Petrochemicals

Lower alkenes
Chemicals industry uses 10% of available
petroleum and NG as feed, 4-5% as fuel
Ethylene, Propylene, butadiene
Produced from steam cracking of various
refinery streams.
Dehydrogenation reactions.
Lower alkenes or olefins an important feed
for products we will discuss (ex. LDPP or
HDPP)

Steam cracking:
Free radical reactions form and propagate, decompose
to an olefin plus hydrogen radical, etc.
Obeys first order kinetics
Reaction rate increases with partial pressure, and
secondary reactions do as well.
Uncatalysed reaction takes place in furnace tubes.
Near atmospheric pressure, 30-40% steam,
temperatures 750 oC -850 oC but as high as 900 oC.

Rate constants as a function of T

Reactivity increases with chain length

Industrial Process
A mixture of HC and steam is passed through
tubes inside a furnace
Heating occurs by convection and radiation
Considerable heat input at a high temperature
level
Limited HC partial pressure
Very short residence times (<1 s)
Rapid quench of product to preserve
composition otherwise pyrolysis takes place

Dehydrogenation
Recently, the demand for propenes and
butenes has been increasing.
Direct production for these specific
alkenes is important
Selectively dehydrogenate the specific
alkane (ie propane to form propylene)
Alkane dehydrogenation is highly
endothermic

 Variables in these processes include:

Type of catalyst used
Reactor design
Method of heat supply
Method for catalyst regeneration

Major dehydrogenation processes

Major outlets for alkenes

Uses of ethylene

LDPE
HDPE
LLDPE
Ethylene oxide
Dichloroethane
Ethylbenzene
Vinyl acetate
Acetaldehyde
Ethanol

15%
23 %
13 %
13 %
10-11 % (to make vinyl chloride)
7%
( to make styrene)
3%
2%
1%

Synthesis Gas, Syngas

A mixture of CO and H in varying ratios
Uses:
refinery hydrotreating, hydrocracking
Ammonia
Alkenes (via Fischer Tropsch reaction)
Methanol, higher alcohols
Aldehydes
acids

 Produced from coal, natural gas, etc.

Major processes:
Steam reforming of NG or light HC in the
presence of O2 or CO2
Partial oxidation of heavy HC with steam
(H2O) and O2
Partial oxidation of coal with steam (H2O) and
O2
Raw materials depend on cost and availability

Reactions to form Syngas

General reactions
(1) C + H2O CO + H2
(2) C + O2 CO
(3) CO + H2O CO2 + H2

(steam reforming, endothermic)

(partial oxidation, exothermic)
(water gas shift)

NG as a feed:
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)

CH4 + H2O CO + 3H2 (steam reforming, endothermic)

CO + H2O CO2 + H2 (water gas shift)
CH4 + CO2 2CO + 2H2
CH4 C + CO
2CO C + CO2
CH4 + O2 CO + H2 (partial oxidation)
CH4 + 2O2 CO2 + 2H2O
CO + O2 CO2
H2 + O2 H2O

Production of Syngas

Steam reforming
High temperatures
Nickel catalyst contained in tubes heated by a
furnace
May contain 500-600 tubes that are 7-12 m long
with ID of 70-130 mm
Convection section and radiation section
Feed pretreatment required to remove sulfur
Coke deposits can form that deactivate the
catalyst and can block the furnace tubes, so
excess steam is used to prevent this

Steam reforming

Ammonia synthesis
3H2+N2

2NH3

DH+ -91.44 kJ/ml

A major product of the CPI

Early sources were natural (saltpeter), or byproduct of coke ovens
Major use in fertilizers (agricultural), explosives (increasing due to
WWI)
In 1909 Fritz Haber established the conditions under which nitrogen,
N2(g), and hydrogen, H2(g), would combine using
medium temperature (~500oC)
very high pressure (~250 atmospheres, ~351kPa)
a catalyst (a porous iron catalyst prepared by reducing magnetite, Fe3O4).
Osmium is a much better catalyst for the reaction but is very expensive.

Requires a H2:N2 ratio of 3:1

N2 sources is air, H2 from syngas

The key to development of the Haber process was the availability of reliable thermodynamic data
At atmospheric P it was noted that NH3 did not form from a mixture of the reactants
Haber extrapolated to lower T and concluded that a feasible process could be developed
Low T and high P are favoured

Uses of ammonia
Fertiliser

Chemicals

Explosives

ammonium sulfate, (NH4)2SO4

ammonium phosphate, (NH4)3PO4
ammonium nitrate, NH4NO3
urea, (NH2)2CO
nitric acid, HNO3, which is used in making explosives such as TNT (2,4,6-trinitrotoluene),
nitroglycerine which is also used as a vasodilator (a substance that dilates blood vessels) and PETN
(pentaerythritol nitrate).
sodium hydrogen carbonate (sodium bicarbonate), NaHCO3
sodium carbonate, Na2CO3
hydrogen cyanide (hydrocyanic acid), HCN
hydrazine, N2H4 (used in rocket propulsion systems)
ammonium nitrate (NH4NO3)

Fibres & Plastics

nylon, -[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and other polyamides

Refrigeration

used for making ice, large scale refrigeration plants, air-conditioning units in buildings and plants

Pharmaceutical

used in the manufacture of drugs such as sulfonamide which inhibit the growth and multiplication of bacteria that
require p-aminobenzoic acid (PABA) for the biosynthesis of folic acids, anti-malarials and vitamins such as the B
vitamins nicotinamide (niacinamide) and thiamine

Pulp & Paper

ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods to be used

Mining & Metallurgy

Cleaning

used in nitriding (bright annealing) steel,

used in zinc and nickel extraction

Methanol
Coupled by:

CO+ 2H2 CH3OH

CO2+3H2 CH3OH+H2O
CO+H2O CO2+H2

Second large scale process involving catalyst and high P

Equilibrium data:

 Catalyst selectivity is very important, as other products

may form.
Cu/ZnO/Al2O3 catalysts are newer catalysts that enable
lower P

Methanol synthesis

Methanol uses
Formaldehyde
Methyl tert-butyl ether (MTBE) used as
octane booster

Fischer Tropsch Synthesis

German scientist who discovered in 1923 that syngas
could be converted to a wide range of HC and alcohols
Economically not competitive
Used in South Africa (Sasol) to produce fuels from coal
Recently used to convert NG to liquid fuels