Chapter 4: Petrochemical technology based on Ethylene

PETROCHEMISTRY 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
Instructor: DAO THI KIM THOA § High productivity form steam cracking
Department of Oil and Gas Processing, Faculty of Chemical Engineering, University of § Less by-product
Technology, HCMC National University

Ethylene extracts
How do you think about this statement?

Polyethylene
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. Vinyl chlorua Poly vinyl chlorua
Methanol is widely produced from natural gas or coal at locations with abundant Ethyl benzene Styrene Polystyrene
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 Ethylene oxide Ethylene glycol
oil prices. Ethylene Vinyl acetate Poly vinyl acetate
Acetaldehyde Acid acetic
MTO also helps to fill the gap between propylene demand and supply Acid acrylic Poly acrylate
from steam crackers and refineries by producing olefins at high ratios
of propylene to ethylene. Ethanol
a - olefin Oxo-alcohol

OCP? LAB
 Ethylene demand Product profile from 26 millions ton Ethylene in USA in 1998

Alpha olefins and linear alcohols 6%

Vinyl acetate 3%
Worldwide

1997: 79 millions tons 2005: 114 million tons Others 7%

EG 13%

Styrene 7%
U.S
HDPE 24%
1998: 26 millions ton
PVC 15%

LDPE 14%
LLDPE 11%

1. Petroleum supplied 96 % fuel demand for transportation

2. USA consumed ¼ worldwide petroleum.
II. POLYMER
• Mỹ consumed >24% worldwide petroleum, 2.8 gal gasoline/(day, person).
• China 9%, 0.2 gal gasoline/(day, person). Longchain, large molecule
• Japan 6%, 1.8 gal gasoline/(day, person). Factors of the strength of polymer: 3
• German, Russia, India 3%, 1.4 gal gasoline/(day, person). Large molecule
Hardness
3. Middle East has the largest and cheapest petroleum reserve.
Cryslatinity
• 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, Application: 6
Venezuela, Russia, Libia , and Nigeria. 1. Plastic
• USA: only 2%. 2. Fiber
• Production cost: 3. Elastomer
ØCanada : >30$/barrel
4. Coating
ØUSA : 15-20$
ØSaudi Arabia: 2$ 5. Adhesive
6. Miscellaneous
4. Petroleum is the largest source of green house gas.
5. 69% petroleum is used for transportation.
 Polymer structures
Plastic Recycling

• SPI: Society of the Plastics Industry

• Born: 1988
• Common with: PET and HDPE
• Thermoplastic
• Thermoset

Polyethylene: LLDPE:
LDPE: Idea: polymer alike LDPE but formed in mild condition like HDPE.
To high, P high, polymerization by free radical mechanism. Co-monomer: 1-butene, 1-hexene, 1-octene
Polymer more branch than HDPE (lower density, less crystallinity) Crystallinity: reduce from 85-95% of HDPE to 50% of LDPE.
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
 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

Hydro-chlorination Acetylene
Vinyl chlorua Adding acid clohydric into acetylene

+ Gas, colourless, melting point: -153,8 oC, boiling point: -13,4 oC, d4-20 = 0,9834 CH º CH + HCl ® CH2 =CHCl
DHo298 ~ – 100 kJ/mol
+ Mainly to produce PVC.
+ In industry: VCM (CH2 = CHCl) is synthesed by several methods. Reaction: gas phase
Catalyst: HgCl2
Temperature: 100 - 170 oC
Pressure: 30 bars
Conversion: 98 %
By-products: acetaldehyde, 1-1 di-chloro ethane:
Introduce the VCM Technology in Handbook (p. 227/233). CH2 = CHCl + HCl ® CH3 –CHCl2

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

 Chlorination Ethylene
Ethylene: cheaper than acetylene. Combine acetylene and ethylene
2 stages: chlorination of ethylene and then is pyrolysed of di-chloro ethane.
a. Chlorination of ethylene to form di-chloro ethane.
To use up HCl from process using ethylene: combine both.

CH2 = CH2 + Cl2 ® CH2Cl – CH2Cl

DHo298 : - 185 kJ/mol.
Availability: cheap acetylene source or there is
Liquid phase, FeCl3, 50 – 90 oC, low pressure 3 – 5 bars, high conversion: 100 %. availability of mixture of acetylene – ethylene.
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 C
o

P: 25 – 30 bars.

Oxy-chlorination ethylene A. Chlorination:

Crude oil naphtha ethylene EDC VCM + HCl

CuCl2, KCl,
KCl, Al2O3
CH2=CH2 + 2HCl + 1/2 O2 CH2ClCH2Cl Salt Cl2
230oC, 3 atm,
atm, -H ethylene dichloride PVC
2O

550oC, 30 atm B. Oxy-chlorination:

-HCl
catalyst
Crude oil naphtha ethylene EDC VC + HCl
PVC and co-polymers CH2=CHCl
Vinyl chloride 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

 † 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.

(*): Petrochemical in nontechnical language.

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: There are 3 processes

v Short chain polymer 1. Ziegler process:

v There are two types of ethylene oligomers: Aluminium triethyl + Ethylene

Ø a-olefin: applicaions:
§ Surfactant To low Vegetable oil,
animal fat
§ Plasticizer
Aluminium trialkyl
§ Lube oil additive
§ Co-monomer for LLDPE Ethylene
To high +O2
Ø Oxo alcohol: applications:
§ Detergent a- olefin +H2O
Alkoxide Oxo alcohol
C4 – C24
§ Plasticizer C5 – C25

+ H2 + CO

• (CH3CH2)3Al + 1 ½ n CH2=CH2 [CH3(CH2)n+1]3Al

Alpha olefin: dehydrogenation n-paraffin
dehydrochlorination monochloroparaffin
oligomerization ethylene over Ziegler catalyst
• [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:
3. SHOP (The Shell Higher Olefin Process)
Ø Oxo-alcohol: CH3CH2(CH2CH2)xOH
Ø a - olefin: CH3CH2(CH2CH2)xCH=CH2
To make desired length
v Length: 4 - 24 C
v Desired length: 12 - 14C for surfactant application

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

Idea: methathesis

Competition
2CH2=CH-CH3 CH2=CH2 + CH3-CH=CH-CH3
propylene ethylene butene-2

2. Shell process: a- olefin

Ethylene
C4 – C40
Nikel chloride, 1,4-butandiol

There are 4 reactions

Ø Oligomerization

Ø Isomerization

Ø Metathesis

Ø Linear hydrofomylation

(*): Petrochemical Processes. Sami Matar, Lewis F. Hatch.

 1. Oligomerization 4. Isomerization

NiCl2 b. C4-C8 a - olefin C4-C8 olefin

CH2=CH2 H-(CH2=CH2)x-CH=CH2 noäi
1,4-butandiol c. C16-C40 a - olefin C16-C40 olefin noäi
x=1-19
2. Distill a - olefin: Example:

CH3CH2CH=CH2 CH3CH=CHCH3
a. C10-C14 a - olefin
b. C4-C8 a - olefin 5. Metathesis C4-C8 and C16-C40 inner-olefin
c. C16-C40 a - 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
3. Hydrofomylation C10- C14 a - olefin
6. Distill inner-olefin
C10-C14 a - olefin C11-C15 alcohol
a. C10 – C14 olefin noäi
Example: b. C4 – C8 olefin noäi
+ H2,, CO + H2
CH3(CH2)7CH=CH2 CH3(CH2)7CH2-CH2-CHO CH3(CH2)9-CH2OH c. C16 – C40 olefin noäi
C10 a - olefin C11 alcohol

7. Hydrofomylation
H2, CO
CH3 (CH2)8 CH=CH-CH3 CH3 (CH2)8 CH2-CH2-CH2 - CHO
Complex catalyst

CH3 (CH2)11 CH2- OH

Catalyst
8. Repeat step 5, 6, and 7 Rh: orient linear
Co: orient branch (shift)

(*): Rhodium catalyzed Hydroformylation

 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, …

(*): 2014 Petrochemical Processes Handbook

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

PdCl2, CuCl2, HCl, H2O Liquid phase

CH2=CH2 + ½ O2 CH3CHO
120oC, 3 atm T: 65oC
Catalyst: mangane acetate
v Before: acetaldehyde from ethanol
v Wacker reaction + N-butanol
v However: the production of acetaldehyde reduced gradually. -
2CH3CHO OH CH3CH(OH)CH2CHO H+ CH3CH=CHCHO +H2O
Ø 1975: 1.5 billions pounds
Ø 1995: 0.6 billions pounds + H2
CH3CH2CH2CH2OH

Raise the cause of the reduction of acetaldehyde with time? • 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.