNH

H

H

Hc

c

H

HH

H

Ethane C2H8

H

H

H

H

Hc

c

c

H

H

cHH

H

Butane (n-butane) C4H10

H H

HydrotreatingHydrotreating

All ranges of All ranges of products are products are treated.treated. NHDS (Naphtha NHDS (Naphtha

Unit)Unit) Treats GasolineTreats Gasoline

DHDS (Diesel Unit)DHDS (Diesel Unit) Treats DieselTreats Diesel

HydrocrackerHydrocracker Treats Gas oils.Treats Gas oils.

ISOM Unit will also ISOM Unit will also treat gasoline.treat gasoline.

Caustic washing Caustic washing will remove light will remove light mercaptans and mercaptans and HH22SS

Removing ImpuritiesRemoving Impurities

DEA PlantDEA Plant DEA absorbs HDEA absorbs H22S S

Chemically.Chemically. Releases it in Releases it in

Regenerators.Regenerators. HH22S is combusted S is combusted

with Hwith H22 and air and air Elemental Sulfur is Elemental Sulfur is

removed.removed.

Sour Water.Sour Water. Water absorbs the Water absorbs the

Ammonia and H2SAmmonia and H2S Sour water is Sour water is

stripped Removing stripped Removing the Hthe H22S and NHS and NH33 gases.gases.

Vapor RecoveryVapor Recovery

CrackingCracking Making usable products Making usable products

from less valuable heavy from less valuable heavy oils.oils. Breaking Large molecules Breaking Large molecules

in to smaller ones.in to smaller ones. Heavy gas oils and Resid Heavy gas oils and Resid

are not worth as much as are not worth as much as jet and gasoline.jet and gasoline.

HydrotreatingHydrotreating

Cracking in Controlled Cracking in Controlled Environment.Environment. Catalyst is used to make Catalyst is used to make

Reaction Conditions less Reaction Conditions less severe.severe.

Temperature controls rate Temperature controls rate of reaction.of reaction.

Broken Bonds are Broken Bonds are saturatedsaturated with Hydrogen. with Hydrogen.

Produces Paraffinic Produces Paraffinic productsproducts

HydrocrackingHydrocracking

CokingCoking Thermal cracking.Thermal cracking.

Heating oil under Heating oil under pressure to cracking pressure to cracking temperature.temperature.

Quickly reducing pressure Quickly reducing pressure in the drums causing in the drums causing hydrocarbons to crack hydrocarbons to crack into smaller chains and into smaller chains and carbon to solidifycarbon to solidify

With out the presence of With out the presence of HydrogenHydrogen

Produces unsaturated Produces unsaturated olefins.olefins.

ReformingReforming Reformulates paraffinic material Reformulates paraffinic material

into higher octane molecules.into higher octane molecules. AromaticsAromatics IsomersIsomers NaphthenesNaphthenes

Breaking the Hydrogen - carbon Breaking the Hydrogen - carbon bond.bond.

Produces Hydrogen as a by-Produces Hydrogen as a by-product.product. Major Refinery Hydrogen ProducerMajor Refinery Hydrogen Producer

H HH

HH

c

c

c

c

c

H

H

H

Pentane (n-pentane) C5H12

H

H

H

H

HH

H

H

H

Hc

c

c

H

H

cH

H

c

HH

Iso-pentane(2,methylbutane)

H

H

Hcc

c

cH

H

H

HH

ButeneC4H8

H

H

cc

c c

Hcc

H

H

H

cH

H

Toluene (aromatic)

IsomerizationIsomerization Similar to Reforming.Similar to Reforming. Benzene Saturation – Bensat Reactor.Benzene Saturation – Bensat Reactor.

No Aromatic formation – using isomers for No Aromatic formation – using isomers for increase in octane of product.increase in octane of product.

Re-arrange molecular shape. Re-arrange molecular shape. Straight Chains to Branched Chains.Straight Chains to Branched Chains. Increases Octane and RVP.Increases Octane and RVP.

H HH

HH

c

c

c

c

c

H

H

H

Pentane (n-pentane) C5H12

H

H

H

H

HH

H

H

H

Hc

c

c

H

H

cH

H

c

HH

Iso-pentane(2,methylbutane)