Petrochemical technology based on propylene

Instructor: DAO THI KIM THOA

 Propylene

Colorless gas, sweet odour, melting point: -185 oC, boiling point: - 47.7 oC, d204:
0.508, limited soluble in water, soluble in ethanol and ether, flammable, (limit in air
2.4 – 11.1 %vol. )

CH2=CH
H - C- H
H

H: allylic hydrogen
 Chemicals and polymers from propylene
Polypropylene 30% propylene
Propylene oligomers
Acrylic acid
Acrylo nitrile 15% propylene
Propylene oxide 15% propylene
Cumene 10% propylene
Phenol
Bisphenol A
Epoxy resins
Polycarbonate resins
Phenolic resins
Acetone Methyl methacrylate
Isopropyl alcohol 12% propylene
Acetone
N-butyraldehyde 2-ethylhexanol 10% propylene
n-butyl alcohol
Iso-butyraldehyde isobutyl alcohol
Epichlorohydrin Epoxy resins
Glycerol
 Reactions
Polymerization and oligomerization

xt
a. CH3-CH=CH2 poly-propylene
xt
b. CH3-CH=CH2 propylene dimer, C6H12
propylene trimer, C9H18
propylene tetramer, C12H24

Oxidation
O2, O2,
c. CH3-CH=CH2 CH2=CH-CHO CH2=CH-COOH
cat. cat.
acrolein acrylic acid
ROH,
CH2=CH-COOR cat.
Acrylic ester
O2, NH3
d. CH3-CH=CH2 CH2=CHCN + by-product (HCN + CH3CN)
cat. Acrylo-nitrile aceto-nitrile
 Cl2, H2O NaOH
e. CH -CH=CH CH -CHCH Cl CH CH-CH + NaCl
3 2 3 2 3 2
O O
H
propylene oxide

CH3 H
H C-C- OOH or C H -C-CH
3 6 5 3
CH3 OOH

t- butyl ethylbenzene
hydroperoxide hydroperoxide
f. CH -CH=CH CH CH-CH +
3 2 3 2
O
CH3 propylene oxide
H C-C- OH or C H CHOH
3 6 5
CH3 CH3
t-butyl alcoholl phenyl methyl carbinol

-H2 O C H CH=CH
6 5 2
Styrene
 C H O2
g. CH3- CH=CH2 6 6 C6H5CH C6H5C-OOH diluted H2SO4
cat. cat.
Cumene Cumene
Hydroperoxide

C6H5 OH + CH 3COCH3
Phenol Acetone

H2O -H2
h. CH3 CH=CH2 CH3 CHCH3 CH3 COCH3
H2SO4 cat.
Isopropyl acetone
Alcohol

H2
CH3CH2CH2 CHO CH3CH2CH2CH2OH
cat.
CO + H Butyraldehyde n - butanol
i. CH3 CH=CH2 2
cat. H2
(CH3)2 CHCHO (CH3)2 CHCH2OH
cat.
iso butyraldehyde iso butanol
 Cl2 500oC Cl2 H2O
j. CH3 CH=CH
2 ClCH2 CH=CH 2 ClCH2 CHCH 2 Cl + ClCH2 CHCH 2 OH
+ HCl
allyl chloride O Cl
H
1,3- dichloro- 1,2- dichloro-
2- hydroxy- 3- hydroxy-
propane propane

ClCH CH- CH
2 2 - HCl
O Ca(OH)
2
Epichlorohydrin
 POLY PROPYLENE
CH2 CH

CH3 CH3 CH3 CH3 CH3

n H H H H H

H H
H H H H H
C C H H H H

H CH3
iso-tactic
n

CH3 H CH3 H CH3 CH3 CH3 H

H H H H H H H H H H

H H H H H H H H H H
H CH3 H CH3 H H H CH3
syndio-tactic a-tactic
POLY PROPYLENE

Poly propylene with 99 % isotactic:

Ø Chemicals resistance
Ø Limited water adsorption
Ø Low density
Ø Mechanical resistance
Ø Safe
Ø Easily to be processed
Ø Light and rigid: suitable to used in car parts
Ø Fiber, cheap.
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
ACROLEIN

• Property: acrolein ( CH2=CHCHO) is an unsaturated aldehyde, liquid, colorless,

(pure), unpleasant odour, high acitivity, easily to be polymerized.
• Application: make acrylic acid and acrylic ester.
CH CH=CH + O cat. CH =CHCHO + HO
3 2 2 2 2
propylene acrolein
Catalyst: CuO (Shell process)
Bi2O3 /MoO3 (Sohio process)
T : 300- 360 oC
P: 1- 2 atm

ACRYLIC ACID
CH =CHCHO + 1/2 O CH =CHCOOH
2 2 2

Catalyst: MoO3, V2O5

T: 250 oC
Acid acrylic and esters: are used to make acrylic resin for adhesive, paint, and
plastic.
Acrylonitrile CH2 CH CN

Acrylic acid CH2 CH C OH

Acrylate CH2 CH C O R

Alcohol + organic acid

ester
 ACRYLONITRILE

(CH =CHCN)
2
· Ammoxidation: transfer methyl group to nitrile group by using
NH and O over mixed oxides.
3 2

CH =CHCH + NH + 3/2 O CH =CHCN + 3H O

2 3 3 2 2 2
DHo298 = –518 kJ/mol

Highly exothermic: need heat relieve

By-product: aceto-nitrile: CH3CN
hydrogen cyanide: HCN
can be sold
Application: make acrylic fiber, acrylic resin, plastic.
ABS resin: co-polymer of acrylo-nitrile with butadiene and styrene
SAN: an important polymer: co-polymer of styrene with acrylonitrile.

There are 2 technologies: fixed bed and fluidized bed but the modern is fluidized bed.
(*): Petrochemical Processes, Sami Matar, Lewis F. Hatch.
 QUESTION?

What are the major differences between a fixed bed catalyst process and a fluidized
bed process? What are the advantages of a fluidized bed process? The
disadvantages?
 PROPYLENE OXIDE
+ Liquid, melting point -112 oC , boiling point: 35 oC , d204 0.830, less soluble in
water (compare to ethylene oxide)
+ Application: make polyether-polyol (60–65 %), propylene glycol (20–25 %),
surfactant, …

Chloro-hydrination:
CH3CH=CH2 + HOCl CH 3CH(OH)CH2Cl
No catalyst Hypochlorous acid propylene chlorohydrin
T: 35 oC
P: 1 atm
Yield: 87-90 %
By-product: propylene dichloride (6 - 9 %)
Dehydro-chlorination with solution 5% Ca(OH)2

2CH3CH(OH)CH2(Cl) + Ca(OH) 2 2CH3CH-CH2 + CaCl2 + 2H2O

O
B y-product: propylene dichloride: propylene dichloride: CH3CH(Cl)CH2(Cl): used as solvent
® Evaluation:
+ consumed energy
+ disposed salt needed to be processed
 Chlorohydrin route to
propylene oxide

+ To limit the formation of by-product dichloride-propane, using solute chlorine solution (diluted
HOCl + HCl), leading to the low concentration of propylene chlohydrine( 3-5 %)
+ Wash column: using alkali to remove HCl
+ Concentration of Ca(OH)2: 10–15 %
+ Steam: push PO out of the reaction zone to prevent the deep hydrogenolysis to form propylene
glycol.
Direct oxidation is not used for propylene because of low selectivity. The reaction is
favorable to oxidation at allylic hydrogen to form acrolein. This is very different from
ethylene. Ethylene oxide is made by direct oxidation of ethylene.
The alternative to make propylene oxide is undirect oxidation of propylene based on
peroxide – epoxidation. The process has 2 steps.
• Form hydroperoxide (R–OOH)
Oxidation iso-butane to form tert-butyl hydroperoxide, liquid phase reaction, T: 100 -
130 oC, P: 30 – 35 bar.
(CH3)3 C–H + O2 ® (CH3)3 C–OOH
•Epoxidation of propylene
O
(CH3)3C–OOH + CH3–CH=CH2 ® CH3–CH–CH2 + (CH3)3C–OH
Liquid phase reaction, catalyst naphthenate molybdate, T: 80 – 110 oC, P: 30 – 40 bar.
Yield: > 90 %

What co-product should we have if we use ethyl-benzene?

 PROPYLEN GLYCOL

Properties and applications

+ Relatively viscous liquid, melting point - 60 oC, boiling point 187.3 oC , d420
1.038, colorless, odorless, sweet, complete soluble in water.
+ Make unsaturated polyester plastic (50 %), cosmetic, pharmaceuticals,
cigarette (moisture), plasticizer, cattle food, anti-freeze, …

Hydration of propylene oxide

O HO HO

CH3–CH–CH2 + H2O ® CH3 –CH –CH2 Propylene glycol

O
CH3
n CH3–CH–CH2 + H2O ® HO–[CH –CH2O]n–H Poly-propylene glycol

To limit the reaction forming di-tri propylene glycol, use abundant of water to dilute PO.
T 200 oC, P 12 bar, H2O: PO = 15: 1.
 CUMENE
CH3-CH-CH3

Cumene is isopropyl benzene: liquid, colorless, soluble in organic solvent, non-soluble

in water.
Production: alkylation of benzene by propylene.
+ CH2 =CHCH3 CH(CH 3)2

ΔH = -113 KJ/mol

Reaction: liquid or gas phase.

Liquid phase: T: 50 oC, P: 5 atm, catalyst: H2SO4
Feed: ethylene: small, it is non-active in the reaction condition.
butylene: from butyl-benzene, it can be ejected at the bottom.

Gas phase: T: 250 oC, P: 40 atm, catalyst: H3PO4

To prevent polyalkylation: feed: mixture of propane and propylene (40 %).
benzene/propylene: high.

Selectivity: 97 %
 Cumene plant

Catalyst: kieselguhr (H3PO4/silica-alumina)

The reaction is exothermic so needed to cool down the product stream.
Benzene: adsorb heat

What can we learn about the supported catalyst beds?

(*): Petrochemical in nontechnical language.
 PHENOL and ACETON from CUMENE

CH3CHCH3 (CH3)2COOH
+ O2
Cumene cumene hydroperoxide
Catalyst: metal salt
T: 100 - 300 oC
P: 2 - 3 atm
(CH3)2COOH OH
H+
+ CH3 C CH3

=
O
Cumene hydroperoxide phenol acetone

T: 80 oC
P: < 1 atm

Tell the funny story about the old scientist who discovered this productive reaction.
Phenol: white crystal with specific odour, become red when exposed to light, soluble in water,
solution is weak acid.
Early, phenol is used as antiseptic, preservative of organs (creosote), wood preservative.
Application: 50 % of fenol is used for making fenolic resin.
Phenol and acetone to make bis-phenol A, an important monomer to make polycarbonate and
-
epoxy resin.
Phenol is also an intermediate for so many products.

OH
+ CH3 C CH3 CH3
H+

=
HO C OH
O
Phenol acetone CH3
bis- phenol A

Acetone: volatile solution with sweet smell, soluble in water, alcohol, and so many
hydrocarbons, a symmetric ketone.
Aplication: ideal solvent for paint.
chemical with so many applications.
 Make: methyl methacrylate

Hydro cynation of acetone by HCN.

O
CH3
=

CH CCH + HCN CH C-CN

3 3 3
OH
Followed by the reaction with H2SO4 and CH3OH to form MMA
CH3 CH3 + _
CH C- CN + H SO CH =C-C-NH HSO
3 2 4 2 3 4

=
OH O
CH3 _ CH3
+
CH =C-C-NH HSO + CH OH CH =C- COOCH + NH HSO
2 3 4 3 2 3 4 4
=

Weak: NH4HSO4 abundant.

MMA: used to make poly methacrylate resin.
 phenol plant

(*): Petrochemical in nontechnical language.

 ISOPROPANOL
Iso-propanol is an important alcohol in petrochemistry, standing at the second after
methanol in respect of demand.
The first chemical from olefin.
Property: colorless liquid, pleasant smell, soluble in water, much soluble in liquid
hydrocarbon than methanol and ethanol.
Application: 50 % for making acetone. The rest is for making ester of many acid, used
as solvent.

• Direct hydration propylene in liquid or vapor phase. The reaction is relatively

exothermic.
CH3–CH=CH2 + H2O ® CH3CH(OH)CH3 ; DHo298 = - 51.5 kJ/mol
+ Liquid phase, high pressure 80 - 100 atm, catalyst: ion exchange resin, 150
oC, co-product: di-isopropyl ether .

+ Vapor phase: T: 200 oC, P: 25 atm, catalyst: WO3/silicagel (ICI process).

 Liquid phase reaction, propylene conversion 75 %; IPA yield 93.5 %; by-product yield
di-isopropyl ether: 5 %.
Weak: energy consume.
(*): The Petrochemical Processes, Sami Matar, Lewis F. Hatch.
Un-direct hydration: 1. Make isopropyl hydrogen sulfate
2. Hydrolysis
H2SO4: 85 % Isopropyl alcohol plant
Y: 70 %
P: 70 atm
T: 300 oC

+
CH3CH=CH2 + H+ [CH3CHCH3]
CH3CH=CH2 + H2SO4 CH3CH-OSO3H
CH3

CH3CH-OSO3H + H2O CH3CH-OH + H2SO4

CH3 CH3

Why does hydration give IPA but not n-propyl alcohol?

 Dehydrogenation
CuO 2
(ZnO)
2
CH CHOHCH CH CCH + H
3 3 3 3 2

=
450 – 550 oC O

Yield: 95 %

Oxidation

CH CHOHCH + O CH CCH + H O
3 3 2 3 3 2 2

=
O
Catalyst: free
T: 90 – 140 oC
P: 15 – 20 atm
By-product: H2O2

Now: acetone is mainly produced from cumene (combined with fenol).

 Allyl chloride

Chlorination propylene: to form allyl chloride: CH2=CHCH2Cl

Allyl chloride: colorless liquid, insoluble in water, soluble in organic solvent, violent acrid
smell and caustic.
Application: to make allyl alcohol, glycerol, epichlohydrin

CH =CHCH + Cl CH =CHCH Cl + HCl

2 3 2 2 2

T: 500 oC
P: 1 atm
Substitution of H (allylic) by chlorin.
By-product: HCl
Application: make glycerol by making epichlohydrin.
 Epichlorohydrin

CH =CHCH Cl + Cl + H O ClCH CH(OH)CH Cl + HCl

2 2 2 2 2 2

2 ClCH CH (OH)CH Cl + Ca(OH) 2CH - CHCH Cl + CaCl +2H O

2 2 2 2 2 2 2
O
epichlorohydrin

CH - CHCH Cl + 2H O HOCH CH(OH)CH OH + HCl

2 2 2 2 2
O Glycerol

Glycerol: a trihydric alcohol, used for making polyurethane foam, alkyd resin, plasticizer.
 BUTYRALDEHYDES
CH3 CH2 CH2 CHO

Hydroformylation of propylene (oxo reaction)

CH3
CH3 CH=CH 2 + CO + H 2 CH 3 CH2 CH2 CHO + CH 3 CH - CHO

n- butyraldehyde iso - butyraldehyde

on purpose product by-product

Catalyst?
Butyraldehyde is normally to be hydrogenated to make corresponding alcohol.
Process scheme to make butyraldehyde
(*): 2014 Petrochemical Processes Handbook
 N- BUTANOL
CH CH CH CH OH
3 2 2 2

hydrogenation
CH CH CH CHO + H CH CH CH CH OH
3 2 2 2 3 2 2 2

High yield

Applications: used as solvent, esterification.

Example: ester of n-butanol with acrylic acid is for paint, adhesive, and plastic.

Special point: make primary alcohol but not secondary alcohol like other reactions.
P: high.
Catalyst: Ni or Cu chromite carried on innert: kieselguhr, silicagel, alumina.
 2-ETHYLHEXANOL
CH (CH ) CH(C H )CH OH
3 23 2 5 2
2-Ethylhexanol is a colorless liquid, soluble in many organic solvents, is one of the chemicals
for making plasticizer for PVC (react with phthalic acid to form di-2-ethylhyxyl phthalate).
2-Ethylhexanol: aldol condensation of butyraldehyde to form 2-ethylhexanal, aldehyde is
dehydrated and hydrogenated to form 2-ethylhexanol.

C2 H 5
2 CH3CH2CH2CHO CH3(CH2)2CHOHCHCHO

C2 H 5 C2 H 5
CH3(CH2)2CHOHCHCHO CH3(CH2)2CH=CCHO + H2O

C2 H 5 C2 H 5
CH3(CH2)2 CH=CCHO + H CH3(CH2)3CHCH2OH
2

2-Ethylhexanol is a colorless liquid.