Organic Chemistry




Carbon Based
Carbon forms bonds
with many different
elements.
Carbon wants to bond
4 times.
Bonding is the force
that holds atoms in a
molecule together.
Bonding

Covalent Bonds


Atoms in a molecule
share electrons.

Making or Breaking
bonds.

Ionic Bonds


One atom gives up an
electron to the other.
Attracted by charges.


Each bond has a
specific Bond energy.
Energy, usually heat,
will break bonds.
Energy is giving off
when bonds from.
What is Process Chemistry

Study of Hydrocarbons found in Crude oil




Classifications
Structure and Chemical symbols
Study of the Chemical and Physical
changes taking place in a refinery.
Study of equipment used in separating
and chemically changing crude products.




Mixture of
Hydrocarbons and
Impurities
Carbon - 84%
Hydrogen - 14%
Sulfur - 1 to 3%





Nitrogen - less than
1%
Oxygen - less than
1%
Metals - less than 1%
Salts - less than 1%
BS&W
A Little History

"Drake's Folly"



In 1859, at Titusville, Penn., Col. Edwin Drake drilled
the first successful well through rock and produced
crude oil.
Petroleum was prized mostly for its yield of
kerosene until the turn of the century. Gasoline
was burned off
By the 1920s, crude oil as an energy source not just as a curiosity - came into its own
Remarkably varied substance



It can be a strawcolored liquid or tarblack
Red, green and
brown hues are not
uncommon
Some flow about as
well as cold peanut
butter.
Basic Types of Crude oils

Paraffinic



Naphthenic


Mostly cyclo-paraffins
Sweet


Mostly Paraffin
Waxy
Little or no Sulfur
Sour

Lots of Sulfur
Hydrocarbons

A group of Compounds in Organic
Chemistry.




Referred to as “Oils” or Petroleum.
Compounds are mainly Hydrogen and Carbon
Can contain other elements such as Sulfur,
Nitrogen, and Heavy Metals.
Closely related to vegetable oils, and
alcohols.
Classifications of Hydrocarbons

Alkanes (Paraffin’s) - Single Bonds





Chains, Branched changes (Isomers), or rings
(Cyclo-)
Alkenes (Olefin’s) - Contain at least one
double bond
Alkynes – Triple bonds
Aromatics – Base is a Benzene ring
Naphthalenes – Cyclo-paraffins
H
c
H
H
H
c
H H
Ethane C2H8




Straight or Branched
Chains.
All Bonds are single
bonds.
Ending in – “ane”
Chemical Symbols


Alkanes
CnH2n+2
Referred to as normal

nbutane or nC4.


H
c
H
H
H
c
c
H
H
H
c
H
H
H
Ranging from C1 to
C50+
Saturated
Hydrocarbons




Meaning it has its full
amount of Hydrogen
No double bonds.
Paraffinic / Waxy
Stable compounds
H
Top Ten Paraffin's
H
c
H
H
Methane CH4





Methane
Ethane
Propane
Butane
Pentane
CH4
C2H6
C3H8
C4H10
C5H12





Hexane
Heptane
Octane
Nonane
Decane
H
H
c
H
H
H
H
H
c
c
c
H
H
H
H
c
H
H
Hexane (n-Hexane) C6H14
H c
H
H
c
H
c
H
c
H
H
H
C6H14
C7H16
C8H18
C9H20
C10H22
H
H
c
H
H
H
c
c
c
c
H
H
H
H
H
H
Decane (n-decane) C 10H22
H
c
c
H
H
H
H
c
H
H
H
c
c
H
c
H
H
H H
H
Butane (n-butane) C4H10



Included in the Alkanes and Alkenes.
Branched Chains
Indicated by





Isomer’s
iso-Hexane, or
i-Hexane
H
c
H
H
H
H
H
c
c
H
c H
H
Iso-butane
Same Chemical formula different molecular
shape.
Different Properties.
The Larger the Chain, the more isomers it can
have.
H
Naphthenes
H

Cyclo-paraffin’s





Different Chemical Formula from
straight chained paraffin.
CnC2n
Ringed Saturated hydrocarbons
May have one ring or several
combined.
Different properties than
straight chains or isomers of
the same Carbon content.
H
c
H
H
c
H c
H c
H
H
c H
H
cyclo-pentane
H
H
c
H
c H
H
H
c
c
H
H
H
c
H
c
H
H
cyclo-hexane
H
c
H
c
H
Butene
C4H8



H
H
Alkenes
Ending in –ene
Referred to Olefins
CnH2n. For 1 double
bond
Diolefins

2 double bonds
H
H c
H
H
c
c
H
H
c
c
H
H
Pentadiene C5H8

Unsaturated
Hydrocarbons


Chemical symbols


c
Straight or Branched
Chains
Double bonded
hydrocarbons.


H
H
c
H

Are lacking some
hydrogen due to double
bonds.
Formed in refinery in
cracking without the
presence of hydrogen.
Break down readily in
treating reactors
Alkynes



Triple bonded
hydrocarbons
Ending in –yne
Chemical symbols




H
c
H
c
c
H

H
c
c
H
Pentyne C5H8
H
H
c H
ethyne C2H2
Unsaturated
hydrocarbons
CnH2n-2 For 1 triple
bond.
H
H c

Lacking hydrogen due
to triple bonds
Triple bond is slightly
stronger than double
bond
Formed in the same
way as Alkenes
Break down readily in
treating reactors
H
H
c
c
H c
c H
c
H
c
Aromatics
H
Benzene (aromatic)

Base is benzene ring


Cyclo-alkene




Methyl, Ethyl
Common names
Benzene
Toluene
Xylene
PNA’s

Can have sub groups




Polynuclear aromatics
Two or more benzene
rings
Environmentally unfriendly H c c H
H c
c H
c
H
c
c
c
H
c
c
H
H
polynucleararomatic
PNA
H
O
Impurities
H
Water
H
N
H
c
H

Sulfides


c


S
c
H
H H
Sulfides
c
H
H

Pyroles

H c
c
H
pyrole
Nitrogen compounds
found in crude.
 Bottom Sediment and
R-SH
Water.
Ethyl mercaptan
H
 BS&W
added to Natural gas
H H
S
c
H
c
Skunk odor.
H H
Phenols

c
H
Mercaptans (Thiols)


R-S-R
H
H
Mercaptan
Alcohol like molecules
From Crude to your car.

Separating the good
from the ugly.





Distillation
Removing impurities
Catalytic processes
Blending
Refined Products
Compounds in Crude



Each Compound has
different physical
properties.
These properties are
used in the separation
or distillation process.
Mainly based on
boiling point

Crude oil is separated
into other mixtures.






LPG
Gasoline
Jet Fuel
Diesel
Gas oils
Resid and/or coke.
Viscosity

Measurement of thickness of a liquid.



How easily it pours or flows
The heavier the material the higher the
viscosity (usually)
Test method for diesel, jet, and lube oils.
Vapor Pressure and Flash point


Referred to as RVP (Reid Vapor Pressure)
Equilibrium of liquid and vapor in a closed
atmosphere.



The lighter the material the higher the vapor
pressure. More volatile.
Flash point – temperature which compound will
ignite.
Volatility.
BP °F
Product
Range
Hydrocarbon
BP
°F
Product
Range
Methane - C
-258
Natural Gas
Octane-C8
258
Gasoline
Ethane – C2
-127
Natural Gas
Nonane-C9
304
Gasoline/
Distillate
Propane – C3
-43
LPG
Decane-C10
345
Gasoline/
Distillate
iso-Butane – C4
11
LPG
Undecane-C11
385
Gasoline/
Distillate
n-Butane – C4
31
LPG/ Gasoline
Dodecane-C12
421
Distillate
Pentane – C5
96.8
Gasoline
Tridecane-C13
456
Distillate
Hexane – C6
155
Gasoline
OctadecaneC18
601
Distillate
Benzene – C6
176
Gasoline
Eicosane-C20
651
Distillate/
Gas oil
Cyclohexane – C6
177
Gasoline
Gas Oils-C20+
Heptane-C7
209
Gasoline
Hydrocarbon
650-1100 °F
Boiling Ranges
IBP
3%
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%
FBP
LUX
HUX
JFA Jet
39
60
62
64
68
76
80
120
126
136
147
163
169
184
154
178
188
194
202
212
219
237
252
266
281
308
333
370
241
280
294
312
325
335
360
393
413
478
478
530
568
626
Hot Drum 1st Fract 2nd Fract 1st Fract
Liquid OH Liquid OH Liquid Bottoms
7
79
94
157
200
220
244
260
277
291
318
337
351
380
-39
12
17
36
90
146
185
201
219
242
266
289
318
359
-36
15
22
76
95
143
170
194
201
217
238
252
263
289
272
305
323
357
404
460
536
615
678
728
778
848
900
987
RCO
2nd Stg
LPS
Bottoms
1st Stg
LPS
Bottoms
418
490
521
575
637
678
714
746
782
824
872
931
974
1070
97
104
136
202
294
394
513
620
692
753
819
898
949
1041
97
102
134
187
247
309
376
451
561
664
736
816
879
993
Boiling Points

What is IBP


S/R
Stove Oil
Naptha
Initial boiling point
What is FBP

Crude Unit Basic products
Final boiling point
Sim Dist IBP
3 % (deg. F)
5 % (deg. F)
10% (deg. F)
20% (deg. F)
30% (deg. F)
40% (deg. F)
50% (deg. F)
60% (deg. F)
70% (deg. F)
80% (deg. F)
90% (deg. F)
95% (deg. F)
98% (deg. F)
Sim Dist FBP
55
79
85
98
144
162
191
204
217
232
257
278
292
309
333
206
253
268
293
324
351
379
405
430
455
482
514
538
563
587
VDF
Diesel
VDF Gas
Oil
344
406
426
455
491
518
540
559
577
595
615
640
662
685
717
480
561
588
630
675
698
716
732
747
763
783
810
835
867
917
Vac
Heavy
Gas Oil
532
597
621
658
703
734
763
788
817
846
880
930
968
1011
1063
Distillation


Physically separating compounds from a mixture
based on boiling points.
Each compound in the mixture has a different
boiling point.
Fractionation



Simple distillation fine
tuned.
The taller the tower
and more trays adds in
separation.
Debutanizer


Removes Butane and
lighter
Dehexanizer/Splitter

Removes Hexane and
lighter.
Natural Gas

Natural Gas


Contains mainly
Methane and
Ethane
Referred to as




C1 Methane
C2 Ethane
Found with crude
oil but removed at
the sight.
Low heat energy
LPG

Liquefied Petroleum Gas.







Propane (C3)
Butane (C4)
In crude oil
Produced from refinery
processes
Sold as product
Butane can be used in
gasoline blending.
Low heat energy
Gasoline

Gasoline Contains







Pentane
Hexane
Heptane
Octane
Nonane
(C5)
(C6)
(C7)
(C8)
(C9)
Gasoline boil in the range
of 55 to 400 degrees
Fahrenheit.
More heat energy than
LPG
Jet Fuel and Diesel


Jet fuel and Diesel are
group as Distillates
Jet fuel boil in the range
of 200 to 550 degrees


Heat energy higher than
gasoline
Diesel, at about 300-700
degrees.

Higher heat energy
H
c
H
H c
H
c
H
H
H
c
H
H
H
H
H
c
H
H
H
H
c
c
H
H
c
H
H
H
c
c
H
H
H
H c
c
H
H
H
c
H
c
c
H
H
H
H
c
H
H
H
c
c
H
H
c
H
H
H
Gas oils and Resid.


Heavy oils - C14 and larger
Can be used as





Bunker Fuel
Feed Stocks to Cracking units
and Coker.
Asphault
Gas oils boil in the range of
600 –1100 degrees.
Greatest heat energy
Hydrogen Plant

Main producer of Hydrogen for the
Hydrocracker.


By-products are CO and CO2


High Purity Hydrogen.
CO2 Sold as product
Steam Reforming Process
Hydrotreating

Catalytically removes
impurities.





Mostly Sulfur and Nitrogen.
Consumes Hydrogen
Produces H2S and NH3
Fuel specifications and
environmental concerns.
Makes corrosive salts.
H
H
H
c
H
S
S
H
c
H H
Mercaptan
H
H
c
H
H
c
H H
Ethane C2H8
H
H H
H
N
H
H
c
c
H c
c
H
pyrole
H
H
c
H
H
c
c
H
c
H
H
H H
H
Butane (n-butane) C 4H10
H
H N H
Ammonia
Hydrotreating

All ranges of products
are treated.

NHDS (Naphtha Unit)


DHDS (Diesel Unit)


Treats Gasoline
Treats Diesel
Hydrocracker

Treats Gas oils.


ISOM Unit will also
treat gasoline.
Caustic washing will
remove light
mercaptans and H2S
Removing Impurities

DEA Plant




DEA absorbs H2S
Chemically.
Releases it in
Regenerators.
H2S is combusted with
H2 and air
Elemental Sulfur is
removed.

Sour Water.



Water absorbs the
Ammonia and H2S
Sour water is stripped
Removing the H2S and
NH3 gases.
Vapor Recovery
Cracking

Making usable products from
less valuable heavy oils.



Breaking Large molecules in to
smaller ones.
Heavy gas oils and Resid are
not worth as much as jet and
gasoline.
Hydrotreating
Hydrocracking

Cracking in Controlled
Environment.




Catalyst is used to make
Reaction Conditions less severe.
Temperature controls rate of
reaction.
Broken Bonds are saturated
with Hydrogen.
Produces Paraffinic products
Coking

Thermal cracking.




Heating oil under pressure to
cracking temperature.
Quickly reducing pressure in
the drums causing
hydrocarbons to crack into
smaller chains and carbon to
solidify
With out the presence of
Hydrogen
Produces unsaturated
olefins.
H
H
c
H
c
H
H
c
c
c
H
H
H
H
H
Reforming
H
H
Pentane (n-pentane) C 5H12
H
c
H
H
H
c
H
H
c
H

c
H
H
H
c
Reformulates paraffinic material
into higher octane molecules.
H
H
Iso-pentane
(2,methylbutane)

H

H
c
c
H c
c H
c
H
c


c
H
H
H
Toluene (aromatic)
H
c
H
Butene
C4H8
H
c
H
H
c
H
c
H
H

Aromatics
Isomers
Naphthenes
Breaking the Hydrogen - carbon
bond.
Produces Hydrogen as a byproduct.

Major Refinery Hydrogen Producer
Isomerization


Similar to Reforming.
Benzene Saturation – Bensat Reactor.


Re-arrange molecular shape.


H
No Aromatic formation – using isomers for
increase in octane of product.
H
H
c
H
H
Straight Chains to Branched Chains.
Increases Octane and RVP.
H
H
H
c
c
c
c
H
H
H
H
H
Pentane (n-pentane) C 5H12
c
H
H
H
c
c
H
c
H
H
H
c
H
H
H
Iso-pentane
(2,methylbutane)
H