1. Air Pollution Control Technologies
VOC Incinerators

2. VOCs
Includes pure hydrocarbons and partially oxidized compounds (organic acids, aldehydes, ketones)
There are hunderds of individual compounds with each with its own properties and chracteristics
Combustion processes, various industrial operations and solvent evaporation are the main sources

3. VOC Incineration
Vapor incinerators are also called thermal oxidizers and afterburners
They can be also used successfully for air polluted with small particles of solids or liquids.
Incineration can be used for odor control, to destroy a toxic compound, or to reduce the quantity of photochemically reactive VOCs released to the atmosphere

4. VOC Incineration
VOC vapors might be in a concentrated stream (such as emergency relief gases in a petroleum refinery) or might be a dilute mixture in air ( such as from a paint-drying oven)
In the case of a dilute fume in air two methods are used
Direct thermal incineration
Catalytic oxidation

5. VOC Incineration
In some sources (such as printing presses or parts-painting stations), emissions need to be captured by hoods and a common duct system and routed to a thermal oxidizer (TO)
Total VOC reduction in this case depends on both the destruction efficiency of TO and capture efficiency
Total efficiency will be equal to destruction efficiency times capture efficiency

6. VOC Incineration
The main disadvantage of the VOC incineration is the high fuel cost
Some of the products of combustion of some VOCs are themselves pollutants
When a chlorinated HC is burned HCl and Cl2 will be emitted and then additional control for these pollutants might become neccessary

7. Alternatives to VOC Incineration
Biofilter
Wet scrubber
Recovery of the vapors (recompression, condensation, carbon adsroption or liquid absorption)
If very stringent control objective exists, only incineration can achieve that
e.g. Reduction in concentration from 10,000 ppm to 5 ppm for some malodorous organic sulfur compounds.

8. Oxidation Chemistry
Consider only the case of a premixed dilute stream of a pure HC in air
CxHy + (b)O2+3.76(b)N2xCO2+(y/2)H2O+3.76(b)N2
CxHy the general formula for any HC
b= x+(y/4)
3.76=the number of moles of N2 present in air for every mole of O2

9. Oxidation Chemistry (b)O2+3.76(b)N2xCO2+(y/2)H2O+3.76(b)N2
The actual detailed mechanisms of combustion are complex and do not occur in a single step as might be inferred from above eqn.
The mechanism involves a branching chain reaction and further complicated by the larger number of possible intermediates for higher order HCs.

10. Oxidation Chemistry (b)O2+3.76(b)N2xCO2+(y/2)H2O+3.76(b)N2
The actual detailed mechanisms of combustion are complex and do not occur in a single step as might be inferred from above eqn.
The mechanism involves a branching chain reaction and further complicated by the larger number of possible intermediates for higher order HCs.

11. Major Reactions in CH4 Oxidation
CH4 +O2CH3·+HO2
CH3·+O2CH2O·+OH
CH4+OHCH3 ·+ H2O
CH2O+OHHCO ·+ H2O
CH2+O2HO2 ·+ HCO ·
HCO+O2CO+HO2 ·
HO2+CH4H2O2+CH3 ·
HO2+CH2OH2O2+HCO ·
OH · wall
CH2O · wall
Chain initation
Chain propagation
Chain branching
Chain propagation
Chain termination

12. Developing Global Models
Instead, global models ignores many of the detailed steps and ties the kinetics to the main stable reactants and products
Since CO is a very stable intermediate, the simplest two step model for HC oxidation is:
CxHy+(x/2+y/4)O2xCO+(y/2)H2O 11.2
xCO+(x/2)O2xCO

13. Global Model Kinetics
Using Eqs 11.2 and 11.3 a global kinetic model that is of the first order in each reactant results in the rate equations:
rHC=-k1[HC][ O2]
rCO=xk1[HC][ O2] – k2[CO][ O2] and in the presence of excess O2:
rHC=-k1[HC]
rCO=xk1[HC]– k2[CO]
A third equation for CO2:
rCO2=-k2[CO]

14. Global Model Kinetics
Those 3 equations represent a special case of a general set of consecutive first order irreversible reactions:
ARS
Levenspiel (1962) presented solutions for the concentration of all components as a function of dimensionless reaction time for various k2/k1 ratios. k1 k2

15. The Three T’s Temperature Time Turbulence
For good destruction afterburners should be designed for temperatures C, for residence times of sec, and for flow velocities of ft/sec
Afterburner is now a standart as part of a hazardous waste incinerators requiring %99.99 destruction and removal efficiency of the Principal Organic Hazardous constituents

16. The Three T’s
In mathematical sense 3Ts are related to 3 characteristic times:
tC=1/k Chemical time
tr=V/Q=L/u Residence time
tm=L2/De Mixing time
V: Volume of the reaction zone, m3
Q: Flow rate (at T in the afterburner) , m3/s
L: Length of the reaction zone, m
u: gas velocity, m/s
De: effective (turbulent) diffusion coef. m2/s

17. The Three T’s Peclet number: Pe= Mixing time/residence time
Damkohler number:
Da=Residence time/chemical time
If Pe is large and Da is smallmixing is the rate controlling process in the afterburner
If Pe is small and Da is largechemical kinetics is the rate controlling process

18. Predicting VOC Kinetics
Kinetics are surely important to the proper desing of an afterburner but kinetic data are scarce and difficult and costly to obtain by pilot studies
So past methods of determining the desing or operating temperature of an incinerator were very rough at best

19. Predicting VOC Kinetics 1. Ross’s Approach
Ross (1997) summarized the older methods by suggesting Tdesign be set several hunders degrees (F) above the VOC autoignition temperature
Autoignition T: the temperature at which cobmustible mixtures of the VOC in air will ignite without an external source
Substance
Autoignition T, (F)
Acetone
1000
Acrolein
453
Ethanol
799
Hydrogen Sulfide
500
Cyclohexane
514
Styrene
915
Phenol
1319
Toluene
1026
Excessively high design Ts will result in very high estimated costs for purchasing and operating a VOC incinerator

20. 2. Lee and coworkers’ Approach
A purely statistical model to predict the Ts required to give various levels of destruction in an isothermal plug flow afterburner based on their experimental studies
T99.9= W1+117W2+71.6W3+80.2W W5-20.2W W7+87.1W8-66.8W9+62.8W W11
T99= W W2+67.1W3+72.6W W5-23.4W W7+85.2W8-82.2W9+65.5W W11
T99.9= T for 99.9% destruction efficiency, F
W1=number of carbon atoms
W2= aromatic carbon flag (0=no,1=yes)
W3= C C double bond flag (0=no,1=yes)
W4= number of N atoms
W5= autoignition Temperature, F
W6= number of O atoms
W7= number of S atoms
W8= hydroge/carbon ratio
W9= allyl (2-propenyl) compound flag (0=no,1=yes)
W10= carbon-double-bond-chlorine interaction (0=no,1=yes)
W11= natural log of residence time

21. Predicting VOC Kinetics 3. Cooper, Alley and Overcamp’s Approach
Combined collision theory with empirical data and proposed a method to predict an effective first order rate constant k for HC incineration over the range from 940 to 1140 K.
The method depends on MW and the type of the HC
Once k is found, Tdesign can be obtained
A: pre-exponential factor
Z’: collision rate factor (from Figure 11.5 for alkanes, alkenes, and aromatics)
S=steric factor: to account for the fact that some collisions are not effective in producing reactions becasue of molecular geometry S=16/MW
yO2: mole fraction of O2 in the afterburner
P: absolute pressure, atm
R’: gas constant, L-atm/mol-K

22. Predicting VOC Kinetics 3. Cooper, Alley and Overcamp’s Approach
The activation energy E= (MW) (From figure 11.6)
Now k can be calculated for any desired temperature.
In an isothermal pluf flow reactor (PFR) the HC destruction efficiency, the rate constant and the residence time are related as:

23. Predicting Overall Kinetics
The destruction of VOC occur quickly relative to CO destruction
The kinetics of CO destruction have been studied by many researchers
Howard published the following expression for CO oxidation (valid for the range of K)
Destruction rate of CO =
1.3(10)14e-30,000/RT{O2}1/2 {H2O}1/2{CO}
Where { }indicates concentration in mol/cm3
This equation can be combined with the VOC kinetic.

24. Example 11.1
Estimate the temperature required in an isothermal plug flow incinerator with a residence time of 0.5 sec to give 99.5% destruction of toluene by using 3 methods given.
Method 1.
autoignition T F= = 1326 F

25. Example 11.1 Method 2. Lee et al.
T99.9= (7) (1026) (11.4) ln(0.5)
T99= (1026) (1.14) ln(0.5)
T99.5 can be calculated by taking a linear average:
T99.5=(T99.9+T99)/2=1378 F

26. Example 11.1 Method 3. Cooper et al. First calculate required value k
E= (MW)+46.1
S=16/MW=16/92=0.174
Z’=2.85(10)11
Then calculate A
Now find T

27. Catalytic Oxidation
Catalyst: is an element or a compound that speeds up a reaction without undergoing permananet change itself
Gaseous molecules diffuse to and adsorb onto the surface of the catalyst
After reaction product gases desorb and diffuse back into the bulk gas stream
The detailed mechanisms of the reaction are not known but the reaction proceeds much faster and/or at much lower T

28. Design Considerations for Thermal Oxidizers
The process of a VOC thermal oxidizer involves selection of
Operation T
Residence time
Sizing the device to achieve those with the proper flow velocity
Factors:
O2 content
Type of operation (continous or intermittent)
Concentration of VOCs

29. Design Considerations for Thermal Oxidizers
To minimize the cost, it is desirable to keep the stream to be treated as low as possible
i.e. Not dilute VOC streams with too much air
However most insurance regulations limit the max VOC concentraiton to 25% of the lower explosive limit (LEL) of the VOC

30. LEL and UEL Limits

31. LEL and UEL Limits

32. Design Considerations for Thermal Oxidizers
Organic
LEL (% by volume in air)
Acetone
2.15
Benzene
1.4
Ethane
3.2
Ethanol
3.3
Methane 5
Propane
2.4
Toluene
1.3

33. Design Considerations for Thermal Oxidizers
Material and energy balances are performed to the device to calculate the flow rate of fuel gas required to raise the air T at a given flow rate to the required T.
2 Methods
The traditional approach: assume an isothermal plug flow reactor
The use of computer program to handle the calculations and allows for non-isothermal operation

34. Method 1. Traditional Approach
Material and energy balance:
Burner
Flame mixing chamber
Reactionchamber
Fuel Gas (G)
Burner air (BA)
Polluted air (PA)
Exhaust gas (E)
Mass flow rates (kg/min)
Net heat of combustion Lower heating value kj/kg
Material Balance
Energy Balance
h: Specific enthalpy kj/kg
Xi:Fractional conversion of VOCi

35. Method 1. Traditional Approach
If we assume that enthalpy functions of all streams similar to those for pure air and consider all heat losses (qL)as a simple fraction of the heat input (fL):

36. Method 1. Traditional Approach
Fuel gas is mixed with the outside ambient air in a preset ratio Rb, then MBA=RBMG, also T of burner air equals to T of fuel gas then the equation takes its final form:

37. Example 11.2
Calculate the mass flow rate of CH4 required for an afterburner to treat 2645 acfm of polluted air. It is estimated that the burner will bring in 200 scfm of ouside air. The fuel gas enters at 80 F and the burner air enters at 80 F. The lower heating value (LHV) of CH4 is Btu/lb. Assume 10% overall heat loss and ignore any heat gained by the oxidation of the pollutants.
SOLUTION
From Appendix Table B.2, densities of the inlet PA and BA are and lb/ft3.
MPA = 2465 acfm (0.060 lb/acf)=148 lb/min
MBA = 200 scfm (0.074 lb/acf)=14.8 lb/min
Appendix Table B.7 enthalpies:
hTE= 328 hTBA= 4.8 hTBA= 33.6 hTG= 4.8

38. Example 11.2 MG = 2.53 lb/min SOLUTION
MPA = 2465 acfm (0.060 lb/acf)=148 lb/min
MBA = 200 scfm (0.074 lb/acf)=14.8 lb/min
hTE= 328 hTBA= 4.8 hTBA= 33.6 hTG= 4.8 Btu/lb
fL:0.1
MG = 2.53 lb/min

39. Sizing the Device
To ensure adequate mixing and to approach the condition of plug flow a linear velocity of ft/sec recommended
Usually the residence time sec is enough
For hazardous waste incinerator residence time must be 2 sec or longer
For biomedical waste incinerator residence time must be 1 sec or longer

40. Sizing the Device Length of the reaction chamber (L) is given by
L=utr
The volumetric flow rate (Q)from the ideal gas law:
The diameter of the chamber (D)

41. Example 11.3
Specify the length and the diameter of the afterburner of Example 11.2 given that the design velocity in the main chamber is 15 ft/sec and the desired residence time is 1 sec

42. Solution Length of the reaction chamber L=utr=15(1.0) = 15 ft
ME= =165 lb/min
The volumetric flow rate (Q)from the ideal gas law:
The diameter of the chamber (D)

43. General Approach
Start with equation and 22 for a small slice of the afterburner
Treat each small slice as a CSTR
The fraction combusted depends on T, k and residence time in the CSTR
Assume an inlet T and kinetic model of 11.6 and 11.7 for both VOC and CO
Because of the heat losses and gains Texit and Tinlet are different
Use iterative appraoch to find outlet T and CO and VOC concentrations
Repeat the procedure for all small CSTRs
If the outlet VOC and CO concentrations are not those desired, start with a new assumed inlet T.

44. Design Considerations for Catalytic Oxidizers
Can reduce the required temperatures by hunders of degrees and can save considerable amount of space for equipment as compared with thermal oxidizers
Catalysis is usually a noble metal such as palladium or platinum deposited on an alumina support in a configuration to give miniumum pressure drop
The pressure drop consideration is often cirtical for incinerator design

45. Design Considerations for Catalytic Oxidizers
A honeycomb arrangement typically results in a pressure drop of ” H2O/inch of bed depth
Packed bed of 1/8” diameter pellets ” H2O/inch of bed depth

46. Design Considerations for Catalytic Oxidizers
Catalyst activity refers to the degree to which a chemical reaction rate is increased compared with the same reaction without the catalyst. They can also be very selective. Such activity and selectivity translated into lower operating temperatuerd required for the desired percentage of destruction.

47. Design Considerations for Catalytic Oxidizers
Table 11.4 Some T used for catalytic incineration
Compound
Reported Temperatures, C H2
20, 121 CO
150, 260, 315
n-pentane
310
n-decane
260
benzene
227,302
toluene
230,302
MEK
282,340

48. Basic Design Equation [VOC]L/[VOC]0=e-L/Lm If Re<1000 Then
[VOC]L :concentration of the VOC at length L
[VOC]0= inlet concentration of the VOC
L=length of catalyst bed
Lm=length of one mass transfer unit
If Re<1000 Then
Lm=ud2/17.6D
u: linear velocity in the channel
d=effective diameter of the channel
D=diffusivity, m2/s

49. Basic Design Equation [VOC]L/[VOC]0=e-L/Lm If Re<1000 Then
[VOC]L :concentration of the VOC at length L
[VOC]0= inlet concentration of the VOC
L=length of catalyst bed
Lm=length of one mass transfer unit
If Re<1000 Then
Lm=ud2/17.6D
u: linear velocity in the channel
d=effective diameter of the channel
D=diffusivity, m2/s

50. Basic Design Equation If the flow is turbulent then Lm=2/fa(Sc)2/3
f: Fanning friction factor
a=surface area per unit voluem of bed, m-1
Sc=Schmidt number (m/pD)
The calculated length (usually 2-10” for 99% removal)should be doubled for the safety of the design
Catalyst surface area ft2 per waste gas