PETROCHEMISTRY

Chap 4

Instructor: DAO THI KIM THOA

Department of Oil and Gas Processing, Faculty of Chemical Engineering, University of
Technology, HCMC National University
 Chapter 4: Petrochemical technology based on Ethylene

I. Introduction

“King of petrochemicals”
Source: steam cracking, catalytic cracking

Property:
§ Gas, colorless, pleasant smell, sweet; melting point: - 169.2 oC ; boiling
point: -103.7 oC ; flammable.
§ Simple, active
§ Reasonably cheap
§ High productivity form steam cracking
§ Less by-product
 How do you think about this statement?

The conversion of methanol to olefins (MTO) is a means to produce ethylene and

propylene from feedstock derived from sources other than crude oil or condensates.
Methanol is widely produced from natural gas or coal at locations with abundant
reserves. By utilizing methanol derived from these cost advantaged raw materials,
MTO enables low costs of production for ethylene and propylene in a world with high
oil prices.

MTO also helps to fill the gap between propylene demand and supply
from steam crackers and refineries by producing olefins at high ratios
of propylene to ethylene.

OCP?
 Ethylene extracts

Polyethylene
Vinyl chlorua Poly vinyl chlorua
Ethyl benzene Styrene Polystyrene
Ethylene oxide Ethylene glycol
Ethylene Vinyl acetate Poly vinyl acetate
Acetaldehyde Acid acetic
Acid acrylic Poly acrylate
Ethanol
a - olefin Oxo-alcohol
LAB
 Ethylene demand

Worldwide

1997: 79 millions tons 2005: 114 million tons

U.S

1998: 26 millions ton

 Product profile from 26 millions ton Ethylene in USA in 1998

Alpha olefins and linear alcohols 6%

Vinyl acetate 3%

Others 7%
EG 13%

Styrene 7%

HDPE 24%
PVC 15%

LDPE 14%
LLDPE 11%
 1. Petroleum supplied 96 % fuel demand for transportation
2. USA consumed ¼ worldwide petroleum.
• Mỹ consumed >24% worldwide petroleum, 2.8 gal gasoline/(day, person).
• China 9%, 0.2 gal gasoline/(day, person).
• Japan 6%, 1.8 gal gasoline/(day, person).
• German, Russia, India 3%, 1.4 gal gasoline/(day, person).

3. Middle East has the largest and cheapest petroleum reserve.

• USA: the largest market
• Saudi Arabia: the largest supply.
• > 50% reserve located in Middle East, Saudi Arabia holded 20%.
• Order of petroleum reserve: Saudi Arabia, Canada, Iran, Iraq, Kuwait, UAE,
Venezuela, Russia, Libia , and Nigeria.
• USA: only 2%.
• Production cost:
ØCanada : >30$/barrel
ØUSA : 15-20$
ØSaudi Arabia: 2$
4. Petroleum is the largest source of green house gas.
5. 69% petroleum is used for transportation.
II. POLYMER
Longchain, large molecule
Factors of the strength of polymer: 3
Large molecule
Hardness
Cryslatinity

Application: 6
1. Plastic
2. Fiber
3. Elastomer
4. Coating
5. Adhesive
6. Miscellaneous
Polymer structures
 Plastic Recycling

• SPI: Society of the Plastics Industry

• Born: 1988
• Common with: PET and HDPE
• Thermoplastic
• Thermoset
Polyethylene:
LDPE:
To high, P high, polymerization by free radical mechanism.
Polymer more branch than HDPE (lower density, less crystallinity)
Thermal limit: 80 - 95 oC in a short time.
HDPE:
Catalyst: Ziegler-Natta : (C2H5)3Al
Reaction condition: less severe
Less branch than LDPE
Higher tensile strength than LDPE
Less resilience than LDPE because it is more rigid
Thermal limit: 110-120 oC
LDPE: film
HDPE: bottle
 LLDPE:
Idea: polymer alike LDPE but formed in mild condition like HDPE.
Co-monomer: 1-butene, 1-hexene, 1-octene
Crystallinity: reduce from 85-95% of HDPE to 50% of LDPE.
 LDPE HDPE LLDPE

Initiator or catalyst O2 or peroxide Ziegler Ziegler

To (oC) 200-300 60 60
P (atm) 1300-2600 0-20 0-20
Structure Branch Straight Straight, short
% Crystalinity 55 85-95 55
Co-monomer - - 1-butene
Elongation(psi) 1200-2000 3000-5500 2000-2500
Density(g/cc) 0.915-0.925 0.945-0.965 0.915-0.925
(*): 2014 Petrochemical Processes Handbook
 Vinyl chlorua

+ Gas, colourless, melting point: -153,8 oC, boiling point: -13,4 oC, d4-20 = 0,9834
+ Mainly to produce PVC.
+ In industry: VCM (CH2 = CHCl) is synthesed by several methods.

Introduce the VCM Technology in Handbook (p. 227/233).

 Hydro-chlorination Acetylene

Adding acid clohydric into acetylene

CH º CH + HCl ® CH2 =CHCl

DHo298 ~ – 100 kJ/mol

Reaction: gas phase

Catalyst: HgCl2
Temperature: 100 - 170 oC
Pressure: 30 bars
Conversion: 98 %
By-products: acetaldehyde, 1-1 di-chloro ethane:

CH2 = CHCl + HCl ® CH3 –CHCl2

Evaluation: Old method, simple, less investment, but acetylene is costly.

 Chlorination Ethylene
Ethylene: cheaper than acetylene.
2 stages: chlorination of ethylene and then is pyrolysed of di-chloro ethane.
a. Chlorination of ethylene to form di-chloro ethane.

CH2 = CH2 + Cl2 ® CH2Cl – CH2Cl

DHo298 : - 185 kJ/mol.

Liquid phase, FeCl3, 50 – 90 oC, low pressure 3 – 5 bars, high conversion: 100 %.
By-products: tri-chloro ethane and others chloro ethane, chloro ethylene.

b. Pyrolysis of di-chloro ethane to form VCM

Free radical mechanism.

CH2Cl – CH2Cl ® CH2 = CHCl + HCl

DHo298 = + 70 kJ/mol
T: 500 – 550 oC
P: 25 – 30 bars.
 Combine acetylene and ethylene

To use up HCl from process using ethylene: combine both.

Availability: cheap acetylene source or there is

availability of mixture of acetylene – ethylene.
 Oxy-chlorination ethylene

CuCl2, KCl, Al2O3

CH2=CH2 + 2HCl + 1/2 O2 CH2ClCH2Cl
ethylene dichloride
230 oC, 3 atm,- H 2O
550oC, 30 atm
-HCl

PVC and co-polymers CH2=CHCl

Vinyl chloride
A. Chlorination:

Crude oil naphtha ethylene EDC VCM + HCl

Salt Cl2
PVC

B. Oxy-chlorination:
catalyst
Crude oil naphtha ethylene EDC VC + HCl

Air oxygen

1. Chlorination: CH2=CH2 + Cl2 CH2Cl-CH2Cl

to
2. Pyrolysis: CH2Cl-CH2Cl CH2=CHCl + HCl

3. Oxy-chlorination: CH2=CH2 + 2HCl + 1/2O2 CH2Cl=CH2Cl + H2O

(*): Petrochemical in nontechnical language.
† VCM from ethane: ideal but not easy.

† VCM from acethylene: not favorable because acetylene is costly and so

sensitive.

† There are 2 types of PVC: hard and flexible.

† Application: pipe, coating material, mould, grind, film, flat, bag, cassette player,
auto seat cushion, roof, wall, …

† MSDS: evidence of the fact that VCM can cause liver cancer with very low
content (ppm).

† Store: VCM vaporizes at 7oF: contained in pressure container with liquid phase.

† VCM is very active: like styrene, can polymerizes, phenol is the good inhibitor.
PVC is the most common polymer in vinyl family

Ø PVAC: polyvinyl acetate

Ø PVA: polyvinyl alcohol

Ø PVdC: polyvinyl acetal
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
 Poly Styrene

ZSM 5, 420oC, 200-300 psi

Benzene + ethylene. ethyl-benzene
or AlCl3 – HCl, 40-100oC, 2-8 atm

Ethyl-benzene. Metal oxide or mixed oxides styrene + H2

600 – 700oC, 1 atm

Styrene: mainly to product polymer:

üPS: poly-styrene
üSBR: styrene-butadiene-rubber

Key application: fabrication. Foam PS is the polymerization of

styrene with pentane, low density, for insulation and fabrication.
(*): Petrochemical Processes. Sami Matar, Lewis F. Hatch.
(*): Petrochemical Processes. Sami Matar, Lewis F. Hatch.
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
4. Vinylacetate:
• Liquid, colorless, active, easily to be polymerized, boiling point 72.7 oC , d420 0.935.

• Application: monomer for polyvinyl acetate, polyvinyl alcohol, copolymer of vinyl

acetate.
• In America: 1.5 millions ton/year in1994, range 40 in the world.

Before:
CH =CH + CH3COOH + Hg(-O-CO-CH3)2 CH2=CH-OCOCH3

Currently:
CH2=CH2 + CH3COOH + 1/2 O2 CH3COOCH=CH2
vinyl acetate

Reaction in liquid phase, like oxidation of ethylene to acetaldehyde, the only difference
is there is acetic acid. So, by-product is acetaldehyde with mol fraction is:
acetaldehyde: vinyl acetate : 0.3:1 to 2.5:1.
Drawback: corrosive and by-product.
Reaction in gas phase: oxy-acylation ethylene takes place in tube reactor, T: 117 oC, 5
atm, catalyst Pd(OCOCH3)2 over carrier which is stable to acetic acid. Coversion 10-15
% , selectivity 94 %.
Application of PVAC: water paint and adhesive.
II. Oligomers:

v Short chain polymer

v There are two types of ethylene oligomers:

Ø a-olefin: applicaions:
§ Surfactant
§ Plasticizer
§ Lube oil additive
§ Co-monomer for LLDPE
Ø Oxo alcohol: applications:
§ Detergent
§ Plasticizer
 There are 3 processes

1. Ziegler process:

Aluminium triethyl + Ethylene

To low Vegetable oil,

animal fat
Aluminium trialkyl

Ethylene
To high +O2

a- olefin +H2O
Alkoxide Oxo alcohol
C4 – C24
C5 – C25

+ H2 + CO
Alpha olefin: dehydrogenation n-paraffin
dehydrochlorination monochloroparaffin
oligomerization ethylene over Ziegler catalyst
• (CH3CH2)3Al + 1 ½ n CH2=CH2 [CH3(CH2)n+1]3Al

• [CH3(CH2)n+1]3Al + 3CH3CH2CH=CH2
• 3CH3(CH2)n-1-CH=CH2 + (CH3CH2CH2CH2)3Al
• n=4,6,8 …

• (CH3CH2CH2CH2)3Al + 3CH2=CH2
• (CH3CH2)3Al + 3CH3CH2CH=CH2

• Alpha olefins is an important base to produce biodegradable detergent (AOS –

alpha olefin sulfonate):

• RCH=CH2 + SO3 RCH=CHSO3H

• RCH=CHSO3H + NaOH RCH=CHSO3Na + H2 O
v There are 2 products:
Ø Oxo-alcohol: CH3CH2(CH2CH2)xOH
Ø a - olefin: CH3CH2(CH2CH2)xCH=CH2

v Length: 4 - 24 C
v Desired length: 12 - 14C for surfactant application

Another source: natural: vegetable oil or animal fat (C6 - C18)

Competition

2. Shell process: a- olefin

Ethylene
C4 – C40
Nikel chloride, 1,4-butandiol
 3. SHOP (The Shell Higher Olefin Process)

To make desired length

Idea: methathesis

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

propylene ethylene butene-2
(*): Petrochemical Processes. Sami Matar, Lewis F. Hatch.
 There are 4 reactions

Ø Oligomerization

Ø Isomerization

Ø Metathesis

Ø Linear hydrofomylation
 1. Oligomerization
NiCl2
CH2=CH2 H-(CH2=CH2)x-CH=CH2
1,4-butandiol
x=1-19
2. Distill a - olefin:

a. C10-C14 a - olefin
b. C4-C8 a - olefin
c. C16-C40 a - olefin

3. Hydrofomylation C10- C14 a - olefin

C10-C14 a - olefin C11-C15 alcohol

Example:
+ H2,, CO + H2
CH3(CH2)7CH=CH2 CH3(CH2)7CH2-CH2-CHO CH3(CH2)9-CH2OH
C10 a - olefin C11 alcohol
4. Isomerization

b. C4-C8 a - olefin C4-C8 olefin

noäi
c. C16-C40 a - olefin C16-C40 olefin noäi
Example:

CH3CH2CH=CH2 CH3CH=CHCH3

5. Metathesis C4-C8 and C16-C40 inner-olefin

CH3CH=CHCH3 + CH3 (CH2)8 CH=CH(CH2)8CH3 2 CH3 CH=CH(CH2)8CH3
C4 inner-olefin C20 inner-olefin C12 inner-olefin

6. Distill inner-olefin
a. C10 – C14 olefin noäi
b. C4 – C8 olefin noäi
c. C16 – C40 olefin noäi
7. Hydrofomylation
H2, CO
CH3 (CH2)8 CH=CH-CH3 CH3 (CH2)8 CH2-CH2-CH2 - CHO
Complex catalyst

CH3 (CH2)11 CH2- OH

8. Repeat step 5, 6, and 7

 Catalyst
Rh: orient linear
Co: orient branch (shift)

(*): Rhodium catalyzed Hydroformylation

(*): 2014 Petrochemical Processes Handbook
 Chemical
1. Ethylene oxide

Properties
+ Colorless gas, liquefied below 12 oC, soluble in water and organic solvent.
+ High activity, reacts with any chemicals containing hydrogen like water, alcohol,
organic acid, amine.
Applications
+ To make ethylene glycol, ethanol amine, ethoxylate, …
Chlorohydrination
0.5 CaO
CH2=CH2 + HOCl CH2OHCH2Cl CH2 - CH2 + 0.5 CaCl2 + 0.5 H2O
Ethylene chlorohydrin O
v 0.9 ton ethylene/ton ethylen oxide
v 2 ton chlorine
v 2 ton lime
1960 v 0.817 ton ethylene/ton ethylene oxide
v High price of chlorine v No chlorine
v Need to be scaled up v No lime
v New reaction
Ag catalyst
CH2 =CH2 + 0.5 O2 CH2 – CH2 DHo298 = –147 kJ/mol
O
Side reaction:
CH2 = CH2 + 3O2 ® 2 CO2 + H2O ; DHo298 = –1.421 kJ/mol

Highly exothermic, reduce ethylene oxide yield and destroy catalyst.

T: 200 – 300 oC
t: short: 1 s.
(*): 2014 Petrochemical Processes Handbook
 Ethylene glycol
Properties and applications
+ Liquid, sweet, colorless, soluble in water, melting point (– 13.2 oC), boiling point
197.2 oC.
+ To make polyethylene terephthalate (PET), anti-freeze additive, …

Synthesis.
Hydration ethylene oxide in diluted sulfuric acid.
O
CH2–CH2 + H2 O ® HO-CH2-CH2OH ; DHo298 = –75 kJ/mol

T: 100 – 150 oC ; t: 30 mins.

Co-product: di, tri-ethylene glycol.
Increase ratio of H2O/ ethylene oxide and reduce contact time: limit the formation of
high ethylene glycol. H2O/ethylene oxide: 20 gives 90 % mono-glycol.
(*): 2014 Petrochemical Processes Handbook
2. Acetaldehyde

PdCl2, CuCl2, HCl, H2O

CH2=CH2 + ½ O2 CH3CHO
120oC, 3 atm

v Before: acetaldehyde from ethanol

v Wacker reaction
v However: the production of acetaldehyde reduced gradually.
Ø 1975: 1.5 billions pounds
Ø 1995: 0.6 billions pounds

Raise the cause of the reduction of acetaldehyde with time?

•Acetaldehyd is an intermediate for the production of
+ Acid acetic: CH3CHO + ½O2 ® CH3COOH

Liquid phase
T: 65oC
Catalyst: mangane acetate

+ N-butanol
-
2CH3CHO OH CH3CH(OH)CH2CHO H+ CH3CH=CHCHO +H2O

CH3CH2CH2CH2OH + H2

• CH2=CH2 + PdCl2 + H2O CH3CHO + 2HCl + Pd°

• Pd°+ 2CuCl2 PdCl2+2CuCl

• 2CuCl + 1/2O2 + 2HCl 2CuCl2+H2O
3. Ethanol
Hydration
H3PO4, SiO2
CH2=CH2 + H2 O C2H5OH
300oC, 70 atm

v Ethanol is mainly to blend gasoline.

v USA: courage to make ethanol from grain
v Brazil: ethanol from sugar can
v Ethanol gives energy lower than energy to make it.
v Applications: gasoline additive, cosmetic, make up remover, coating, ink, detergent,
food, drug, solvent.