All the materials should be utilized to their bes advantages.
Biomasses are considered as renewable materials. Therefore, there is a major driver to replace fossils such as crude oil with renewable biomass as feeding stock in chemical engineering. For the same reason, environmental engineering (EE) should also select biomass as feeding stock for anaerobic digestion whenever it is feasible. For example, in designing a WRRF organic compounds in wastewater could be considered as the feeding stock to produce energy. In designing EEIS, if chemicals or materials are not avoidable, each unit process should be designed with maximal efficiency to reduce footprint on the environments.
Mass balance, stoichiometry, and reaction kinetics are the three pillars in effective design of reactors such as batch, continuous stirring tank reactor (CSTR), plug‐flow reactor (PFR), and packed bed reactor (PBR). Each reactor should achieve its maximum efficiency at minimal volume to avoid short circulation and dead zone. From the mass transfer efficiency perspective, the mass transfer efficiency of PFR, CSTR, and batch reactors decreases sequentially.
A balanced chemical equation gives stoichiometric information on what reactants are reacting and what products are formed. It also gives quantitative information on how much reacts and how much is formed. To show stoichiometric relationship, mole is used in the chemical reaction equation. A mole is a fixed number of molecules that could be expressed as gram‐mole (g‐mol) or pound‐mole (lb‐mol). One g‐mol contains 6.022 × 1023 molecules, while one lb‐mol contains 2.7 × 1026 molecules.
The combustion of 1 mol of methane requires 2 mol of oxygen and produces 1 mol of carbon dioxide and 2 mol of water. Therefore, the stoichiometric equation is
Combustion of propane gives energy; therefore, it reflects the intrinsic heat value of the organic compound. In traditional EE, the amount of organic compounds is expressed as the amount of oxygen needed to oxidize them to CO2. Historically, degradation of organic compounds in wastewater is achieved through activated sludge (AS). To facilitate design, theoretical oxygen demand is the amount of O2 required to completely oxidize a chemical substance to CO2 and H2O based on stoichiometry. Biochemical oxygen demand (BOD) is the amount of O2 consumed by a substance in a standard test using microorganisms for oxidation. Chemical oxygen demand (COD) is the amount of O2 consumed by a substance in a standard test using strong chemical oxidant such as potassium dichromate. As a result, wastewater treatment plants (WWTPs) are designed to provide sufficient oxygen to degrade organic compounds in wastewater. Unfortunately, aeration is extremely energy intensive and consumes about one‐half electricity in a typical WWTP. In the last hundred years, the intrinsic energy of wastewater was not considered as energy resource. Even worse, the AS process incorporates water that should have been the product into sludge as wastes. As a result, sludge disposal costs another one‐third of electricity needed by the WWTP.
In WTP or WWTP design, whenever it is possible chemicals should not be added to water or wastewater for many reasons: (i) Addition of chemicals is extremely expensive over the life span of an EEIS. Chemical dosing equipment entails capital cost, while operation and maintenance (O&M) add cost. (ii) Reaction by‐products such as DBPs during chlorination could be formed. (iii) Sludge is produced as the waste which has to be separated and disposed. Indeed, sludge disposal could be as high as one third to one half of the operation and maintenance costs. The following example shows the capital and O&M costs at different flow rates:
Table 7.1 Capital cost and operation and maintenance cost of acid feed (96% H2SO4) at different flow rates. Table 7.2 Unit capital cost and unit operation and maintenance cost of acid feed (96% H2SO4) at different flow rates. Table 7.3 Unit cost ratio of acid feed (96% H2SO4) at different flow ratios. Table 7.4 Capital cost and operation and maintenance cost of acid feed (37% HCl) at different flow rates. Table 7.5 Unit capital cost and unit operation and maintenance cost of acid feed (37% HCl) at different flow rates. Table 7.6 Unit cost ratio of acid feed (37% HCl) at different flow ratios.
Q (MGD)
2006 capital cost ($)
2006 operation and maintenance costs ($/year)
1
23 868.26
4 988.82
2
24 714.14
6 466.51
4
26 090.77
9 421.88
6
27 267.50
12 377.26
8
28 330.61
15 332.63
10
29 316.48
18 287.99
20
33 577.31
33 064.77
40
40 505.34
62 618.07
60
46 422.95
92 171.04
80
51 766.51
121 723.68
100
56 719.83
151 275.98
Q (MGD)
Unit capital cost ($/kgal)
Unit O&M costs ($/kgal)
1
23.87
0.0137
2
12.36
0.0089
4
6.52
0.0065
6
4.54
0.0057
8
3.54
0.0053
10
2.93
0.0050
20
1.68
0.0045
40
1.01
0.0043
60
0.77
0.0042
80
0.65
0.0042
100
0.57
0.0041
Q/Q0
Unit capital cost/unit capital cost0
Unit O&M costs/unit O&M costs0
1
1.0000
1.0000
2
0.5177
0.6481
4
0.2733
0.4722
6
0.1904
0.4135
8
0.1484
0.3842
10
0.1228
0.3666
20
0.0703
0.3314
40
0.0424
0.3138
60
0.0324
0.3079
80
0.0271
0.3050
100
0.0238
0.3032
Q (MGD)
2006 capital cost ($)
2006 operation and maintenance costs ($/year)
1
43 212.16
30 501.52
2
56 211.88
57 491.08
4
77 368.33
111 467.76
6
95 452.67
165 441.17
8
111 790.97
219 411.34
10
126 942.03
273 378.29
20
192 423.93
543 165.23
40
298 896.17
1 082 506.81
60
389 839.84
1 621 552.01
80
471 961.32
2 160 316.17
100
548 085.60
2 698 813.80
Q (MGD)
Unit capital cost ($/kgal)
Unit O&M costs ($/kgal)
1
43.21
0.0836
2
28.11
0.0788
4
19.34
0.0763
6
15.91
0.0755
8
13.97
0.0751
10
12.69
0.0749
20
9.62
0.0744
40
7.47
0.0741
60
6.50
0.0740
80
5.90
0.0740
100
5.48
0.0739
Q/Q0
Unit capital cost/unit capital cost0
Unit O&M costs/unit O&M costs0
1
1.0000
1.0000
2
0.6504
0.9424
4
0.4476
0.9136
6
0.3682
0.9040
8
0.3234
0.8992
10
0.2938
0.8963
20
0.2227
0.8904
40
0.1729
0.8873
60
0.1504
0.8860
80
0.1365
0.8853
100
0.1268
0.8848
Traditionally, chlorination is used in disinfection for economic reasons. For example, Table 7.7 shows that the annual capital and O&M costs of chlorination at 1 MGD are $39 831.77 and $16 551.66, respectively, while the annual capital and O&M costs of UV disinfection at 1 MGD are $21 617.18 and $4 014.69, respectively. Clearly, the O&M cost of UV disinfection is significantly lower than chlorination. At 100 MGD, however, the annual capital and O&M costs of chlorination are $371 543.92 and $77 792.03, while the annual capital and O&M costs of UV disinfection are $2 009 248.43 and $410 206.17, respectively. More importantly, Figure 7.5 shows that the unit cost ratio to baseline flow rate at 1 MGD slightly increased. Apparently, this trend is contradictory to the economy of scale. The major reason for this is that the probability of the failure lamp and maintenance is much higher at large flow rate than that at a smaller flow rate.
Table 7.7 Capital cost and operation and maintenance cost of disinfection with chlorine at different flow rates. Table 7.8 Unit capital cost and unit operation and maintenance cost of disinfection with chlorine at different flow rates. Table 7.9 Unit cost ratio of disinfection with chlorine at different flow ratios. Table 7.10 Capital cost and operation and maintenance cost of disinfection with ultraviolet at different flow rates. Table 7.11 Unit capital cost and unit operation and maintenance cost of disinfection with ultraviolet at different flow rates. Table 7.12 Unit cost ratio of disinfection with ultraviolet at different flow ratios.
Q (MGD)
2006 capital cost ($)
2006 operation and maintenance costs ($/year)
1
39 831.77
16 551.66
2
46 929.77
17 402.64
4
58 975.19
18 990.26
6
69 608.12
20 496.97
8
79 416.46
21 953.66
10
88 653.99
23 374.36
20
129 781.85
30 141.88
40
199 576.47
42 789.50
60
261 186.67
54 808.99
80
318 019.05
66 440.17
100
371 543.92
77 792.03
Q (MGD)
Unit capital cost ($/kgal)
Unit O&M costs ($/kgal)
1
39.83
0.0453
2
23.46
0.0238
4
14.74
0.0130
6
11.60
0.0094
8
9.93
0.0075
10
8.87
0.0064
20
6.49
0.0041
40
4.99
0.0029
60
4.35
0.0025
80
3.98
0.0023
100
3.72
0.0021
Q/Q0
Unit capital cost/unit capital cost0
Unit O&M costs/unit O&M costs0
1
1.0000
1.0000
2
0.5891
0.5257
4
0.3702
0.2868
6
0.2913
0.2064
8
0.2492
0.1658
10
0.2226
0.1412
20
0.1629
0.0911
40
0.1253
0.0646
60
0.1093
0.0552
80
0.0998
0.0502
100
0.0933
0.0470
Q (MGD)
2006 capital cost ($)
2006 operation and maintenance costs ($/year)
1
21 617.18
4 014.69
2
41 694.27
8 108.90
4
81 848.43
16 375.97
6
122 002.60
24 564.38
8
162 156.77
32 752.78
10
202 310.93
40 941.19
20
403 081.77
81 961.90
40
804 623.43
164 081.96
60
1 206 165.10
246 123.36
80
1 607 706.77
328 164.77
100
2 009 248.43
410 206.17
Q (MGD)
Unit capital cost ($/kgal)
Unit O&M costs ($/kgal)
1
21.6172
0.010999
2
20.8471
0.011108
4
20.4621
0.011216
6
20.3338
0.011217
8
20.2696
0.011217
10
20.2311
0.011217
20
20.1541
0.011228
40
20.1156
0.011238
60
20.1028
0.011239
80
20.0963
0.011239
100
20.0925
0.011239
Q/Q0
Unit capital cost/unit capital cost0
Unit O&M costs/unit O&M costs0
1
1.0000
1.0000
2
0.9644
1.0099
4
0.9466
1.0198
6
0.9406
1.0198
8
0.9377
1.0198
10
0.9359
1.0198
20
0.9323
1.0208
40
0.9305
1.0218
60
0.9299
1.0218
80
0.9296
1.0218
100
0.9295
1.0218
Nitrogen in municipal wastewater originates from human urine and excreta. Of 100% influent nitrogen, 85% is in the treated wastewater, and 15% is in the digested sludge solids. About 40% is ammonia and 60% is bound in organic matter. The annual per capita nitrogen ranges from 4 to 6 kg/cap/year that results in 35 mg/l total nitrogen in wastewater stream (Figure 7.9).
Total nitrogen is the sum of organic, ammonia, nitrate, nitrite, and gaseous nitrogen. Decomposition of nitrogenous organic matter releases ammonia to solution:
Nitrifying bacteria will oxidize ammonia to nitrite and nitrate under aerobic conditions as shown in (7.6):
Denitrification will take place under anaerobic or anoxic conditions. Organic matter (AH2) is oxidized by nitrate which serves as the hydrogen acceptor. The end product is nitrogen gas:
Primary sedimentation removes less than 15% of total nitrogen, while AS removes another 10%. As a result, only 4% BOD contributed by N could be removed. In anaerobic digester, 40% of the organic nitrogen in the sludge could be converted to ammonia, and 10% of the original 25% is recycled to the treatment plant and appears in the effluent, which then contains 85% of the influent nitrogen. Typically, nitrogen removal in conventional biological treatment systems is less than 40%. Therefore, tertiary treatment referred as nitrification/denitrification is required to achieve 1 mg/l discharge standard in most states of the United States.
Conventional activated sludge (CAS) is designed to remove carbonaceous BOD with minimal removal of ammonia nitrogen. The high ammonia content and low BOD provide greater growth potential for the nitrifiers relative to the heterotrophs. Therefore, the nitrification process at an increased sludge age compensates for lower operating temperature to ensure the growth rate of nitrifying bacteria. In effluent, some of these bacteria is lost and would be supplemented by newly produced bacteria. Temperature, pH, and dissolved oxygen concentration are the important parameters. The dissolved oxygen level should be greater than 1.0 mg/l at optimal pH near 8.4. Lime or soda ash may be needed to raise the pH to the optimum level in the nitrification tank to supplement the depleting alkalinity. Ammonia nitrogen loadings should vary from 160 to 320 g/m3/day at 10–20 °C, respectively, with aeration period from 4 to 6 h.
Nitrate can be reduced to nitrogen gas by facultative heterotrophic bacteria in an anoxic environment. An organic carbon source such as methanol is needed to act as a hydrogen donor and to supply carbon for biological synthesis. Methanol is commonly used due to its high biodegradability. Since methanol is expensive, the cost of methanol is the major limit of denitrification process. Biodegradable organic matter can be used as an oxygen acceptor (hydrogen donor) for the conversion of nitrate to nitrogen gas. Therefore, a portion of raw wastewater could supply the carbonaceous BOD required:
In the past engineering design, a biological nitrification/denitrification process requires the mixing of raw organic matter with nitrified wastewater. As a result, an aerobic zone is needed for nitrification and an anoxic zone for denitrification (Figure 7.10).
Methanol reacts with nitrate as follows:
Since the effluent from nitrification also contains dissolved oxygen and nitrite, the total methanol required as a hydrogen donor in denitrification can be estimated using Equation 7.10:
In addition, methanol is a carbon source in bacterial synthesis (Figure 7.11). Assuming that 30–50% excess methanol is needed for bacteria synthesis, the total methanol demand can be calculated using Equation 7.11:
where
A plug‐flow tank with underwater mixers is usually followed by a clarifier for sludge separation and return in designing the denitrification system. The retention time from 2 to 4 h is required for denitrification of a domestic wastewater depending on nitrate loading and temperature. Since methanol is expensive, traditional denitrification following nitrification is gradually being replaced by anaerobic ammonium oxidation (Anammox).
The conventional biological nitrification and denitrification requires costly methanol. Therefore, a huge energy unit consumption up to 4.0 kWh/kg‐N is required. As a result, this denitrification process is considered as unsustainable design in wastewater treatment. To reduce this energy consumption and to eliminate the addition of methanol, anaerobic ammonia oxidation (anammox) was discovered in 1990 (Van Loosdrecht and Salem, 2006). In anammox, ammonium is the electron donor, and nitrite is the electron acceptor that is converted anaerobically into mainly nitrogen gas and some nitrate by anammox bacteria (Strous et al., 1998). Figure 7.12 shows that anammox is the shortcut between ammonia and nitrate under biological degradation by planctomycetes. Since NO2− donates electron to ammonia, it reduces aeration and sludge production and eliminates methanol requirement as shown in Figure 7.12.
Table 7.13 shows the optimal parameters for the anammox process.
Table 7.13 Optimum anammox parameters.
Anammox parameters | Optimum data |
Temperature (°C) | 30–35 |
pH | 7.0–8.0 |
SRT (days) | 11+ |
HRT (h) | 8 |
Nitrite to ammonia ratio | 1–1.3 |
Quantitatively, anammox could reduce organic carbon (methanol), aeration, and sludge production by 100, 60, and 90%, respectively (Van Loosdrecht and Salem, 2006; Siegrist et al., 2008). The energy demand of the semibatch reactor (SBR) sidestream treatment systems ranged from as low as 0.8 kWh/kg‐N to around 2 kWh/kg‐N. For example, Wett et al. (2010) reported 1.2 kWh/kg‐N. Compared with a conventional nitrification and denitrification (N/DN) sidestream treatment with an energy demand of approximately 4.0 kWh/kg‐N (only accounting for electricity consumption in the sidestream), the savings of PN/A SBR systems are at least 50% depending on the oxygen transfer efficiency of aeration type. Therefore, more than 100 plants have anammox worldwide in 2014. SBR consists of 50% of all the plants, while granular systems include moving bed biofilm reactors (Rosenwinkel and Cornelius, 2005).
Nitrite is both an essential substrate and an inhibitor to the reaction. Strous et al. (1999) suggested that nitrite concentrations greater than 100 mg‐N/l will completely stop the reaction. Egli et al. (2001) showed that anammox was only inhibited at nitrite concentrations higher than 182 mg‐N/l. However, as high as 350 mg‐N/l barely caused a 50% inhibition of the anammox process (Dapena‐Mora et al. 2007). Inhibition frequency and time are all important for the performance of anammox. For these reasons, more than 50% of operation problems of anammox are due to the buildup of either nitrite or nitrate (Lackner et al., 2014).
Figure 7.13 illustrates the patented OLAND scheme and the mainstream line of WWTPs, respectively.
Table 7.14 shows that the chemical costs of nitrification/denitrification of $1.839 million/year due to addition of methanol could be completely eliminated with the anammox process. Indeed, anammox is the key technology in retrofitting traditional WWTP to energy‐positive WWTP in Austria.
Table 7.14 Eliminate addition of methanol using sidestream reactor.
Process parameters | Unit | Nitrification/denitrification | Nitritation/denitritation | PN/anammox |
Aerobic reactor volume | m3 | 8 559 | 6 587 | 6 587 |
Anoxic reactor volume | m3 | 4 431 | 4 431 | N/A |
Oxygen demand SOTR | kg/h | 545 | 580 | 663 |
Aeration power consumption | kWh/day | 1.70 | 1.81 | 2.07 |
Methanol demand | kg/day | 11 298 | 6 998 | 0 |
Energy cost | $/year | 61 999 | 65 964 | $75 448 |
Chemical costa | $/year | 1 839 188 | 1 139 254 | 0 |
a Assume blower efficiency is 18 Wh/m3: fine bubble diffusers 25%.
• 2012 electricity price assumed to be $0.10/kWh.
• 2012 methanol price assumed to be $446/metric ton.
Efficiency of material could be achieved through the optimal design of reactors for many reasons: (i) the optimal reactor could reduce reactor volume that in turn reduce the embedded material and energy; (ii) smaller reactor would have better hydraulic conditions for reactions to take place and therefore reduce the operation cost; and (iii) the life cycle capital and O&M costs could be reduced. To design the most efficient reactor, mass balance can be described by Equation 7.13, which shows that the flux accumulation in the reactor equals feeding flux minus outgoing flux plus the generation of that component in the reactor:
Therefore, the general mole balance equation of accumulation is
where
XA is the equivalent of moles of A reacted over moles fed and is usually used as a master variable:
XA is the conversion factor between 0 and 1. At 0, A did not react. At 1, all of A has reacted. XA, if the right hand is divided by volume at both nominator and denominator, could also be defined as follows:
Therefore, the master equation could be expressed as follows:
Variables to consider in reactor design are the limiting reagent that is the reagent with the highest coefficient value and the time to achieve a certain conversion from mole balance in a batch reactor. Conversion factor XA applies to all of the components in the system: NA, FA, and CA. The main differences among batch reactor, CSTR, and PFR are that (i) batch reactors rely on time, not volume to dictate the results required, (ii) CSTR relies on total volume required regardless of rate due to steady‐state concentration, and PFR relies on volume required due to reaction rate. A chemical reactor volume for given experimental kinetic data can be found through the Levenspiel plot (Levenspiel, 1999), which uses conversion factor as the master variable. CSTR always operates at the lowest reaction rate:
The reason the isothermal CSTR volume is usually greater than the PFR volume is that the CSTR is always operating at the lowest reaction rate (e.g. ). The PFR on the other hand starts at a high rate at the entrance and gradually decreases to the exit rate, thereby requiring less volume because the volume is inversely proportional to the rate (Figures 7.20 and 7.21). However, for autocatalytic reactions, product‐inhibited reactions, and nonisothermal exothermic reactions, these trends will not always be the same.
Table 7.15 Reaction rate vs. conversion factor. Table 7.16 Oxidation rate vs. conversion factor. Table 7.17 vs. conversion. Table 7.18 Conversion and reaction rate profiles. The purpose of reactor design is to optimize the reactor volume. The reason is simple: the smaller the size, the lower the cost to achieve the same conversion factor.
Table 7.19 Price and volume of Pfaudler reactors.
Raw data
X
−rA
0.00
0.00530
0.10
0.00520
0.20
0.00500
0.30
0.00450
0.40
0.00400
0.50
0.00330
0.60
0.00250
0.70
0.00180
0.80
0.00125
0.85
0.00100
X
0
0.1
0.2
0.3
0.4
0.6
0.7
0.8
0.832
0.74876
0.665531
0.582459
0.499083
0.333148
0.249977
0.166368
1.201923
1.335542
1.50256
1.71686
2.003675
3.001673
4.000361
6.010766
X
0
0.1
0.2
0.3
0.4
0.6
0.7
0.8
0.832
0.74876
0.665531
0.582459
0.499083
0.333148
0.249977
0.166368
1.201923
1.335542
1.50256
1.71686
2.003675
3.001673
4.000361
6.010766
0.072115
0.080133
0.090154
0.103012
0.12022
0.1801
0.240022
0.360646
X
0
0.2
0.4
0.6
0.8
0.832
0.665531
0.499083
0.333148
0.166368
V(m3)
0
0.016093
0.036863
0.066426
0.116948
7.4.1 Cost of Different Volume Reactors
Pfaudler reactors
Reactor capacity (gal)
Price (thousands of dollars)
ln(volume)
ln(price)
5
27
1.61
3.30
50
35
3.91
3.56
500
67
6.21
4.20
1000
80
6.91
4.38
4000
143
8.29
4.96
8000
253
8.99
5.53