Ho Chi Minh city University of Technology, VNU–HCM

Faculty of Chemical Engineering

Division of Organic Chemistry

Chemical Technology of
Organic Compounds
Lecturer : Dr. Nguyễn Đăng Khoa
Room 211 B2
Tel: 38647256 ext. 5681
Email: khoand1989@hcmut.edu.vn
Introduction_ Chemical processes

Crude oil

Gas Naptha Kerosene Diesel Others

C1-C4 C5-C9 (Paraffin) C14-C20 C18-Cxx
C10-C16

Saturated hydrocarbons
(inert chemicals)
Conversion process (3 reasons) 2
Chemicals based on methane
Urea HNO3 N2H4 Amines

Direct
conversion – 4%
Ammonia
C2H2, C2H4
Indirect
conversion
(96%) Syn gas
Hydrocarbons
CO H2 FT
process

Methanol
CS2 C2H3Cl HCN
C2H2Cl2
CHCl3
CCl4
HCHO CH3COOH Methyl Methyl Methyl MTBE Gasoline
ester chloride amine
Methane _ Direct conversion

Carbon disulfide - CS2

 Viscose fiber,
 Cellophane

Hydro cyanide - HCN

 Acrylonitrile,
 Methyl methacrylate
 Adiponitrile
Oxamide  Sodium cyanide
 Oxamide

Chloromethanes
 Polymers
 Freon

4
Methane _ Indirect conversion

5
Methane _ Indirect conversion

Steam Partially Water gas Water gas

reforming oxidation Shift reaction-1 Shift reaction-2
CH4 + 1/2O2 CO + H2O CO + H2O

CO + 2H2 CO2 + 2H2 CO2 + 2H2

T (>1200oC) 350 – 400oC 190 – 260oC

P (30- 80 bar) Fe3O4 - Cr2O3 CuO - ZnO

H2 CO CO2 

Steam reforming 75 15 10 100

Partially oxidation 50 45 5 100

6
Methane _ Indirect convert to methanol

7
Methane _ Indirect convert to methanol

8
Methane _ Indirect convert to ammonia

9
Methane _ Indirect convert to ammonia
Steam Partial Water Gas
Natural gas reforming oxidation Shift 3
1 2
Air
Methanation
4

CH4 + H2O 2 CO + 3 H2
CH4 + 0.5 (O2 + 3.76 N2) CO + 2H2 + 1.88 N2 CO2 removal

CO + H2O CO2 + H2
3H2 + CO CH4 + H2O
4H2 + CO2 CH4 + 2H2O
5
N2 + 3 H2 2 NH3

NH3 NH3 synthesis

6
Methane _ Indirect convert to ammonia

Phú Mỹ Fertilizer Plant Require: 900 million m3 of gas

produce: Ammonia (540,000 tons per year)
Urea (800,000 tons per year)
Original from: Bạch Hồ well
Cửu Long and Nam Côn Sơn basin

Cà Mau Fertilizer Plant Require: 500 million m3 of gas

Produce: Urea (800,000 tons per year)
Original from: Bạch Hồ well
Cửu Long and Nam Côn Sơn basin
Malaysia
Chemicals based on methane
Urea HNO3 N2H4 Amines

Direct
conversion – 4%
Ammonia
C2H2, C2H4
Indirect
conversion
(96%) Syn gas
Hydrocarbons
CO H2 FT
process

Methanol
CS2 C2H3Cl HCN
C2H2Cl2
CHCl3
CCl4
HCHO CH3COOH Methyl Methyl Methyl MTBE Gasoline
ester chloride amine
Chemicals based on methane
Use for:
Chemicals based on ethylene

 Simple structure
 High reactivity
 Inexpensive
 Easy in synthesis
 High selectivity
Ethylene _ Polymerization

HDPE  High density

 Less branches
 110-120oC
 Tensile strength
 Resilience
 Bottle structure

Polymerization [O]
LDPE  Low density
 More branches
 85-95oC
 Film structure

Monomer
LLDPE  Co-polymer
Ethylene _ Polymerization

LDPE HDPE LLDPE

Catalysts O2 or peroxide Ziegler catalyst Ziegler catalyst
Reaction temp. (oC) 200-300 60 60

Reaction press (atm) 1300-2600 0-20 0-20

Arrangement Branches Liner Liner and short branches

Crystallization (%) 55 85-95 55

Co-monomer - - 1-butene

Tensile strength (psi) 1200-2000 3000-5500 2000-2500

Resilience (%) 500 10-100 500

Density (g/cm3) 0.915-0.925 0.945-0.965 0.915-0.925

Ethylene _ Chlorination and oxidation

 Ethane  Difficulty in synthesis

 Ethylene

 Acetylene  Expensive and low

selectivity

13 billion
kilograms are
produced annually
Ethylene _ Chlorination and oxidation
 Chlorination
CuCl2 or FeCl3 500oC, 3 atm
CH2=CH2 + Cl2 CH2ClCH2Cl CH2=CH-Cl + HCl
50oC
 Oxidation
CuCl2-KCl/Al2O3
CH2=CH2 + 2HCl + 1/2 O2
200oC, 3 atm

PVC:  Additives
 Phenol
 Leaching
 Other derivatives : polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal
Ethylene _ Oxidation

Liner alcohols
Ethoxylates
Detergents
[O]

Long-chain fatty acids

Ethoxylates
Detergents

H+

Amines
Ethanolamines
Detergents
Ethylene _ Oligomerization

Ethylene [O]
To

- olefin Alkoxide Liner alcohols

C4 – C24
CO + H2
Ethylene _ Oligomerization
General reaction

For example

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Ethylene _ Oligomerization
Synthesis of biodegradable detergents (AOS)

Synthesis of detergents (LABS)

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Ethylene _ Liner alcohols (Even carbons)

[O]

H2O
 Cl0–Cl2 : Plasticizers
 Cl2–Cl6 : Biodegradable detergents
 Cl6–Cl8: wash and wear polymers
 C20–C26: lubricants

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Ethylene _ Liner alcohols (Odd carbons)
1. Oligomerization

NiCl2
CH2=CH2 (CH2=CH2)x x=1-19
1,4-butandiol

2. Distillation of  - olefin:
a. C10-C14  - olefin

b. C4-C8  - olefin

c. C16-C40  - olefin

3. Hydrofomylation C10- C14  - olefin

C10-C14  - olefin C11-C15 alcohol

4. Isomerization

b. C4-C8  - olefin C4-C8 olefin noäi

c. C16-C40  - olefin C16-C40 olefin noäi

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Ethylene _ Liner alcohols (Odd carbons)
1. Oligomerization

NiCl2
CH2=CH2 (CH2=CH2)x x=1-19
1,4-butandiol

2. Distillation of  - olefin:
a. C10-C14  - olefin

b. C4-C8  - olefin

c. C16-C40  - olefin

3. Hydrofomylation C10- C14  - olefin

C10-C14  - olefin C11-C15 alcohol

4. Isomerization

b. C4-C8  - olefin C4-C8 symmetric olefin

c. C16-C40  - olefin C16-C40 symmetric olefin

CH3CH2CH=CH2 CH3CH=CHCH3 25
Ethylene _ Liner alcohols (Odd carbons)
5. Metathesis C4-C8 and C16-C40

CH3CH=CHCH3 CH3 (CH2)8 CH=CH(CH2)8CH3 2 CH3 CH=CH(CH2)8CH3

C4 olefin C20 olefin C12 new symmetric olefin

6. Distillation
a. C10 – C14 symmetric olefin
b. C4 – C8 symmetric olefin
c. C16 – C40 symmetric olefin

7. Hydrofomylation
H2, CO
CH3 (CH2)8 CH=CH-CH3 CH3 (CH2)8 CH2-CH2-CH2 - CHO
Rh Cat

CH3 (CH2)11 CH2- OH

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Ethylene _ Liner alcohols (Odd carbons)
How to synthesize these below compounds
CH3 (CH2)4 CH2- OH

CH3 (CH2)8 CH2=CH2

+
CH3 (CH2)4 CH2- O-C(O)-CH3

CH3 (CH2)4 CH2- O-C(O)-CH3

CH3 (CH2)9 CH2- O-C2H4-OC2H4-OH

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Ethylene _ Hydration

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