PETROCHEMISTRY

Instructor: DAO THI KIM THOA

 Chapter 6: Petrochemical technology based on C4 olefins and di-olefin
I. Introduction:
v C4 olefins
v Making fewer chemicals than ethylene and propylene.
v However, C4 olefins and di-olefin is the feed for huge-demand chemicals like:
MTBE, adiponitrile, 1,4-butadiol, and poly-butadiene.
v Butadiene is not only important monomer for synthetic rubber but also an
intermediate for important chemicals like sulfolane, 1,4-butandiol, and chloroprene.
II. General:
1. Chemicals from n-butenes: 1-butene, cis-2-butene, and trans-2-butene.
a. Oxidation:
_ Acetic acid/ Acetic anhydride
_ MEK
_ Maleic anhydride
b. Epoxidation:
_ Butylene oxide
c. Hydration:
_ Sec-butanol
d. Metathesis:
_ Propylene
e. Oligomerization:
_ C8 and C12 olefins
2. Chemicals from iso-butylene:
a. Oxidation:
_ Methacrolein/ Methacrylic acid
_ MEK
_ Maleic anhydride
b. Epoxidation:
_ Iso-butylene oxide
c. Addition of alcohol to iso-butylene:
_ MTBE/ ETBE
d. Hydration:
_ Tert-butyl alcohol
e. Carbonylation:
_ Neo-pentanoic acid
f. Dimerization:
_ Di-isobutylene.
3. Chemicals from butadiene:
_ Adiponitrile
_ Hexamethylene diamine
_ Adipic acid
_ Butandiol
_ Chloroprene
_ Cyclic oligomer
_ Sulfolane
_ Poly-butadiene
III. Chemicals from n-butenes:
- N-butene: 1-butene, cis-2-butene, trans-2-butene.

- Source: C4 olefin cut from catalytic cracking, steam cracking after de iso-
butylene.
- Mixture can be used:
Ø Direct
Ø Separate to 2 streams: - 1-butene
- cis- and trans-2-butene
- 70 % of 1-butene: co-monomer in making LLDPE
One portion: make butylene oxide
The rest: accompany with 2-butenes to make chemicals.
 Iso-butane

Iso-butane

Iso-butane

Iso-butane
(*): The petrochemical Processes, Sami Matar, Lewis F. Hatch.
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
1. Oxidation
- Mixture of n-butenes (1-butene, 2-butenes) is feed.
a. Acetic acid
v Now, acetic acid is mainly from carbonylation of methanol.
v Besides, acetic acid can be from catalytic oxidation of n-butene.

CH3CH =CHCH3 + 2O 2 CH3C OH

2
O

Vapor phase reaction.

To: 270 oC, Catalyst: Ti/V2O5, Yield: 70 % acetic acid, 25 % CO, 3 % maleic
anhydride.
v Applications: esterification agent: vinyl acetate, ethyl, butyl acetate used in
pharmaceuticals, pesticide, pigment.
Chemical to make acetic anhydride.
b. Acetic anhydride:
v Acetic anhydride: solution with unendurable smell, nauseous, corrosive, caustic,
should be careful when process.
v Making: 2 stages:

CH3-C-OH CH2=C=O + HO
2
=

O ketene

CH2=C=O + CH3-C-OH CH3-C-O-C-CH3

=
=
=
O O O
acetic anhydride

v Applications: make acetic ester.

acetyl salicylic acid (aspirin).
c. Methyl ethyl ketone

v Methyl ethyl ketone (MEK, 2-butanone): colorless liquid like acetone but
higher boiling point (79.5 oC).
v Makeing: liquid phase oxidation
Wacker reaction (PdCl2/CuCl2)

3 CH2=CH-CH2-CH3 + 3 O2 2 CH3-C-CH2-CH3 + 4 H2 O

=
O

v Y: 88 % MEK
v Application:
Ø Solvent for paint, adhesive.
Ø Selective solvent for lube oil dewax.
Ø Making chemicals.
d. Methyl isobutyl ketone:
Application: like MEK.
1960-1970: MiBK replaced ethyl acetate and butyl acetate of being solvent for
paint.
However, MEK is now the best choice.
Reason: MiBK is pollutant.
Application: main application of MiBK is: extraction in metallurgy,
pharmaceuticals, adhesive, make methyl isobutyl carbinol.
d. Maleic anhydride:
v Maleic anhydride: solid, melting point 53 oC, dissolve in water, alcohol and
acetone, not dissolve in hydrocarbon solvent.
v Making: oxidation of n-butenes

O
CH3-CH=CH-CH3 + 3 O2 O= =O + 3 H2O

T: 400 – 440 oC.

P: 2 - 4 atm.
Catalyst: MoO3, V2O5 (mix), P2O5 (promoter).
Y: 45 % MA.
2. Epoxidation:
v Butylene oxide.
v Making: like PO by chlorohydrination + epoxidation.

CH3-CH2-CH=CH2 + HOCl CH3-CH2-CH-CH2

OH Cl
butylene chlorohydrin

CH3-CH2-CH-CH2 + Ca(OH)2 2 CH3-CH2-CH-CH2 + CaCl2 + 2H O

2

OH Cl
O

v Applications:
Ø Make butylene glycol: for synthesis plasticizer, stabilizer for
chlorination solvent.
Ø Intermediate for making surfactant and pharmaceuticals.
3. Hydration
v Sec-butanol: solution with specific odor, boiling point 99.5 oC, soluble in
water but less than IPA and ethyl alcohol.
v Synthesis: feed: mixture of n-butenes.
2 stages:
Ø React with H2SO4: form carbonium ion intermediate.
Hydrolysis.

CH2=CH-CH2-CH3 _ --
+
+
CH3CH-CH +HSO4 / SO4
H + 2-CH3
CH3-CH=CH-CH3

CH3-CH2-CH-CH3 + HO
2 CH3-CH2-CH-O-SO H (CH3-CH2-CH)2-O-SO3
+ H2SO
4 CH3
3
+ CH3
OH

v By-product: di-sec-butyl ether.

v Applications
Ø Make MEK by dehydrogenation.
Ø Solvent, paint remover, intermediate.
4. Metathesis

CH3-CH=CH-CH3 + CH2=CH2 2 CH3-CH=CH2

v Metathesis: the reaction converts 2 olefins to 1 olefin in the middle of chain

length.
v Reverse reaction: 2-butene and ethylene to polymer-grade propylene.
v C4 feed: 2-butenes (1-butene: is not favorable, form by-product)
Example:
1-butene + 2-butenes 2-pentene + propylene
5. Oligomerization:
v 2-butenes (after remnove 1-butene): can be oligomerized in liquid phase with
heterogeneouse catalyst to form C8 and C12 olefin.
v Exothermic reaction.
IV. Chemicals from iso-butylene
1. Oxidation: make MA (methacrylic acid)

Oxidation
_ Propylene acrolein acrylic acid
_ Iso-butylene methacrolein methacrylic acid

CH2=C-CH3 CH2=C-CHO
+ O2 + HO
CH3 CH3 2

methacrolein

CH2=C-CHO CH2=C-COOH
+ O2
CH3 CH3
methacrylic acid

Ammoxidation of iso-butylene methacrylonitrile: low yield

propylene acrylonitrile
2. Epoxidation: make iso-butylene oxide
v There are 2 ways
Ø Chlorohydrination + epoxidation.
Ø Direct oxidation.
CH3
CH3-C=CH2 CH3-C-CH2
CH3
+ 1/2 O2
O
Iso-butylene oxide

Catalyst process: Y: 82 %
Non-catalyst process: Y: 28.7 % (by-product, acetone, tert-butyl-alcohol, iso-
butylene glycol).

3. Addition of alcohol to iso-butylene: make MTBE/ ETBE

v Catalyst: poly-styrene sulfonate resin.
v Y: 98 % MTBE.
4. Hydration: make tert-butyl alcohol
+ CH3
CH3-C=CH2 H
+ H2O CH3-C-OH
CH3
CH3
v Reaction
Ø Liquid phase
Ø Catalyst: H2SO4 (50 - 65 %)
Ø T: 10 - 30 oC
Ø Y: 95 %
v Apllication
Ø Intermediate because tertiary-butyl carbonium is formed easily.
Ø Solvent, paint remover, RON booster additive.
Ø Tert-butyl alcohol is also a by-product of the PO production from tert-butyl
hydroperoxide. So, abundant tert-butyl alcohol could be used to make iso-
butylene (by dehydration) with high purity to make MTBE.
5. Carbonylation: make neo-pentanoic acid
CH3 +
CH3-C=CH2 +
+ H + CO CH3-C-CO
CH3 CH3

CH3 + CH3
CH3-C-CO + H2O CH3-C-COOH
CH3 CH3
neo-pentanoic acid

6. Dimerization: make di-iso-butylene

v Catalyst: acid.
v Product: mixture of isomers of di-iso-butylene.
v Application
Ø Alkylation agent in plasticizer production.
Ø Lube oil additive.
V. Chemicals from butadiene:
v Butadiene: di-olefin hydrocarbon is promising.
Ø Chemical diversifying.
Ø Low cost.
Ø Available.
v Butadiene:
Ø Colorless gas, not soluble in water but in alcohol.
Ø Easily to be liquefied under pressure.
Ø Can be easily polymerized with free radical initiator.
v Source:
Ø By-product of steam cracking, catalytic cracking.
Ø Those two processes supply 90 % butadiene demand.
Ø The rest comes from dehydrogenation n-butane and n-butenes.
1. Adiponitrile:
v Adiponitrile: colorless liquid, less soluble in water but alcohol, mainly
used to make nylon 6/6.

2 CH2=CH-CH=CH2 + 2Cl2 Cl-CH2-CH=CH-CH2-Cl + CH2=CH-CH-CH2

1,4-dichloro-2-butene Cl Cl

v Mechanism: free radical chlorination. 3,4-dichloro-1-butene

v Reaction: vapor phase, T: 200 - 300 oC.

Cl-CH2-CH=CH-CH2-Cl + CH2=CH-CH-CH2 + 4 NaCN 2N=C-CH2-CH=CH-CH2-C=N + 4NaCl

Cl Cl

N=C-CH2-CH=CH-CH2-C=N + H2 N=C-(CH2)4-C=N

adiponitrile
2. Hexa-methylene-di-amine
v Hexa-methylene-di-amine
Ø Colorless crystal, dissolve in water and alcohol.
Ø Used to make nylon 6/6.
v Synthesis: catalyst hydrogenation adiponitrile, liquid phase.

N=C-(CH2)4-C=N + 4 H2 H2N-(CH2)6-NH2

v T: 200 oC.
v P: 30 atm.
v Catalyst: Co
v Application: HMD + adipic acid nylon 6/6
3. Adipic acid
v Synthesis: catalytic carbonylation butadiene, liquid phase.

+ HOOC-(CH2)4-COOH
CH2=CH-CH=CH2 + 2 CO 2 H2O

v T: 220 oC
v P: 75 atm
v Catalyst: RhCl2 + CH3I
v Y: 49 %
v Main process to make adipic acid: catalytic oxidation cyclohexane.
4. Butandiol
v From propylene: carbonylation of allyl acetate.
v From maleic anhydride.
v From butadiene
Ø Acetoxylation
CH2=CH-CH=CH2 + 2 CH3-C-OH CH3-C-O-CH2-CH=CH-CH2-O-C-CH3

=
O O O
1,4-diacetoxy-2-butene
T: 80 oC
P: 27 atm
Catalyst: Pd, Te
Ø Hydrogenation
CH3-C-O-CH2-CH=CH-CH2-O-C-CH3 CH3-C-O-(CH2)4-O-C-CH3
+ H2

=
=
=
=

O O O O

T: 80 oC 1,4-diacetoxyhutane
P: 60 atm
Catalyst: Ni/Zn
Ø Hydrolyse
CH3-C-O-(CH2)4-O-C-CH3
+ 2 H2O HO-(CH2)4-OH + 2 CH3COOH
=
=

O O Recycle
5. Chloro-prene
v Chloroprene
Ø Liquid, boiling point 59.2 oC, slightly soluble in water, soluble in alcohol.
Ø The main use of chloroprene is to polymerize it to neo-prene rubber.
v Synthesis: high temperature chlorination to a mixture of dichlorobutenes, which is
isomerized to 3,4-dichloro-1-butene. This compound is then dehydrochlorinated to
chloroprene
CH2=CH-CH=CH2 + Cl2 CH2-CH=CH-CH2
Cl Cl

CH2=C-CH=CH2 _ HCl CH2=CH-CH-CH2 isomer CH2=CH-CH-CH2

Cl Cl Cl Cl Cl

v Application: make neo-prene (polymer).

6. Sulfolane: tetra-methyl sulfone
+ H2
CH2=CH-CH=CH2 + SO2 SO
2
SO2

T: 75 oC
@ 125 oC: sulfolane is decomposed to butadiene and SO2.

v This a a simple method to separate butadiene out of C4 olefins mixture because

olefins do not react with SO2.
v Applications: extractive solvent to extract aromatics from reformate and coke
furnace.

7. Cyclic oligomer of butadiene

v Butadiene can be oligomerized to form cyclic dienes, trienes.

1 2 9 7
8
5 CH2=CH-CH=CH2
3 + 1
6

4 5
4 2.
3
5
5% dimer 1,5,9-
1,5-cyclooctadiene cyclododecatriene
8. Poly-butadiene:
v Butadiene can be polymerized by free radical or ion or catalyst.
v Initiator free radical: cumene hydro-peroxide: make random polymer.

v Anion initiator.
v Catalyst.
v Property: cis-1,4-poly-butadiene: high elastic, low thermal accumulation, high
anti-abration, high antioxidation.
v However: less mechanical stability. In order to improve: using co-polymer with
trans-PB (block) or natural rubber (small amount).