PETROCHEMISTRY

Instructor: Dao Thi Kim Thoa

Petrochemical technology based on
methane
Properties

Methane is a colorless and odorless gas, lighter than air, hard to be liquefied,
boiling point: -161.5 oC

Main portion in natural gas, methane can be used as clean fuel gas.
Chemistry: not easy to react at normal condition.
There is only few chemicals directly derived from methane.
Most of the chemicals can be syntheses from synthesis gas.

methane

Carbon disulfur Acid cyanic Cloride methane Synthesis gas

Methane, LPG, Naphtha FO, Residue Coal

Partial oxidation
Steam reforming Gasification

CO + H2

Amonia Methanol F-T

Urea Formaldehyd Synthetic fuel

Acid nitric Acetic acid
Hydrazine MTBE

Considering the way to go through!

 Methane reforming

The production of synthesis gas by methane reforming is carried out by one or

more of the following processes
• Steam reforming
• CO2 reforming
• And/or partial oxidation (oxygen-enhanced reforming)

(*): Methane and Its Derivatives, Sunggyu Lee

 Steam reforming
Ni, 700 - 800 oC,
CH4 30 – 50 atm
naphtha + H2 O CO + H2
CH4
naphtha + H2 O CO2 + H2
To, P: high: metallic reactor
• The metal catalysts active for steam reforming of methane are the group VIII
metals, usually nickel.
• Although other group VIII metals are active, they have drawbacks: iron rapidly
oxidizes, cobalt cannot withstand the partial pressures of steam, and the precious
metals (rhodium, ruthenium, platinum, and palladium) are too expensive for
commercial operation.
• Rhodium and ruthenium are ten times more active than nickel, platinum, and
palladium. However, the selectivity of platinum and palladium are better than
rhodium.
• The supports for most industrial catalysts are based on ceramic oxides or oxides
stabilized by hydraulic cement.

(*): Methane and Its Derivatives, Sunggyu Lee

Partial oxidation

T (1200 – 1500oC), P (30- 80 bar)

CH4 + ½ O2 CO + 2 H2

Differ from steam reforming: catalyst free.

Energy is in-situ.

Synthetic composition (%V)

H2 CO CO2 S
Steam reforming 75 15 10 100
Partial oxidation 50 45 5 100
 Water Gas Shift
CO + H2O ⇄ CO2 + H2 ; DHo298 = – 41 kJ/mol (exothermic)
High temperature Water Gas Shift
Fe3O4 - Cr2O3 , 350 – 400 oC
High temperature: limit coke formation (2CO ⇄ CO2 + C ; DHo298 = -172.5 kJ/mol)
Fast reaction.
Equilibrium: 3 %mol CO

Low temperature Water Gas Shift

CuO – ZnO , 190 – 260 oC
Equilibrium: 0.1 % mol CO
CuO: active component
ZnO: carrier to protect Cu from the adsorption of containing S substrate.
 Chemicals derived directly from methane

1. Carbon disulfur (CS2)

CH4 (k) + 2S2 (k) ® CS2 (k)+ 2H2 (k) ; DHo298 = +150 kJ/mol
Endothermic, 675 oC, 2 atm, alumina catalyst. Yield: 85 – 90 %.
Application: syntheses of tetrachlorua carbon , xanthate (ore flotation
chemical), ammonium thiocyanate (corrosion inhibitor)

2. Hydro cyanic (HCN)

Properties: colorless liquid (Tb = 25.6 oC), soluble in water forming weak acidic
solution, high poisonous, normally used to be intermediate chemical because of
high activity.
Andrussaw process: 2CH4 + 2NH3 + 3O2 ® 2HCN + 6H2O
Catalyst: Pt-Rh alloy
T: 1100 oC.
Application: make acrylonitrile, adiponitrile (synthetic fiber), oxamide (fertilizer)
3. Chloro methane:
Chlorination methane by Cl2 with temperature or light.
Substitution hydrogen by chlorine step by step: CH3Cl (methyl chloride) ,
CH2Cl2 (methylene chloride), CHCl3(chloroform), CCl4 (tetrachloride carbon)

Methyl chloride: polymer silicon, tetramethyl lead, methylation agent, solvent,

refrigerating medium.
Methylene chloride: paint remover, oil remover, solvent, …
Chloroform: refrigerating medium, teflon, …
Tetrachloride carbon: freon (refrigerating, aerosol), …
 AMONIA Steam
CH4
reforming
CH4 + H2O CO + 3 H2

Partial
Air oxidation

CH4 + 0.5 (O2 + 3.76 N2) CO + 2H2 + 1.88 N2

WGSR
CO + H2O CO2 + H2
NH3
CO2 removal
Fe, 800 oF, 4000 psi
N2 + 3 H2 2 NH3 3H2 + CO CH4 + H2O
4H2 + CO2 CH4 + 2H2O
NH3
3H2 + N2 methanation
synthesis
Properties: colorless, pungent odor, melting point -7.7 oC , boiling point -
33.3 oC, d420: 0.6650, soluble in water, in ethanol, ether.
Application: make urea(fertilizer, plastic), acid nitric-nitrate (fertilizer,
explosive), frigerating medium, caprolactame (fiber), inert medium
(metallurgi), …

Reaction: N2 + 3 H2 ⇄ 2 NH3 ; DHo298 = – 92 kJ/mol

The reaction is favorable at low temperature and high pressure.
 Ammonia synthesis:
+ One-through conversion: low
+ High pressure: high cost of energy (pressure pump)
+ Low temperature: lower the reaction rate
 NH3 synthesis technology

+ Sulfur removal: HDS, wash out by amine

+ Conversion of CO: CO + H2O ® CO2 + H2
+ CO2 removal: absorption by K2CO3 or amine MEA
+ Methanation: 3H2 + CO ® CH4 + H2O ; DHo298 = – 206 kJ/mol
(complete conversion at T > 300 oC, catalyst Ni/alumina)
+ Wash by liquid nitrogen: for the removal of CO, CH4 (methane is not poisonous to
catalyst but lower the reaction rate) and supply N2 to make proper H2/N2.
Using catalyst to boost the reaction rate.
In industry: metal at group VIII: mainly is Fe3O4, with promoter Al2O3, K2O,
SiO2, MgO, CaO, … for increasing surface area, stability, coke resistance.
+ Catalyst is good in the range of 400 oC. It can not be exceed 550 oC.
+ Poisonous: sulfur containing chemicals, arsenic, halogen and oxygen such as
O2, CO2, CO, H2O.

P: 150 - 250 bar; T: 480 - 500 oC

(*): 2014 Petrochemical Processes Handbook
UREA
Property: solid form, fast dissolve in water, melting point: 132.7 oC , d420: 1.335.
Application: make fertilizer, urea-formadehyde resin
Synthesis:
• 2 NH3(g) + CO2 (g) ⇄ NH2 –COONH4 (l) ; DHo298 = – 151 kJ/mol
(exothermic)
• NH2–COONH4 (l) ⇄ NH2 –CO–NH2 (l) + H2O (l) ; DHo298 = 32 kJ/mol
(endothermic)

NITRIC ACID
Liquid, colorless to light yellow, highly corrosive, highly oxidative.
Synthesis: oxidation of ammonia by air over Pt-Rh catalyst.
4NH3 (k) + 5O2 (g) ® 4NO (g) + 6H2O (g) ; DHo298 = –226.4 kJ/mol
2NO (k) + O2 (g) ® 2NO2 (g) ; DHo298 = –56.5 kJ/mol
3NO2 (k) + H2O (l) ® 2HNO3 (g) + NO (g) ; DHo298 = –33.4 kJ/mol
Application: make ammonium nitrate (fertilizer), explosive, color, …
HYDRAZIN
Liquid, easy to form smoke, colorless, soluble in water, weak base but strong reduce
agent.
Rashing process: 2NH3 + NaOCl ® H2N–NH2 + NaCl + H2O
Puck process : 2NH3 + H2O2 ® H2N–NH2 + 2H2O
Application: rocket fuel (H2N–NH2 + O2 ® N2 + 2H2O + 620 kJ/mol: highly
exothermic), expanding agent (pharmaceuticals, fertilizer), initiator in polymerization
(because of weak bond N–N), oxygen reduce agent in boiler, …
2. Methanol:

Property: melting point: –97.8 oC , boiling point 4.6 oC,

d420: 0.792
Application: make formaldehyde, acetic acid, MTBE,
methyl terephthalate, solvent, …

• Main reaction:
CO + 2H2 ⇄ CH3OH (1) ; DHo298 = – 90,8 kJ/mol
CO2 + 3H2 ⇄ CH3OH + H2O (2) ; DHo298 = – 49,5 kJ/mol
(T: low and P: high)

• Side reaction: Methanation: CO + 3H2 ® CH4 + H2O

Etherification: 2CH3OH ® CH3–O–CH3 + H2O
In industry, there are 2 catalyst generations:
+ ZnO2 – Cr2O3: less activity so that T high: 300 – 400 oC, P high 300 - 350
bar (high cost)
+ CuO: high activity so that T low: 240 – 270 oC, P low: 50 - 100 bar; but it
is easily be poisoned by S and halogenated hydrocarbons.

ICI: P low (50 atm), Cu based catalyst, T: 240 oC

Methanol is produced by the catalytic reaction of carbon monoxide and
hydrogen (synthesis gas). Because the ratio of CO:H2 in synthesis gas from
natural gas is approximately 1:3, and the stoichiometric ratio required for
methanol synthesis is 1:2, carbon dioxide is added to reduce the surplus
hydrogen. An energy - efficient alternative to adjusting the CO:H2 ratio is to
combine the steam reforming process with auto-thermal reforming (combined
reforming) so that the amount of natural gas fed is that required to produce a
synthesis gas with a stoichiometric ratio of approximately 1:2.05.

Read this paragraph within 5 minutes and describe by your own language the
ways to produce exactly synthesis gas with ratio of 1:2.
 air Natural gas

desulfurization

Air separation
Steam reforming

oxygene
Autothermal
reforming
Methanol

Methanol Methanol
distillation synthesis
 Recycled Off gas
synthesis gas
CO2 methanol
H2O

CH4

water
water

Higher
alcohol

Synthesis gas plant

methanol plant
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
(*): 2014 Petrochemical Processes Handbook
 And so on …
(*): 2014 Petrochemical Processes Handbook
 FORMADEHYD
Property:
Vapor phase, melting point: -118 oC, boiling point: -19 oC, d420 0.8153.
Market: formalin is a solution of 37 – 60 % formaldehyde
Application: resin (urea-formaldehyde, phenol-formaldehyde, melamine-
formaldehyde), 1-4 butanediol, hexamethylenetetramine, …
Synthesis:
Oxidation

CH3OH + ½ O2 ® HCHO + H2O ; DHo298 = -156 kJ/mol

Highly exothermic and completely.

By-product: formic acid.
 Acetic acid
Carbonylation methanol

CH3OH + CO ® CH3COOH

BASF process over Co catalyst at 250 oC and 70 bar or new process based on
Rh complex catalyst with CH3I acts as promoter at 150 oC and atmospheric
pressure.
Application: make vinyl acetate (adhesive, film, tissue, fiber), make
pharmaceuticals, color, pesticide.

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

(*): 2014 Petrochemical Processes Handbook
 Methyl Tert Butyl Ether

Trans-esterification:
CH3 CH3
CH3OH + CH3 –C=CH2 ® CH3 –O–C–CH3
CH3
Iso-butylene

Application: octane enhancer for gasoline (RON: 112 - 130)

Besides: ETBE: Ethyl Tertiary Butyl Ether (RON: 120), TAME: Tertiary Amyl
Methyl Ether (RON: 105 - 115).
 3. FISCHER TROPSCH

Co or Ru catalyst
CO + 2H2 ® -(CH2)- + H2O ; DHo298 = –165 kJ
nCO + (2n+1)H2 ® CnH2n+2 + nH2O

Co catalyst:
T: 180 – 210 oC
P: 5 - 15 bar
Product: opening chain hydrocarbons paraffin and olefin (mainly is straight chain
with double chain at the end)
By-product: oxygenated compound (alcohol, aldehyde, ketone, acid, ester).
Application: synthetic fuel.