1.

BUDAPEST UNIVERSITY OF TECHNOLOGY AND

ECONOMICS

1. FACULTY OF CHEMICAL 1. DEPARTMENT OF

AND BIOCHEMICAL CHEMICAL AND
ENGINEERING 2. ENVIRONMENTAL PROCESS
ENGINEERING

HYDROCARBONS AND
PHOTOCHEMICAL
OXIDANTS
Authors: Dr. Bajnóczy Gábor
Kiss Bernadett
The pictures and drawings
of this presentation can be
used only for education !

Any commercial use is

prohibited !
 Hydrocarbons: primary pollutants
(saturated and
unsaturated aliphatic hydrocarbons,
terpenes, mono and polycondensed
aromatic hydrocarbons)

 Photochemical oxidants:
secondary pollutants, forms from the
primary pollutants e.g..: peroxyacyl
nitrates, ozone
 Hydrocarbons
 1 - 4 carbon atoms: gas in the Hydrocarbons in urban air Los Angeles
troposphere (1965)

hydrocarbon (ppm)
 4 < carbon atoms: steam or
liquid/solid particles in the Methane CH4 3,22
troposphere
Toluene C7H8 0,05

n-butane C4H10 0,06

i-pentane C5H12 0,04

The unsaturated Ethane C2H6 0,1

hydrocarbons Benzene C6H6 0,03
photochemically are more n-pentane C5H12 0,03
active in the troposphere
than the saturated ones. Propane C3H8 0,05

ethylene C2H4 0,06

 Terpenes
 Significant amount in the troposphere
 Unit: isoprene molecule CH2=C(CH3)-CH=CH2
 General structure: (C5H8)n
 Monoterpenes: two unites of isoprene e.g. pinene, , camphor,
menthol, limonene.

Organic hydrocarbons (CH)x or (CxHy)

Volatile organic hydrocarbons: VOC
Polycyclic aromatic hydrocarbons in the atmosphere
in form of gas phase
 PAH (polycyclic aromatic hydrocarbons)
 Two or more condensed aromatic rings
 Some of them carcinogenic → strongest effect : benz[a]pyrene, ( BaP )

 First three: in paints-,

pesticides-industrial raw
materials
 The others: in fuel gas of
wood, coal, natural gas
petroleum products
 Polycyclic aromatic hydrocarbons in the
atmosphere in form of condensed or adsorbed
phase
 Polycyclic aromatic hydrocarbons

 Two groups have been

defined (U.S.
Environmental
Protection Agency),
(7-PAH) and (16-PAH).

 All members of 7-PAH

are carcinogenic.

 In the 16-PAH the

7-PAH members and
other non carcinogenic
PAH materials are
involved
 Photochemical oxidants
 Source: oxidation of unsaturated hydrocarbons
 Harmful, irritating molecules
 Members: peroxyacyl nitrates and ozone
 Only the following three can be found in the troposphere :
peroxyacetyl nitrate : PAN, peroxypropionyl nitrate : PPN, peroxybenzoyl nitrate : PBzN
 Natural sources
 Greatest amount: methane → anaerobe decay of organic molecules
 Natural background:
 Methane: 1.0 – 1.5 ppm
 Other hydrocarbons: < 0,1 ppm

 Other hydrocarbons from natural sources pl.: terpenes with pleasant

odor emitted by different plants (e.g. pine tree )

 polycyclic aromatic hydrocarbons from natural sources:

 Forest fires
 Natural weathering of oily rocks
 Natural leakage of crude oil

 Peroxyacyl nitrates:
 No direct natural sources

 ozone
 lightning, 20 – 30 ppbv,.
 Anthropogenic sources
 Majority of the emissions:
 Exhaust gases of burned fuel
 Evaporation of organic solvents (toluene, xylene,
alkanes, esters)

 PAH emission:
 Coal industry (coke manufacturing)
 Mineral oil processing
 Pyrolysis (soot, fuel oil from biomass)

 Peroxyacyl nitrates and ozone

indirect source: from hydrocarbons and nitric oxide
 Formation of hydrocarbons
 Effective factors: air excess ratio (n), flame temperature and the
residence time at high temperature
 Main source: transportation (in spite of the optimal air excess ratio)
 Reason: wall effect

The cooler wall slows the rate of  Boilers with smaller firebox produces much
oxidation in the vicinity of it. more hydrocarbons, carbon monoxide and
The piston pushes out the soot particles than the boilers with large
exhaust gas earlier than the firebox.
time needed for the completed
combustion.
Formation of polycyclic aromatic hydrocarbons I.
Combustion of carbon content fuel, 500 – 800 0C → decay above
Forms in the vicinity of cooler part of the burn => smaller fire box
greater PAH emission

1. Additional reaction with acetylene and ethylene radicals resulting in ring

closure. (Wang-Frenklach mechanism 1997)
H2C=CH2 + H => H2C=CH• + H2
The addition of acetylene radical on the aromatic ring produces more and more
condensed aromatic rings.
(HACA mechanism : hydrogen adsorption and C2H2 addition) .
Formation of polycyclic aromatic hydrocarbons II.

2. The polycondensed aromatic structure forms quickly by the

addition of benzene rings (soot formation).
Emissions of polycyclic aromatic hydrocarbons

PAH és BaP emission of boilers with different size.

source: Huotari J., Vesterinnen R. (1995) , Finland

Household boilers boilers boilers boilers

with solid fuel 1-5 MW 5 – 50 MW >50 MW

PAH
μg/MJ
2-10 (solid)
1000 – 3000 < 10 <5
< 5 (oil, gas)

BaP
μg/MJ
< 20 < 0,1 < 0,01
 Formation of peroxyacyl nitrates
TheThelifetime
alkyl of aldehyde
radicals is shortform
(alkilgyök) in the atmosphere.
alkylperoxy It decays by
radicals
The
Aldehyde
The effect of oxygen
formation
peroxyalkyl on
radicals the
is radicals
possible
mayalkoxy radicals
inoxidize
the reaction
the (alkokszigyök)
NOof unsaturated
or forms results innitrates
the formation
hydrocarbons
peroxyacyl and
by NO2.
of light or hydroxyl
(alkilperoxigyök)
formaldehyde. with to
the acyl radicals
oxygen of which
air. The forms peroxyalkyl
alkylperoxy radicals
ozone.radicals
Theawith oxygen.
hydroxyl radicals
play significant role instarts the process
the oxidation of NOin hydrocarbon
to NO2. polluted air.
 Formation of peroxyacyl nitrates
 Peroxyacyl nitrates concentration depends on:
 Power of acyl radical formation of hydrocarbons

 Ozone concentration

 The rate of nitrogen-dioxide / nitric oxide formation in the

polluted air

Concentration of peroxyacyl nitrates in urban air

1960 years 60 – 65 ppb

Nowadays smaller 10 ppb due to tree way
catalysts in cars
Ozone formation in the troposphere
 Reaction with atomic oxygen
O + O2 = O3 (1)

 The atomic oxygen is served by photolytic dissociation of NO 2

NO2 + hν = NO + O v2 = k2[NO2] (2)

 Ozone may oxidize the nitric oxide to NO2

O3 + NO = NO2 = O2 v3 = k3[O3][NO] (3)

The rate determining step is the photodissociation of NO2.

↓
No ozone formation in the troposphere after sunset,
Concentration maximum in summer at noon.
Decay of PAH compounds in the troposphere

Decay of PAH compounds in the troposphere

 Decay by hydroxyl
radicals

 No reaction with
ozone

 Light helps the decay

 Lifetime: some hours

in the troposphere
especially in sunshine
Elimination of peroxyacyl nitrates from
the troposphere

 Thermal decay by increasing temperature

CH3C(O)OONO2 → CH3C(O)OO• + NO2

 Photochemical decay, longer lifetime during

night
Elimination of ozone from the troposphere

 Strong oxidizing agent => lifetime: some days

 Routes of decay

NO + O3 → NO3• + O
NO + O3 → NO2 + O2
R-CH=CH2 + O3 → RCHO + OH•
O3 + hν → O + O2
 Formation of smog

 The two types of smog: London and Los Angeles

(photochemical)

 LONDON type smog

 Coal fire origin
 In winter
 Early morning
 High humidity
 No sunshine
 Composition: hydrocarbons, soot, sulfur dioxide.
The London smog
 Reasons of London smog
 Emission of pollutants
 Temperature inversion in the troposphere
 During cloudless and windless night → strong infrared
radiation towards the sky
 The surface of soil cools down
 The cool soil cools the air layer above it.
 The upper layers remains warmer
 The vertical mixture is limited
 Quick increase of pollutant concentration
Formation of photochemical smog
(Los Angeles type)
 The main reason is the transportation
 Photochemical smog:
 In summer,
 Mainly at noon,
 Low air humidity,
 Strong sunshine.
 Composition: secondary pollutants (ozone, aldehydes,
NO2, PAN).
 Towns in photochemical smog
1. Peking

Denver Torontó
Smog components in function of time

hydrocarbons

ozone
concentration

aldehydes

hour hour hour hour hour hour hour

Reddish brown dome above the town.

Hydrocarbons, photochemical oxidants, effect on
Plants
 hydrocarbons: no effect
 ozone and peroxyacyl nitrates: toxic

Ozone concentration: summer maximum near the

soil
ozone /
ppb /
Urban 100 – 400

Rural 50 – 120

Tropical forest 20 – 40

Oceans fare from shore 20 -40

Chronic effect above 40 ppb → yellow spots on the

upper side of leaves
Hydrocarbons, photochemical oxidants, effect on

Plants

 Peroxyacyl nitrate :
plant injury shows up
as a glazing and
bronzing of the lower
leaf surfaces

 The resistance depends

on the concentration of
antioxidants in the leaf.
Hydrocarbons, photochemical oxidants, effect on

Humans
 Aliphatic hydrocarbons are not toxic at ambient concentrations.
 Aromatic hydrocarbons are toxic:
 Most dangerous ones :
 benzene
 PAH compounds e.g. benz(a)pyrene
 Photochemical oxidants:
 Eye, throat irritation
 Chronic respiratory disease
 Control of hydrocarbon emission
 Close connection between the hydrocarbon emission and the formation
of photochemical oxidants.
 Control of hydrocarbon emission means control of photocemical oxidants

 Main source: incomplete burning

 Hydrocarbon concentration:
1. Under the lower flammability limit → thermal or catalytic adsorption
2. Over the upper flammability limit → combustion with air and water
 Thermal afterburner I.
 afterburner: auxiliary burner is applied to burn the hydrocarbon content of
the stack gas, temperature 700 – 1000 0C, residence time : 0,5-1 sec.,
efficiency 99%
 regenerative method: alternative streams of a hydrocarbon free and
hydrocarbon polluted fuel gas through a heat storage material.

reganeratív termikus utóégető regeneratív termikus utóthermal

Regenerative égető afterburner
Regenerative thermal afterburner in
use
Thermal afterburner without heat utilization II.

 The hydrocarbon concentration

must be between the lower
and upper flammability limit.

 Used in case of mixed

hydrocarbon, e.g. oil industry

 Water vapor addition to reduce

the soot formation.

C + H2O = CO + H2
 Thermal afterburner III.
1. Recuperative process: the flue gas is reburned, and the heat
content of the purified fuel gas is continuously transferred to the
hydrocarbon contaminated fuel gas.
2. Problem: increase in NO emission

CHx free fuel gas

burner

Heat exchanger

CHx contaminated fuel gas

rekuperatív utóégető
Recuperative afterburner
rekuperatív utóégető
Recuperative afterburner in use
 Catalytic afterburner

 Oxidation at lower temperature (200 – 500 oC),

efficiency ≈ 95%, lower NOx emission
 Not recommended:
 High soot content

 Inorganic particles

 Heavy metals (catalyst poisoning)

 Coal, oil, biomass firing

 Catalytic afterburner
Composition of the exhaust gas from petrol based
automobiles
 Success in cleaning of Gas concentration
exhaust gas petrol hydrocarbons ≈ 750 ppm

based internal Nitrogen oxides ≈ 1050 ppm

combustion engines
Carbon monoxide ≈ 0,68 tf%
(automobiles)
Hydrogen ≈ 0,23 tf%

Carbon dioxide ≈ 13,5 tf%

Oxygen ≈ 0,51 tf%

water ≈ 12,5 tf%

Nitrogen ≈ 72,5 tf%

 Catalytic afterburner
Two way system: oxidation of carbon monoxide and hydrocarbons on Pt catalyst
Three way system: oxidation and reduction of nitrogen monoxide (Pd catalyst)

oxidation

conversion
reduction

Air excess ratio (n)

n = 0,95 – 1,05 air excess ratio acceptable level of the conversion of

(CH)x , CO and NO
 Catalytic afterburner
• requirement: adjustment of air excess ratio.
•lambda meter  measures the oxygen content of the exhaust gas
continuously and regulates the air/fuel ratio.

Adjustment of electronics
air fuel/ ratio
signal receiver

Lambda meter

inert emissions
Engin with
petrol fuel
Harmful emissions

catalyst

compounds
 Catalytic afterburner

 Works at 290 0C – optimum at 400 0C

 Further bonus effect:
 Unleaded fuel
 Reduction of sulfur content of petrol