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Biochemical Reaction Engineering

(CHE 505) P. A. Ramachandran &M.P. Dudukovic Chemical Reaction Engineering Laboratory (CREL), Washington University, St. Louis, MO

3-17-05

CHAPTER 14 ChE 505: Biochemical Reaction Engineering

Che505_bio.doc

Application Examples Biochemical reactions are encountered in a number of environmentally important processes. Some examples are shown here

1. Secondary treatment of wastewater

Wastewater undergoes first a primary treatment. Here the suspended solids are removed. The wastewater now has colloidal matter and dissolved organic compounds. They are then treated by feeding them to microorganisms which use the dissolved organics as their food and converts the waste to CO 2 and H 2 0. The organism grow and multiply thus converting the dissolved organic to a solid waste (sludge) which can be settled and removed. The water is thus purified. Activated sludge process is a common example. Here the treatment takes place in open tanks with either surface aeration or submerged aeration to provide enough oxygen for the microorganisms. There are many other processes to do this as well, for example, the trickling filter. Nutrients such as N and P are needed for the growth of biomass and these are usually present in the wastewater. In some cases there is excess of nutrient and removal of these may be necessary (see #2 below). In other cases an external supply of nutrient has to be provided.

2. Biological nutrient removal.

In some cases there is excess of nutrient in wastewater and only a part of these may be utilized for biomass growth. The excess nutrient in discharged water has many negative environmental consequences. e.g eutrophication, (excess of nutrients leading to algae growth etc) oxygen depletion leading to fish kill etc. hence. removal of these nutrients may be necessary by additional step or as a simultaneous step during the removal of dissolved organics. The process is known as BNR (biological nutrient removal).

3. Anaerobic treatment of wastewater Under suitable conditions, wastewater can also be treated under anaerobic conditions. In contrast, to aerobic process, the anaerobic process is an energy producing process since the byproduct is methane. The quantity of sludge produced is also smaller. Since the sludge disposal costs are often 50% of the wastewater treatment costs this represents a saving as well. Nutrient loadings are also smaller. The treated effluent has however, a higher concentration of dissolved organic. This can be problematic and some form of post-treatment (usually a aerobic treatment) may be needed before the water can be discharged to surfaces. Thus the process is more suitable for relatively high concentration waste streams. (more than 4kg of COD per cubic meter of water).

4. Soil bioremediation Soil remediation is the removal of contaminants from soil either by convective transport techniques, such as flushing, soil vapor extraction and sparging, and by biological degradation. Bioremediation uses naturally occurring microorganisms to degrade wastes in the soil at the polluted site. Moisture and pH of the soil, availability of oxygen to the microorganisms, temperature and nutrients are important factors in treatment effectiveness. Alkanes, benzene and tetrachloroethene are examples of chemicals that can be degraded by bioremediation.

COD and Yield Coefficient COD is a lumped concept useful to characterize waste water. kg /m 3 is the common unit. For a solution of known composition COD can be calculated by a simple stoichiometry of combustion reaction. Organic compounds usually fit a general formula of C α H β O γ N δ and the combustion reaction can be represented as

C

α

H

O

β γ

N

δ

+ ⎜

α

+

β γ

+

δ

O

CO

+

β

4

2

 

2

α

2

2

H

2

O + δNO

2

The substrate kinetics is established by noting that as the organisms grow, the substrate is utilized. Thus the rate of substrate consumption is directly related to the microbial growth rate by a proportionality constant.

dX =−

1

dS

=− Y

dS

dt

U

dt

dt

Here U is called the specific substrate utilization rate. It is also the reciprocal of Y, the specific yield of organisms. Both U and Y are like stoichiometric factors familiar in reaction engineering. In many cases these can be predicted by setting up a reaction stoichiometry. A general molar representation of biomass is C 5 H 7 NO 2 . Some examples are shown below:

Yield calculations:

Example 1:

Oxygen requirements and Y factor:

Use of reaction stoichiometry to compute Y and COD is illustrated below. Reaction is represented by an overall stoichiometry

v

1

(

organic

) +

v O

2

2

+

v NH

3

3

+

v PO

4

3

4

microorganism

⎯⎯⎯⎯⎯→ (

v

5

new cells

) +

v CO

6

2

+

v

7

H

2

O

Based on this Y and O 2 demand can be calculated. Assume organic is glucose and the biomass has a structure C 5 H 7 NO 2 . A balanced reaction is then

3

C H

6

12

O

6

3(180)

+ 8

O

2

+ 2

NH

3

8(32)

2(17)

2

C H NO

5

7

2(113)

2

+ 8

CO

2

+ 14

H

2

O

Biomass produced = 226 g O 2 consumed = 256 g Glucose consumed = 540 g

O 2 demand = 256/540 = 0.47 g / g glucose

Y per glucose = 226/540 = 0.42 g cells / glucose

Also U = 1/0.42 = 2.38 g glucose consumed to produce 1 g of cell.

It is more convenient to write this in terms of COD (chemical oxygen demand). For this

purpose COD of glucose is calculated as follows:

COD of glucose:

C H

6

180

12

O

6

+ 6 O 6

2

192

CO

2

+ 6

H

2

O

COD = 192/180 = 1.07 g O 2 /g glucose

Y

= 0.42 g cells / g glucose x g glucose / 1.07 COD

= 0.392 g cells / g COD

A second approach is to write half reactions for the various oxidation and reduction

processes and balance the rate of these processes. This method is described below.

Consider again the substrate to be glucose.

Oxidation is the electron donor half reaction, shown by equation (2), with rate Rd.

1

C

H

O +

1

H

O

1

24

6

12

6

4

2

4

CO

2

+ H

+

+ e

(2)

Reduction is the electron acceptor half reaction that has two possible routes; respiration,

equation (3a), and

respectively:

synthesis,

equation ( 3b)

that proceed at the rate Rc,

and

Rs

A.

Respiration

 

1

O

+

H

+

+

1 H

O

4

2

 

e

2 2

B.

Synthesis (in presence of nitrates)

 

1

NO

+

5

CO

+

19

H

+

+

1

C H NO

 

+

11

28

3

22

2

28

 

e

28

5

7

2

28

H

2

O

(3a)

(3b)

,

In the above we have assumed that organic matter (food) is the simple sugar (glucose)

and that the culture in question can utilize the nitrate ion to synthesize new biomass by equation (3b). Now, based on data, we assume that the probability of reaction (3a) occurring is fe while the probability of reaction (3b) occurring is fs. Clearly, since the electron must be used by ether route (3a) or (3b), we must have fe+fs=1. In addition, the rate of electron production must equal the rate of electron consumption so that

Rd

+ fs Rs + feRc = 0

(4)

Now, if based on available information we conclude that fs=0.68, and hence fe=1-0.68=0.28, then substituting these values in equation (4) leads to the overall stoichiometry below.

Overall stoichiometry

0.0221

O

1

24

C H

6

12

6

+

(5)

NO

3

+

0.095

O

2

+

0.0221

H

+

0.0221

C H NO

5

7

2

+

0.14

CO

2

+

0.184

H

2

O

Now, if we know the O2 uptake rate we can determine the nitrate or glucose consumption

rate and rate of synthesis of cell mass! Unfortunately, in most real complex systems we do not know that and we need to rely on empirical yield factors defined earlier.

.

The factors, fe and fs can also be related to the free energy changes associated with the respiration and synthesis reaction. The free energy determines how the released energy is partitioned into respiration vs synthesis. The suggested relation for heterotropic bacteria is

f

e

f

e

G

s

= =−

f

s

1 f

e

k

G

R

G

s = energy required for cell synthesis which is calculated by Eq (1) shown later.

k = fraction of energy captured

G

R = energy released from the oxidation-reduction reactions (from the overall process

of oxidation and respiration)

The value of G

material. This is estimated as

s is free energy to convert 1-electron equivalent of carbon source to cell

G

s

=

G

p

G

N

km

k

+∆ +

G

c

G

p

= free energy to convert 1- electron equivalent of carbon source to pyruvate

intermediate.

m = +1 if

G

p is positive or –1 if energy is produced.

G = free energy to convert 1- electron equivalent of pyruvate to 1- electron equivalent of cells. This is normally taken as +31.41 kJ/e - eq

c

G = free energy per 1- electron equivalent of cells to reduce nitrogen to ammonia.

N

This factor accounts for the fact that a nitrogen source has to be converted to ammonia if N 2 is not available in the form of ammonia. The values of 17.46, 13.6, 15.81 and 0.0 are

used for

respectively. Tables of G values are available for a

number of typical bio-chemical half reactions. The values for some reactions are attached here. An illustrative problem is solved below.

NO

3

,

NO

2

, N

2 and

NH

+

4

Example:

Consider acetate as a substrate and CO2 as the electron acceptor. This represents the treatment under anaerobic condition in the absence of oxygen. Find f e and f s based on free energy considerations. Take the fraction of energy used as 0.6

Solution The oxidation half reaction is represented as

1

CH COO

+

3

H

O

1

CO

+

1

8

3

8

2

8

2

8

HCO

3

+ H

+

+ e

and has a free energy of –27.68 kJ per electron from the tabulated values.

In the absence of O 2 (anaerobic conditions) the CO2 acts as an electron acceptor. The respiration reaction is then represented as

1

CO

+

H

+

+

1

CH

+

1

8

2

e

8

4

4

H

2

O

and the free energy is 24.11 kJ/g. eq. of electrons

Overall free energy change is therefore –27.68+24.11 = -3.57 kJ which is our G R value.

The free energy of pyruvate formation is now calculated. This is reaction 15 in the table.

1

CO

+

1

HCO

+

H

+

+

1

CH COCOO

+

2

5

2

10

3

e

10

3

5

G = 35.78 kJ.

H

2

O

Note that the overall pyruvate formation is the sum of oxidation half reaction and the above pyruvate half reaction. Hence G p = -27.68 + 35.78 = 8.1 kJ which is positive. Energy is utilized in pyruvate formation for this substrate (acetate) and m is taken as 1. Note in a general context that puruvate formation from other substrates such as glucose releases energy and is the first step in the Kreb cycle by which we (all species) use the food energy.

G s = 8.1 / 0.6 + 31.41 + 0 = 44.91 kJ/mole.

f

e

44.91

=

1 f

e

0.6.( 3.57)

= 20.96

solving gives fe = 0.9547 and f s = 0.046 g cell / g COD used.

Tables:

44.91 = 1 − f e 0.6.( 3.57) − = 20.96 solving gives fe = 0.9547

Kinetics of Microbial Reactions The growth of the microbial concentration follows a first order dependence and can be described as:

R x =

dX =µ X dt

where X is the concentration of the micro-organisms and µ is a growth constant and R x is the rate of growth (kinetic model) for biomass.

An early model by Monod (1942) showed that the growth constant is a function of the nutrient or the substrate concentration. The relation can be described by the following equation.

µ µ

=

max

S

K

s +

S

where S is the concentration of the substrate and µ max is a maximum growth constant. The other constant in the model is K s . In fact, it can be shown that if S = K s /2 the growth rate is half the maximum value. Hence K s is also called the half velocity constant. The Monod’s equation applies to pure cultures but is also applied to mixed cultures as a first approximation.

Other models for the growth constant µ have also been proposed. Thus Haldane proposed the following model

µ=µ

max

S

K

s

+

S

+

S

2

K

I

where K I is often referred to as the substrate inhibition constant.

In a dynamic growth situation, some organisms are born, some die and some members simply grow in mass. The death rate is added to the model by adding a decay constant and the net growth rate of microbes is represented as:

R

x

=

X

µ

k

d

X

=

µ

max

S

X

K

s

+

S

k

d X

Although the model is simple (a lumped model for microbes), it has served its purpose well in many applications. However, more complete models that incorporate some of the

underlying biochemical mechanisms offer a better representation and predictability. Such models are based on metabolic pathway analysis. Such detailed models are often developed if there are certain design objectives in mind. Otherwise a simple Monod based model is often sufficient.

Typical values of following range:

kinetic parameters for domestic wastewater at 20degC are in the

µ max

K s .

Y

Kd

2-10 g bsCOD/g VSS. Day 10-60 mg/L bsCOD 0.3-0.6 mg VSs/mg bsCOD 0.06-0.15 gVSS/ g VSS day

Here bsCOD refers to biodegradable soluble chemical oxygen demand. VSS refers to volatile suspended solids which is commonly used as a measure of biomass concentration since this is an easily measurable quantity, Materials that can be volatilized and burned off when ignited at 500 +or- 49 deg C are classified as volatile

The effect of temperature on the kinetic parameters is of some interest. The growth constant µ max increases with temperature and reaches a maximum and then decreases rapidly with temperature. This is often fitted by two Arrhenius type of parameters:

The Monod constant is an inverse function of temperature and is fitted as:

1

exp ⎛− ⎜ E

K s

RT

= A

1

The yield constant is assumed to be independent of temperature.

Other effects such as product poisoning may have to be added to the model. One example is alcohol production by fermentation where higher concentrations of alcohol act as poison to the microbial population.

Detailed kinetic models

In this model one attempts to track the key species involved in the process rather than lumping all the species into COD.

Metabolic Pathway Models As an example of metabolic pathway analysis, the growth metabolism model for E. coli was developed by Schuler and co-workers. This model shown schematically in Fig. 2 has 23 stoichiometric constants and 49 kinetic parameters. Most of the kinetic parameters could be estimated from the large number of reported previous studies on the system.

Process Model for Activated Sludge Process The typical flow diagram can be represented as follows:

Primary effluent Effluent Q 0 -Q w , X e , S Q 0 ,
Primary effluent
Effluent
Q 0 -Q w , X e , S
Q 0 , S 0 , X 0
Q 0 + Q R
X,S
secondary
V,X,S
clarifier
reactor
Q R , sludge return
X
sludge
Q u ,X u
underflow
u
Sludge
Q w , X u
waste
Control volume/mass boundary
(a)
Primary effluent Effluent Q 0 -Q w , X e , S Q 0 ,
Primary effluent
Effluent
Q 0 -Q w , X e , S
Q 0 , S 0 , X 0
Reactor
Variable
Q+ Q R
X,S
secondary
clarifier
X, S
Q R , sludge return
X
sludge
Q u ,X u
underflow
u
Sludge
waste
Q w , X u
Control volume/mass boundary
(b)

Figure: Schematics of the two general types of activated sludge systems: (a) completely mixed; (b) plug flow

Model is developed by writing mass balances for the substrate and the biomass. The model equations for a backmixed reactor are as follows:

Cell Balance:

Produced – Died = -In + Out

µ

max

S

K

s

+

S

XV

k XV

d

=−

Q

0

X

0

+

[(

Q

0

Q

which can be rearranged as

µ

max

S Q

w

X

u

+

(

Q

0

Q

w

)

X

e

Q X

0

0

=

K

s

+

S

VX

w

)

X

+ k

d

e

+

Q

w

X

u

]

(7.16)

(7.17)

The same mathematical operations may be applied to the substrate. These will not be repeated but the result will be written at once, which is

µ

max

S

(

Y K

s +

S

) XV

= {(

Q S

0

0

+

(Q

0

Q

w

)S

+ Q S)

w

}

Eq. (7.18) may be manipulated to produce

(7.18)

µ

max

S

Q Y

0

=

K

s

+

S

VX

(S

0

S

)

(7.19)

Equating the right hand sides of Eqns (7-17) and (7-19) and rearranging gives us

Q

w

X

u

+

(

Q

0

Q

w

)

X

e

Q X

0

0

=

Q Y

0

(

 

VX

 

VX

 
 

θ =

 

VX

 

c

Q

w

X

u

+

(

Q

0

Q

w

)

X

e

Q

0

X

0

The ratio,

S

0

S

)

k

d

(7.20)

, is the biomass (or mixed-liquor volatile

suspended solids, MLVSS-the numerator) in the reactor divided by the net rate of biomass wasting (the denominator). The ratio θ represents the average time that the

c

biomass is in the residence in the reactor. It is called by various names, such as mean cell residence time (MCRT), sludge retention time (SRT), and sludge age. The ratio

=θ

V / Q is called the nominal hydraulic retention time (NHRT). The word nominal is

0

used here, since θ is not the actual detention time of the tank. The actual detention time

is

solving for X gives:

R is the recirculated flow. Using θ and θ in Eq. (7-20) and

V

/

(

Q

0

+ Q

R

) where Q

c

X =

θ

c

Y

(

S

0

S

)

(

θ

1

+ k

d

θ

c

)

(7.21)

This is known as the equation for biomass concentration in the reactor. To find S, the exit concentration of the substrate, we substitute Eq. (7.21) for X in Eq. (7.19), this leads to

S

1+

k

d

θ

c

=

K

s

+

S

µ θ

max

c

Rearranging:

S =

K

s

(1

+

k

d

θ

c

)

µ θ

max

c

(1

+ k

d

θ

c

)

(1)

The above equation then provides the performance of the bioreactor as a function of

operating conditions.

(the cell

residence time). The other parameters K s , µ max and k d are biological rate parameters which we cannot control.

The key parameters which the operator can adjust is θ

c

An interesting effect is that the exit concentration in the bioreactor is independent of the inlet concentration. This is unlike a conventional chemical reactor.

θ is sometimes referred to as BSRT or biomass solid retention time. The reactor performance depends on θ (See Eq. 7.21). The concentration of cells in the bioreactor however depends on both θ and θ.

c

c

c

A minimum residence time is required and this is related to the inlet substrate

concentration. This quantity can be obtained by setting X = 0 in Eq (7.21). This would

be yield at S = S 0 . Now, using Eq(1) for S and solving, one obtains

θ

c

>

1

µ max

1 +

⎜ ⎝

⎟ ⎞

⎟ ⎠

K s

S 0

assuming k d = 0 here.

θ c,min K + S s 0 = S 0 µ max S S 0
θ c,min
K
+
S
s
0
=
S 0
µ max
S
S 0

θ

c ,min

or

Eq. (1) holds only if the above condition is satisfied. A plot of S vs θ

c

θ c minimum
θ
c
minimum

Cell concentration profiles are as follows:

X

c θ c minimum Cell concentration profil es are as follows: X Low θ case High

Low θ case

High θ case

min

θ

c

is as follows:

Another important parameter in the design and operation of an activated sludge plant is

the recirculation ratio,

Also at

steady state

around the secondary clarifier.

0 . R may be obtained by performing a material balance

R

=

Q

R

/Q

Since the clarifier is not aerated, dX/dt = 0.

X

t

= 0

. Adopting these facts and performing the material balance produces

(

Q

0

+ Q

R

)

X =

(

Q

0

Q

R

)

X

e

(

+ Q + Q

R

w

)X

u

(7.24)

Solving for the ratio gives:

Q

R

Q

0

(

X

X

e

)

Q

w

(

X

u

X

e

)

=

R

=

Q

0 Q

0

(

X

u

X

)

(7.25)

Trickling Bed System:

A schematic diagram is shown in the next page. Often a first order kinetic model is used

for simplicity.

ln

S

k

'

A

s

=

S

0

Q

a

k’ = rate constant = k X f

X f = microbial concentration in the film A s = surface area for diffusion into biomass Q a = volumetric flow rate

Other detailed models based on Monod’s kinetics can also be derived.

BIOLOGICAL REACTIONS AND BIOREACTORS: FERMENTATIONS

(CHE 471) M.P. Dudukovic Chemical Reaction Engineering Laboratory (CREL), Washington University, St. Louis, MO

BIOLOGICAL REACTIONS AND BIOREACTORS: FERMENTATIONS

Biological reactions are more complex than anything that we have considered so far and the reasons for this are briefly outlined below. Consider a “generic” biological reaction where some organic matter (food) is consumed by a culture of living organisms (bugs) that also consume oxygen due to their respiration (aerobic culture) and in the process generate carbon dioxide, water and more biomass (more bugs). This is represented by equation (1):

Organic matter + O 2 + bugs CO 2 + H 2 O + more bugs

(1)

This process involves oxidation, respiration and synthesis ( of new biomass).

Oxidation is the electron donor half reaction, shown by equation (2), with rate R d .

1

24

C 6 H 12 O 6 +

1

4

1

H 2 O 4 CO 2 + H + + e ;

R d

(2)

Reduction is the electron acceptor half reaction that has two possible routes: respiration, equation (3a), and synthesis, equation (3b), that proceed at the rate R c and R s , respectively.

A. Respiration

1

1

4 O 2 + H + + e 2 H 2 O ;

R

c

B. Synthesis (in presence of nitrates)

1

28

NO 3 + 22 CO 2 + 19

5

1

11

28 H + + e 28 C 5 H 7 NO 2 + 28 H 2 O ;

 

(3a)

R s

(3b)

In the above we have assumed that organic matter (food) is the simple sugar (glucose) and that the culture in question can utilize the nitrate ion to synthesize new biomass by equation (3b). Now, based on data, we assume that the probability of reaction (3a) occurring is f c while the probability of reaction (3b) occurring is f s . Clearly, since the electron must be used by either route (3a) or (3b), we must have f c + f s = 1. In addition, the rate of electron production must equal the rate of electron consumption so that

R d + f s R s + f c R c = 0

(4)

Now, if based on available information we conclude that f s = 0.62, and hence f c = 1- 062=0.38, then substituting these values in equation (4) leads to the overall stoichiometry below.

1

Overall stoichiometry

1

24 C 6 H 12 O 6 + 0.0221 NO 3 + 0.095 O 2 + 0.0221 H +

0.0221 C 5 H 7 NO 2 + 0.14 CO 2 + 0.184

H 2 O

(5)

Now, if we know the O 2 uptake rate we can determine the nitrate or glucose consumption rate and rate of synthesis of cell mass! Unfortunately, in most real complex systems we do not know that and we need to rely on empirical yield factors which will be defined below.

We need now to describe the rate of biomass (bugs) growth, substrate (food, e.g. sugar) consumption rate and oxygen consumption rate.

Biomass Growth Rate

Typically, Monod’s model is used where the rate of formation of the biomass, R x , is proportional to the biomass concentration present in the system, X, as shown by equation

(6)

R x = μX

(6)

The specific growth constant is given by Michaelis Menten kinetic form and depends on the limiting substrate concentration, S, as shown below.

μ

=

μ m S

K s +

S

(7)

The above ignores the death term in the cell rate which has to be included for mature cultures, so that a more complete description of the net biomass formation rate is:

R x = μ m SX

K s +

S k d X

Substrate Consumption Rate

(8)

The substrate consumption rate is customarily given in terms of the biomass production rate and the appropriate yield coefficient. Please, note that the yield coefficient may change with conditions but is most frequently used as constant:

R s =

1

Y x / s

R x

2

(9)

Y x / s = yield coefficient =

Oxygen Consumption Rate

( mg / L ) biomass produced

( mg / L ) substrate consumed

(10)

This rate must also be expressed in terms of an empirical yield coefficient as shown below:

R o =

1

Y x / o

R x

Y x / o = ( mg / L )

biomass produced

( mg / L ) oxygen consumed

(11)

(12)

Balance on well mixed compartment (CSTR at transient conditions)

Well mixed CSTR at unsteady state can now be described by writing the mass balance on biomass, substrate and oxygen as follows:

V

dX

dt

= Q( X o X ) + R x V

t

= 0 X = X i

V

dS

dt

= Q( S o S ) (R s )V

t = 0 S = S i

V

dC o

dt

=

*

Q( C o s C o ) + k s aV ( C o C o ) (R o )V

t = 0 C = C

o

oi

Let dilution rate

D

= Q

V

(13)

(14)

(15)

(16)

Then, rewriting equation (13) to (15) above yields:

3

dX

dt

dS

dt

dC

o

dt

=

D( X o X ) + μ m S S X K s +

1

μ m S

= D( S o S )

Y x / s

K s +

1

S X

μ m S

= D( C o s C o )

Y x / o

K s +

S

In a batch D = 0.

 

(17)

(18)

*

X + k L a( C o C o )

(19)

In steady state CSTR

d

dt = 0. Let us look at a steady state CSTR.

In steady state CSTR with no fresh culture in the feed stream ,X 0 = 0, so that

D = μ

D

= μ m S S Solve for S K s +

S

= K s D D

μ m

for D < D cr

(20)

(21)

(22)

In case that the dilution rate is larger than the critical dilution rate given below, washout occurs and only the steady state at zero biomass concentration is possible.

D

> D cr = μ m S o X = 0 K s + S o

(23)

For admissible values of the dilution rate D the biomass steady state concentration in the effluent (and hence in the reactor due to CSTR assumptions) is given by

X

= X ss = Y x / s ( S o S ) = Y x / s S o K s D

μ m D

(24)

The production rate of the biomass per unit reactor volume is the product DX

To maximize it we need

d

dD ( DX ) = 0 which yields :

4

⎡ K s 1/ 2 ⎛ ⎞ ⎤ ⎥ ⎜ ⎟ ⎣ K s +
K s
1/ 2
⎣ K s + S o
⎢ 1−
(25)
D opt = μ m
⎥ ⎦
⎢ ⎛
⎞ −1/ 2
⎞ ⎤
K s
S o + K s 1−
X opt = Y x / s
K s + S o
⎣ ⎢
⎠ ⎠ ⎦ ⎥
(26)
See diagram below:
S
S
X
DX
DX
D
D cr
D opt

5

Electrochemical Processes

(CHE 505) M.P. Dudukovic Chemical Reaction Engineering Laboratory (CREL), Washington University, St. Louis, MO

Chapter 16 Electrochemical Processes

Electro_chapter16.doc

3-31-05

This chapter considers some applications of electrochemical transport and reactions in environmental engineering. First we review some application examples. Then we provide a review of electrochemical thermodynamics and kinetics of electrode processes. These concepts are useful for design of electrochemical systems for waste treatment. The transport in electrolytic solutions is then discussed followed by application to membrane processes assisted by an electric field (electrodialysis).

The educational outcome of this chapter is as follows:

To indicate application areas where the use of an electric potential is beneficiary

To understand the minimum voltage (Faraday’s law, Nernst equation) and the concept of voltage balance

To understand the kinetics of electrode processes in terms of current-voltage relations (Butler-Volmer equations)

To understand transport in charged membranes.

To do preliminary design of electrochemical reactors.

Application Areas

1. Metal salts recovery from waste water and other process streams Metal salts are frequently found in wastewater. These can be electrochemically processed to recover the metals. Thus we not only treat the waste streams but also generate value from waste.

Potential for metal recovery and some statistical data is shown in the book by Allen and Rosselot. From their data it is seen that the metals in many waste streams are significantly underutilized. Thus there is considerable scope of process development and optimum design in this area.

2. Treatment of organic pollutants Some pollutants such as phenol, aromatic amines, halogenated nitroderivatives can be oxidized to CO 2 and water using electrochemical routes

3. Electric field assisted membrane separations (Electrodialysis) In this process one uses semipermeable ion selective membranes to separate ionic components of the solution. An electric field is applied across the system to facilitate the transport of the ions across the selective membranes. Details of the process and design aspects are considered in a later section.

Additional examples are discussed in the ‘Environmental Electochemistry’ book by K. Rajeshwar.

Thermodynamics

Consider a reaction A +B C+D. From thermodynamics if the free energy change is negative the reaction is spontaneous and energy can be recovered from the reaction. The energy is usually released as heat, for example, combustion reaction of fuels such as hydrogen but can also be released as electrical energy if the reaction is carried out electrochemically as pair of oxidation and reduction reactions at the anode and cathode respectively. The cell potential under idealized condition is related to the standard free energy change of the reaction as:

E

0

cell =

nF G

0

n is the number of electrons transferred and F is the Faradays’ constant = 96500 C/ g-eq and represents the charge to be supplied for 1 g- eq of electron of transported in the external circuit.

If the reaction has a positive change in free energy then the reaction is not spontaneous and needs energy input to carry out the reaction. Again if the reaction is carried out as an electrochemical reaction, the energy can be supplied in form of electrical potential. The minimum energy needed to be supplied is related to the free energy change in the reaction. This value defined here as the decomposition potential or the reaction potential given as:

E

0

r

=

E

0

d

=

nF G

0

where G 0 is the free energy change on the overall reaction under standard conditions.

Note that

E

0

r

=− E

0

cell

Thus if E

vice versa (an electrolyzer or electrochemical reactor).

0

r

is negative, the reaction will yield energy (a galvanic cell ot fuel cell) and

The decomposition potential is more usually calculated by writing the overall reaction as

a sum of oxidation and reduction reaction separately. These are called as half reactions. For example consider the electrolysis of silver nitrate which can be represented by the following reaction:

2 AgNO + H O 2 Ag + 2 H

3

2

+

+

2 NO

3

+ 1/ 2O

2

or more simple since the species are ionized as:

2 Ag + + H 2 0 2 Ag + 2 H + + ½ O 2

This can be represented as two half reactions.

Oxygen production at the anode (Oxidation reaction)

H 2 0 2 H + + 2e - +

½O 2

(i)

Silver formation at the cathode (reduction reaction)

Ag + + e - Ag

(ii)

The potential values for a number of common reactions are tabulated in electrochemistry books. Tables 1 and 2 reproduce some of these values. Note that these values have the same sign as the overall free energy change of the reaction and hence represent the reaction potentials and not the cell potential. Thus if the value is negative it means that the corresponding half reaction has a negative free energy change and is therefore spontaneous. The standard conditions are defined as 1M concentrations for liquid phase components and 1 atm pressure for gas phase species.

The overall potential is then calculated as:

E = E

anode

E

cathode

where both the anode and cathode reaction are written as oxidation reactions. The overall reaction is therefore the difference between the anode reaction and cathode reaction. The actual cathode reaction is the reduction and proceeds in the opposite direction to those shown in the tables. However, both reactions are written as oxidation for the purpose of using these tables and the difference is the net reaction.

Example 1 : Find the minimum potential needs to decompose AgNO 3 form a 1M

Example 1: Find the minimum potential needs to decompose AgNO 3 form a 1M solution

The oxidation reaction is decomposition of water at the anode. From table 1, we find that this reaction has potential change of 1.229V associated with it. (Reaction 15)

The oxidation of silver has a potential of 0.7991V. (Reaction 15 in Table 2)

The overall potential change is:

E

r

= E

anode

E

cathode

= 1.229 -0.799 = 0.43V

which is the minimum potential that needs to be applied to carry out the reaction.

Example 2: Consider the hydrogen-oxygen fuel cell. We can represent the two half reactions (both as oxidation) in the following manner.

Anode: Oxidation of hydrogen (Reaction 4 of Table 1)

H 2 2 H + + 2e -

(E = 0 by convention)

Cathode Oxidation of water (reaction i above) E= 1.229V

E

r

= E

anode

E

cathode

= 0-1.229= -1.229V

E cell (= - E r) therefore +1.229V a positive value here showing that reaction is spontaneous. The reaction generates energy of 1.229V as a fuel cell under these conditions An illustration of a PEM (proton exchange membrane as the porous separator) based fuel cell is schematically shown in Figure 1.

Schematic of a fuel cell

Current flow from cathode to anodeschema tically shown in Figure 1. Schematic of a fuel cell Electrons move thr ough external

Electrons move through external circuit ough external circuit

+ + H 2 H H - + O 2 H 2 O Anode Porous
+
+
H 2
H
H
-
+
O
2
H
2 O
Anode
Porous
Cathode
separator

O 2

2H 2 4H + + 4e -

O 2 +4H + +4e - 2H 2 O

If the reactants are not at the standard conditions, a correction for activity is applied as shown below.

The free energy change of reaction is

0

∆ =∆ +

G

G

a

RT ln

p

a

r

where a p is the product of activities of all products raised to its stoichiometric number in accordance with law of mass action. Similarly a r is the activity of the reactants. Dividing by nF and converting in terms of reaction potential we obtain

E

r

=

E

0

r

+

RT

a

ln

p

nF

a

r

This equation is referred to as the Nernst equation.

The effect of temperature in the reaction equilibrium can be calculated in a similar manner. A linear equation is often used:

E T

(

) =

E

0

+

(

T

T

ref

)

E

0

T

From thermodynamics, it can be shown that

where

E 0

S

0

=

T

nF

S

0 is the entropy change for the reaction.

Example 3: A hydrogen fuel cell is operated at 80C. Find the maximum potential generated in this cell.

Solution:

For the H 2 +O 2 reaction, the entropy change was found to be

Hence

E(80C) = -1.23+ 8.49x10 -4 (80-25) = -1.18 V

S

0 / nF = 8.49 x 10 -4 V/K

S

0 =0.1638 J/K mole.

Example 4: Conditions with cobalt deposition. Cobalt is to be recovered from a solution of cobalt sulfate at a concentration of 0.005M. Find the reaction potential and also find the potential for the competing reaction of hydrogen evolution at the cathode if the pH of the solution is 1. The standard potential for oxidation of cobalt is 0.277 V.

Solution:

The Nernst equation is applied to the Co oxidation. n=2 here.

E

=

E

0

+

RT

2 F

ln C

Co

=0.2089V

The oxidation of water is the anodic reaction. E = 1.229V Hence, the voltage required for Co deposition is 1.02V.

For hydrogen oxidation, the standard reaction potential can be corrected for pH as follows:

E H

2

= +

0

RT

2 F

ln

(

H

+

) 2

where H + =10 -pH

For a pH of 1, the value is –0.0592.

Hence,

E H

2 =

RT

F

(

2.303

)( pH )

=0.052 x 2.303 = 1.1698 V

The reaction potential for hydrogen evolution is 1.17 V which is comparable to that for Co deposition. Hence both reactions are likely to occur at this pH. From an application point of view, a relatively high pH is needed for the Co deposition to become the favored reaction. Thus if the wastewater is acidic then Co recovery is difficult by electrochemical process.

Voltage Balance This is similar to the heat balance in chemical reactors. The overall voltage needed can be expressed as

where

V

T

E r

η

η

A

C

= +η +−η +

r

A

C

E

(

)

IR ( solution ) IR (membrane ) IR ( metal )

+

+

= decomposition voltage predicted from thermodynamics

= anode overpotential = Ea in figure

=cathode overpotential = Ec in figure

IR=voltage drop due to a resistance in the solution and metal.

IR drop in the metal is low in general but can not be ignored of cells that are connected in series.

The components of the above voltage balance are all functions of the current density

except of course the term

current density is lower the voltage drop, but the reaction rate is also correspondingly lower. To quantify the overpotential-current relations, the reaction kinetics is needed as discussed in the next section.

which is determined by thermodynamics. Lower the

E

r

the reaction kinetics is needed as discussed in the next section. which is determined by thermodynamics.

Kinetics of electrode processes

The rate of electrochemical reactions are often expressed in terms of current density rather than in terms of the moles produced per unit time per unit area of the electrode surface. We define the current density as i which is A/m 2 s. The total current at the cathode is the same as the current at the anode. The current density is related to the rate of reaction by the following equation which is a consequence of Faraday’s law. i = n F r where r is the rate of reaction in moles produced/m 2 s

To provide an expression for the rate, r or the equivalent current density consider an electrode reaction represented as a reversible reaction of the type:

R O

+ n

+ ne

where R and O represent the reduced and oxidized species and n is the number of electrons transferred.

The rate is affected by the potential difference between the metal and the adjacent

solution. Let E represent this value.

Then the rate of forward reaction (oxidation) is increased by increasing the value of E, i.e. by having a higher potential at the metal compared to the solution). Similarly, the rate of backward reaction is improved by decreasing E. The effect of potential difference on the rate is thus equivalent to the effect of temperature and the rate is found to depend exponentially on the value of E. The rate is also dependent on the concentration of the species. For as simple elementary reaction the dependency is linear. Combining the effect of both concentration and temperature we can write the rate as:

E =φ φ .

m

s

The rate of forward reaction is therefore proportional to k C

f

R exp (nf β

E )

(

while the rate of backward reaction is proportional to k C O exp

b

nf (

1 β

)E )

where β is a factor between 0 and 1 that represents the efficiency of activation due to electric potential. The factor f represents F/R T which is a factor similar to that in the Arrhenius equation for the effect of rate on temperature.

Net rate is therefore equal to k C

f

R exp (nf β

E )

-

(

k C O exp

b

nf

(

1 β

)E )

.

The rate constants k f and k b are, however, not independent and must meet the thermodynamic consistency. At equilibrium the rate is zero. Also C R and C O are related by Nernst equation which is expressed now in the following rearranged form

C

o

C R

=

[

(

exp nf E

r

0

E

r

)]

Setting the net rate as zero and also using the C R and C 0 values from the above version of the Nernst equation, we can drive the following thermodynamic relation between the forward and backward rate constants.

k

= k

b f

exp

(

nfE

0

r

)

where

students may wish to verify the algebra for clarity).

E

0

r

is the equilibrium potential for the reaction at the standard conditions.

(The

The rate constant k f is often expressed in terms of a rate constant k 0 defined below which is also called as a standard rate constant.

k

f

= k

0

exp

Similarly,

k

b

= k

f

exp

(

nfβE

0

r

)

(

nfE

0

r

)

= k

0

exp

(

nf β E

1

(

)

0

r

)

Substituting and rearranging, the rate can be expressed as

(

r

)

=

k C exp nf

0

R

(

[

β

E

(

E

0

)])

C exp

0

[

(

nf 1

)(

β

E

E

0

)]

Expressing in terms of current, we have

i

=

nFk C exp nf

0

R

(

[

β

E

(

E

0

)])

C exp

0

[

(

nf 1

)(

β

E

E

0

)]

(A)

(B)

Note that if k 0 and β are the two kinetic parameters in this ‘rate’ form.

This provides a working model to represent the kinetics of electrode processes. However, it is more common in the field to express the rate in terms of an overpotential at the electrode surface. That is referred to as the difference between the actual applied potential and the equilibrium potential as η, the surface overpotential

η= E E = E E

eq

r

(C)

If η is greater than zero, the driving force term is positive and hence oxidation is favored. If η is less than zero, the driving force term is negative and hence the reverse reaction (reduction) is favored. If η is zero the system is at equilibrium and the net rate is zero.

Although the net rate is zero at equilibrium, we may consider the rate to be balance of the

forward and backward reaction. can write

. From Eq(A), we

r = r r

f

b

and at equilibrium

r

f

= r

b

*

f

r

=

*

r

b

=

k C exp nf ( E

0

R

[

*

(

β

r

E

0

)]

The corresponding current is referred to as the exchange current.

i

0

= nFr = nFr

f

b

*

*

We use this expression in (B) and also express E in terms of the overall potential.

Hence the current can be expressed as a function of overpotential as: