Propylene

Petrochemical technology based on 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

Instructor: DAO THI KIM THOA H: allylic hydrogen

Chemicals and polymers from propylene

Polypropylene 30% propylene Reactions
Propylene oligomers Polymerization and oligomerization
Acrylic acid
Acrylo nitrile 15% propylene a. CH3-CH=CH2
xt
poly-propylene
xt
Propylene oxide 15% propylene b. CH3-CH=CH2 propylene dimer, C6H12
Cumene propylene trimer, C9H18
10% propylene
Phenol propylene tetramer, C12H24
Bisphenol A
Epoxy resins
Oxidation
Polycarbonate resins
Phenolic resins c. CH3-CH=CH2 O2, CH2=CH-CHO O2,
CH2=CH-COOH
cat. cat.
Acetone Methyl methacrylate acrolein acrylic acid
Isopropyl alcohol 12% propylene ROH,
Acetone CH2=CH-COOR cat.
Acrylic ester
N-butyraldehyde 2-ethylhexanol 10% propylene
O2, NH3
n-butyl alcohol d. CH3-CH=CH2 CH2=CHCN + by-product (HCN + CH3CN)
Iso-butyraldehyde isobutyl alcohol cat. Acrylo-nitrile aceto-nitrile
Epichlorohydrin Epoxy resins
Glycerol
 Cl2, H2O NaOH C H O2
e. CH -CH=CH CH -CHCH Cl CH CH-CH + NaCl g. CH3- CH=CH2 6 6 C6H5CH C6H5C-OOH diluted H2SO4
3 2 3 2 3 2 cat.
cat.
O O Cumene Cumene
H Hydroperoxide
propylene oxide
C6H5 OH + CH 3COCH3
Phenol Acetone

CH3 H
H C-C- OOH H2O -H2
or C H -C-CH h. CH3 CH=CH2 CH3 CHCH3 CH3 COCH3
3 6 5 3
H2SO4 cat.
CH3 OOH
Isopropyl acetone
Alcohol
t- butyl ethylbenzene
hydroperoxide hydroperoxide
f. CH -CH=CH CH CH-CH +
3 2 3 2 H2
O CH3CH2CH2 CHO CH3CH2CH2CH2OH
CH3 propylene oxide cat.
CO + H Butyraldehyde n - butanol
i. CH3 CH=CH2 2
H C-C- OH or C H CHOH
3 6 5 cat. H2
CH3 CH3 (CH3)2 CHCHO (CH3)2 CHCH2OH
cat.
t-butyl alcoholl phenyl methyl carbinol iso butyraldehyde iso butanol

-H2 O C H CH=CH
6 5 2
Styrene

POLY PROPYLENE
CH2 CH

Cl2 500oC Cl2 H2O

j. CH3 CH=CH ClCH2 CH=CH ClCH2 CHCH 2 Cl + ClCH2 CHCH 2 OH CH3 CH3
2
+ HCl
2 CH3 CH3 CH3
allyl chloride O Cl n H H H H H
H
1,3- dichloro- 1,2- dichloro- H
H
2- hydroxy- 3- hydroxy- H H H H H
propane propane H H H
C C H

H CH3
iso-tactic
ClCH CH- CH n
2 2 - HCl
O Ca(OH)
2 CH3 H CH3 H CH3 CH3 CH3 H
Epichlorohydrin 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
Acrylonitrile CH2 CH CN
• 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. Acrylic acid CH2 CH C OH

CH CH=CH + O cat. CH =CHCHO + HO

3 2 2 2 2 O
propylene acrolein
Acrylate CH2 CH C O R
Catalyst: CuO (Shell process)
Bi2O3 /MoO3 (Sohio process)
O
T : 300- 360 oC
P: 1- 2 atm
Alcohol + organic acid
ACRYLIC ACID ester
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
(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.
 PROPYLENE OXIDE
+ Liquid, melting point -112 oC , boiling point: 35 oC , d204 0.830, less soluble in
water (compare to ethylene oxide)
QUESTION? + Application: make polyether-polyol (60–65 %), propylene glycol (20–25 %),
surfactant, …

Chloro-hydrination:
What are the major differences between a fixed bed catalyst process and a fluidized CH3CH=CH2 + HOCl CH 3CH(OH)CH2Cl
bed process? What are the advantages of a fluidized bed process? The No catalyst Hypochlorous acid propylene chlorohydrin

disadvantages? 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 Direct oxidation is not used for propylene because of low selectivity. The reaction is
propylene oxide 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 %
+ 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 What co-product should we have if we use ethyl-benzene?
+ Concentration of Ca(OH)2: 10–15 %
+ Steam: push PO out of the reaction zone to prevent the deep hydrogenolysis to form propylene
glycol.
 CUMENE
PROPYLEN GLYCOL
CH3-CH-CH3

Properties and applications Cumene is isopropyl benzene: liquid, colorless, soluble in organic solvent, non-soluble
+ Relatively viscous liquid, melting point - 60 oC, boiling point 187.3 oC , d420 in water.
1.038, colorless, odorless, sweet, complete soluble in water. Production: alkylation of benzene by propylene.
+ Make unsaturated polyester plastic (50 %), cosmetic, pharmaceuticals, + CH2 =CHCH3 CH(CH 3)2
cigarette (moisture), plasticizer, cattle food, anti-freeze, …
ΔH = -113 KJ/mol
Hydration of propylene oxide
O HO HO Reaction: liquid or gas phase.
Liquid phase: T: 50 oC, P: 5 atm, catalyst: H2SO4
CH3–CH–CH2 + H2O ® CH3 –CH –CH2 Propylene glycol Feed: ethylene: small, it is non-active in the reaction condition.
butylene: from butyl-benzene, it can be ejected at the bottom.
O
CH3
Gas phase: T: 250 oC, P: 40 atm, catalyst: H3PO4
n CH3–CH–CH2 + H2O ® HO–[CH –CH2O]n–H Poly-propylene glycol To prevent polyalkylation: feed: mixture of propane and propylene (40 %).
benzene/propylene: high.
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. Selectivity: 97 %

PHENOL and ACETON from CUMENE

Cumene plant 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
Catalyst: kieselguhr (H3PO4/silica-alumina)
P: < 1 atm
The reaction is exothermic so needed to cool down the product stream.
Benzene: adsorb heat

What can we learn about the supported catalyst beds? Tell the funny story about the old scientist who discovered this productive reaction.
(*): Petrochemical in nontechnical language.
 Phenol: white crystal with specific odour, become red when exposed to light, soluble in water, Make: methyl methacrylate
solution is weak acid.
Early, phenol is used as antiseptic, preservative of organs (creosote), wood preservative.
Hydro cynation of acetone by HCN.
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
-
O
epoxy resin. CH3

=
Phenol is also an intermediate for so many products. CH CCH + HCN CH C-CN
3 3 3
OH
OH Followed by the reaction with H2SO4 and CH3OH to form MMA
+ CH3 C CH3 CH3
H+ CH3 CH3 + _
=
HO C OH
O CH C- CN + H SO CH =C-C-NH HSO
Phenol acetone CH3 3 2 4 2 3 4

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

=
O
Acetone: volatile solution with sweet smell, soluble in water, alcohol, and so many
hydrocarbons, a symmetric ketone. Weak: NH4HSO4 abundant.
Aplication: ideal solvent for paint. MMA: used to make poly methacrylate resin.
chemical with so many applications.

ISOPROPANOL
phenol plant
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).

(*): Petrochemical in nontechnical language.

 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
Liquid phase reaction, propylene conversion 75 %; IPA yield 93.5 %; by-product yield CH3CH-OSO3H + H2O CH3CH-OH + H2SO4
di-isopropyl ether: 5 %. CH3 CH3
Weak: energy consume.
(*): The Petrochemical Processes, Sami Matar, Lewis F. Hatch.
Why does hydration give IPA but not n-propyl alcohol?

Dehydrogenation Allyl chloride

CuO 2
(ZnO) Chlorination propylene: to form allyl chloride: CH2=CHCH2Cl
2
CH CHOHCH CH CCH + H Allyl chloride: colorless liquid, insoluble in water, soluble in organic solvent, violent acrid
3 3 3 3 2
=

450 – 550 oC O smell and caustic.

Application: to make allyl alcohol, glycerol, epichlohydrin

Yield: 95 % CH =CHCH + Cl CH =CHCH Cl + HCl

2 3 2 2 2

Oxidation
T: 500 oC
CH CHOHCH + O CH CCH + H O P: 1 atm
3 3 2 3 3 2 2 Substitution of H (allylic) by chlorin.
=

O By-product: HCl
Catalyst: free Application: make glycerol by making epichlohydrin.
T: 90 – 140 oC
P: 15 – 20 atm
By-product: H2O2

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

 Epichlorohydrin

BUTYRALDEHYDES
CH3 CH2 CH2 CHO
CH =CHCH Cl + Cl + H O ClCH CH(OH)CH Cl + HCl
2 2 2 2 2 2
Hydroformylation of propylene (oxo reaction)
CH3
2 ClCH CH (OH)CH Cl + Ca(OH) 2CH - CHCH Cl + CaCl +2H O CH3 CH=CH 2 + CO + H 2 CH 3 CH2 CH2 CHO + CH 3 CH - CHO
2 2 2 2 2 2 2
O
n- butyraldehyde iso - butyraldehyde
epichlorohydrin

on purpose product by-product

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

Catalyst?
Glycerol: a trihydric alcohol, used for making polyurethane foam, alkyd resin, plasticizer. Butyraldehyde is normally to be hydrogenated to make corresponding alcohol.

Process scheme to make butyraldehyde

(*): 2014 Petrochemical Processes Handbook

 2-ETHYLHEXANOL
N- BUTANOL
CH (CH ) CH(C H )CH OH
CH CH CH CH OH 3 23 2 5 2
3 2 2 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).
hydrogenation 2-Ethylhexanol: aldol condensation of butyraldehyde to form 2-ethylhexanal, aldehyde is
CH CH CH CHO + H CH CH CH CH OH dehydrated and hydrogenated to form 2-ethylhexanol.
3 2 2 2 3 2 2 2

High yield C2 H 5
2 CH3CH2CH2CHO CH3(CH2)2CHOHCHCHO

Applications: used as solvent, esterification. C2 H 5 C2 H 5

Example: ester of n-butanol with acrylic acid is for paint, adhesive, and plastic. CH3(CH2)2CHOHCHCHO CH3(CH2)2CH=CCHO + H2O

C2 H 5 C2 H 5
Special point: make primary alcohol but not secondary alcohol like other reactions. CH3(CH2)2 CH=CCHO + H CH3(CH2)3CHCH2OH
2
P: high.
Catalyst: Ni or Cu chromite carried on innert: kieselguhr, silicagel, alumina. 2-Ethylhexanol is a colorless liquid.