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Solution:
Electron donor: acetate
Electron acceptor: oxygen
Nitrogen source: ammonium
This is the energy available to the cell for synthesis of new cell mass. Now compute for energy
requirement for cellular synthesis and equate it to the energy available. Thus:
Energy required for cell synthesis = Go’c + Go’P + Go’N
Energy balance:
fso*Go’s = feo*Go’R
G o'P G o'N
energy/electron to synthesis fe o G o'C m
k k
A o
energy/electron to energy reaction fs - kG o'r
For anaerobic digestion, the electron acceptor is usually CO2; the bacteria involved are
autotrophs (carbon source is CO2)
Go’a = -5.763 kcal/e- eq for CO2 as electron acceptor; all other values remain the same except for
Go’CS
Go’R = energy released from oxidation of donor and transferred to e- acceptor
=- k(Go’d - Go’a)
= -0.6 (-6.609-5.763)
= 7.42 kcal/e- eq
A= 9.166/7.42
A= 1.235
fs o 0.44; fe o 0.56
Sludge produced: (1/20 * 0.44)/0.125 = 0.176 moles per mol acetate. Compared to aerobic process where the
sludge produced is 0.252 moles per mol acetate, the sludge produced in anaerobic processes is smaller.
In anaerobic reactions, less sludge is produced because the cell is able to derive less energy (Go’R) from the donor
when CO2 is the electron acceptor. More energy is derived if oxygen is the electron acceptor compared to CO 2.
Problem 2. You are hired as an expensive consultant by an industry to explore options of treatment of their
wastewater, which has high nitrate levels and a low level of organic compounds. After some preliminary analyses,
you decide to suggest biological treatment. Your challenge now is to find an appropriate electron donor for
denitrification. You decide to do some calculations based on the stoichiometric approach of McCarty.
a. You are considering methanol, acetic acid, ethanol, glucose and hydrogen as potential electron donors. You
decide to set up a spreadsheet to calculate fs and fe for each electron donor. You can assume that you will
operate the wastewater treatment system that needs to be designed at a solids retention time of 10 days, that
the fraction of biomass that is not biodegradable is 0.2, and that the first order decay coefficient is 0.04 day -1.
You can further assume that the waste stream contains only nitrate (thus, no ammonium is present as the
nitrogen source).
b. For each electron donor, write the balanced reaction normalized to one mole of electron donor.
c. For each electron donor, list the mass of electron donor (mg) that needs to be provided to reduce 1 mg of NO 3-
1
-N.
d. For each electron donor, list the biomass (mg) that will be produced to reduce 1 mg of NO 3-1-N.
f. You also have information available from literature on the mass of electron donor needed and the mass of cells
produced for denitrification (only for methanol, acetic acid, and ethanol). The information, which is based on
several experimental studies that used a variety of treatment systems to accomplish denitrification from wastewater
and drinking water as summarized in Table 2. Compare your answers from parts c and d with the data in Table 2
and list a number of factors that might explain the difference.
Table 1
Electron Donor Cost ($/kg)
Methanol 0.52
Acetic Acid 0.78
Ethanol 0.923
Glucose 0.316
Hydrogen 1.402
Table 2
Electron Donor mg electron donor/mg NO-13-N mg biomass/mg NO-13-N
Methanol 3.37 1.17
Acetic Acid 4.87 1.52
Ethanol 1.76 0.57
Solution:
Given: wastewater with high nitrate (NO3-) levels and low organic compound levels
Required: appropriate donor for denitrification (methanol, acetic acid, ethanol, glucose, and
hydrogen)
G 01p G 01N
f eo G 01 G 01
c + +
A = o = s
= km k
fs G 01R - kG 01r
1
f so = f eo 1 - f so
1 + A
1 + f d bc
f s = f so fe = 1 - fs
1 + bc
m = -1 m = 1 m = 1 m = -1 m =1
fso = 1/(1+A) fso = 1/(1+A) fso = 1/(1+A) fso = 1/(1+A) fso = 1/(1+A)
= 1/(1 + 0.9004) = 1/(1 + 1.2341) = 1/(1 + 1.0746) = 1/(1 + 0.8280) = 1/(1 + 3.7140)
= 0.5209 = 0.4476 = 0.4820 = 0.5470 = 0.2121
fe = 1 - fs fe = 1 - fs fe = 1 - fs fe = 1 - fs fe = 1 - fs
= 1 - 0.4059 = 1 - 0.3453 = 1 - 0.3718 = 1 - 0.4220 = 1 - 0.1636
= 0.5981 = 0.6547 = 0.6282 = 0.5780 = 0.8364
methanol
Rd 1/6 CH3OH + 1/6 H2O 1/6 CO2 + H+ + e-
-feRa -(0.5981) (1/10 N2 + 3/5 H2O 1/5 NO3- + 6/5 H+ + e-)
-fsRc -(0.4019) (1/28 C5H7O2N + 11/28 H2O 1/28 NO3- + 5/28 CO2 + 29/28 H+ + e-)
acetic acid
ethanol
Rd 1/12 CH3CH2OH + 1/4 H2O 1/5 CO2 + H+ + e-
-feRa -(0.6282) (1/10 N2 + 3/5 H2O 1/5 NO3- + 6/5 H+ + e-)
-fsRc -(0.3718) (1/28 C5H7O2N + 11/28 H2O 1/28 NO3- + 5/28 CO2 + 29/28 H+ + e-)
glucose
Rd 1/4 CH2O + 1/4 H2O 1/4 CO2 + H+ + e-
-feRa -(0.5780) (1/10 N2 + 3/5 H2O 1/5 NO3- + 6/5 H+ + e-)
-fsRc -(0.4220) (1/28 C5H7O2N + 11/28 H2O 1/28 NO3- + 5/28 CO2 + 29/28 H+ + e-)
hydrogen
Rd 1/2 H2 H+ + e-
-feRa -(0.8364) (1/10 N2 + 3/5 H2O 1/5 NO3- + 6/5 H+ + e-)
-fsRc -(0.1636) (1/28 C5H7O2N + 11/28 H2O 1/28 NO3- + 5/28 CO2 + 29/28 H+ + e-)
1 mmol CH 3 OH 32 mg CH 3 OH
methanol = 0.0714 mmol NO -3 - N = 2.8574 mg
-
0.7996 mmol NO 3 - N 1 mmol CH 3 OH
____________________________________________________________________________________________
1 mmol CH 3 CH 2 OH 46 mg CH 3 CH 2 OH
ethanol = 0.0714 mmol NO -3 - N = 1.9697 mg
16675
. mmol NO -
3 - N 1 mmol CH 3 CH 2 OH
____________________________________________________________________________________________
1 mmol CH 2 O 30 mg CH 2 O
glucose = - 0.0714 mmol NO -3 - N = 4.1003 mg
0.5224 mmol NO 3 - N 1 mmol CH 2 O
____________________________________________________________________________________________
1 mmol H 2 2 mg H 2
hydrogen =
0.3462 mmol NO -3 - N
0.0714 mmol NO -
3 - N = 0.4125 mg
1 mmol H 2
____________________________________________________________________________________________
donor donor needed biomass produced cost/kg donor total cost / 1mg
(mg) (mg) ($) NO3--N reduced
methanol 2.8574 0.8776 0.52 0.0015
acetic acid 3.6746 0.6925 0.78 0.0029
ethanol 1.9697 0.7727 0.923 0.0018
glucose 4.1003 0.9328 0.316 0.0013
hydrogen 0.4125 0.2703 1.402 0.0006
The first consideration in choosing the appropriate electron donor will be the cost. For the same amount of
nitrate reduced (i.e., 1.0 mg or 0.0714 mmol NO 3--N), the most economic choice will be hydrogen (acetic acid
will be costliest). However, hydrogen does not contain carbon so it can not be the carbon source for this case.
Since the wastewater contains a low level of organic compound, a carbon source will need to be introduced.
This will entail additional cost to the process. Another factor that needs to be considered is the amount of
biomass production. The use of hydrogen as an electron donor will produce the least amount of biomass
while the use of glucose will produce the greatest.
The calculated values are smaller than the experimental values for both mg electron donor per mg nitrate and
mg biomass produced per mg nitrate except for ethanol. This is expected because stoichiometric calculations
are precise methods, that is, the values calculated are ideal/theoretical. The reaction proceeds to completion
such that the exact amounts of reactants are all used up to produce exact amounts of products. On the other
hand, actual reactions are not precise due to a number of errors that can occur. In this way, the efficiency of an
actual process can not be 1. More electron donor may be used up than what is actually needed to reduce a
certain amount of nitrate. Similarly, more biomass may be produced than the theoretical amount.
The values of Yobs were determined experimentally for a domestic wastewater treatment system:
Nitrification (reaction 2) is the conversion of ammonia to nitrate. This reaction can be divided into two sub-
reactions wherein ammonia is converted to nitrite and then the nitrite is converted to nitrate. The first
reaction is acted upon by Nitrosomonas wherein ammonia is the electron donor. The second reaction is acted
upon by Nitrobacter and uses nitrite as electron donor.
The COD and ammonia present in the influent are completely removed by aerobic heterotrophs and nitrifiers
such that a carbon source needs to be introduced (reaction 3). Sometimes, the original waste being treated is
introduced. In this case, the original waste was used.
Yobs fs fe = 1 - fs
-------------------------------------------------------
Reaction 1 heterotroph, ammonia as N source fs 0.7000 0.3000
Reaction 2 autotroph, combination 4.57fs 0.0985 0.9015
Reaction 3 heterotroph, nitrate as N source 0.714fs 0.8683 0.1317
reaction 1
Rd 1/50 C10H19O3N + 9/25 H2O 9/50 CO2 + 1/50 HCO3- + 1/50 NH4+ + H+ + e-
-feRa -(0.3000) (1/2 H2O 1/4 O2 + H+ + e-)
-fsRc -(0.7000) (1/20 C5H7O2N + 9/20 H2O 1/5 CO2 + 1/20 HCO3- +1/20 NH4+ + H+ + e-)
reaction 3
Rd 1/50 C10H19O3N + 9/25 H2O 9/50 CO2 + 1/50 HCO3- + 1/50 NH4+ + H+ + e-
-feRa -(0.1317) (3/5 H2O + 1/10 N2 1/5 NO3- + 6/5 H+ + e-)
-fsRc -(0.8683) (1/28 C5H7O2N + 11/28 H2O 5/28 CO2 + 1/28 NO3- + 29/28 H+ + e-)
Rmass basis 201 C10H19O3N + 177.9400 NO3- + 2.8700 H+ 54.7800 CO2 + 48.6900 H2O + 175.1500
C5H7O2N + 61.0000 HCO3- + 18.0000 NH4+ + 18.4800 N2
Rnormalized C10H19O3N + 0.8853 NO3- + 0.0143 H + 0.2725 CO2 + 0.2422 H2O + 0.8714 C5H7O2N
+ 0.3035 HCO 3- + 0.0896 NH4+ + 0.0919 N2
= 5.6089 mmol O 2 / L
from the balanced equation, 3.75 mmol O2 is consumed per mmol of donor
25 mg NH 4+ - N 1 mmol NH 4+ - N
= x - 1.1218 mmol NH 4+ - N
L 14 mg NH 4+ - N
= 0.6639 mmol NH 4+ - N / L