7
Efficiency of Renewable Materials

All the materials should be utilized to their bes advantages.

7.1 Principle 4

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.

7.2 Stoichiometry

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.

(7.1)images

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

(7.2)images

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.

7.3 Avoid the Addition of Chemicals

7.3.1 Avoid Acid Addition

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.

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

Table 7.2 Unit capital cost and unit operation and maintenance cost of acid feed (96% H2SO4) at different flow rates.

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

Table 7.3 Unit cost ratio of acid feed (96% H2SO4) at different flow ratios.

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
Unit cost/unit capital cost0 vs. Q/Q0 for acid feed (96% H2SO4), unit capital cost0 = 23.87$/kgal, Q0 = 1 MGD, displaying a descending curved line with 11 dots.

Figure 7.1 Unit capital cost/unit capital cost0 vs. Q/Q0 for acid feed (96% H2SO4), unit capital cost0 = 23.87$/kgal, Q0 = 1 MGD.

Unit cost/unit cost0 vs. Q/Q0 for acid feed (96% H2SO4), unit O&M cost0 = 0.0137$/kgal, Q0 = 1 MGD, with solid line, descending dots, and dashed line. Solid and dashed lines represent Power and Linear trendlines.

Figure 7.2 Unit O&M cost/unit O&M cost0 vs. Q/Q0 for acid feed (96% H2SO4), unit O&M cost0 = 0.0137$/kgal, Q0 = 1 MGD.

Table 7.4 Capital cost and operation and maintenance cost of acid feed (37% HCl) at different flow rates.

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

Table 7.5 Unit capital cost and unit operation and maintenance cost of acid feed (37% HCl) at different flow rates.

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

Table 7.6 Unit cost ratio of acid feed (37% HCl) at different flow ratios.

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
8220;Unit capital cost/unit capital cost0 vs. Q/Q0 for acid feed (37% HCl), unit capital cost0 = 43.21$/kgal, Q0 = 1 MGD, displaying a descending curved line with 10 dots.”

Figure 7.3 Unit capital cost/unit capital cost0 vs. Q/Q0 for acid feed (37% HCl), unit capital cost0 = 43.21$/kgal, Q0 = 1 MGD.

Unit cost/unit cost0 vs. Q/Q0 for acid feed (37% HCl), unit O&M cost0 = 0.0836$/kgal, Q0 = 1 MGD, with solid line, descending dots, and dashed line. Solid and dashed lines represent Power and Linear trendlines.

Figure 7.4 Unit O&M cost/unit O&M cost0 vs. Q/Q0 for acid feed (37% HCl), unit O&M cost0 = 0.0836$/kgal, Q0 = 1 MGD.

7.3.2 Replacing Chlorination with UV Disinfection

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.

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
Unit cost/unit cost0 vs. Q/Q0 for disinfection with chlorine, unit capital cost0 = 39.83$/kgal, Q0 = 1 MGD, displaying a descending curved line with 11 dots.

Figure 7.5 Unit capital cost/unit capital cost0 vs. Q/Q0 for disinfection with chlorine, unit capital cost0 = 39.83$/kgal, Q0 = 1 MGD.

Table 7.8 Unit capital cost and unit operation and maintenance cost of disinfection with chlorine at different flow rates.

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

Table 7.9 Unit cost ratio of disinfection with chlorine at different flow ratios.

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
Unit O&M cost/unit O&M cost0 vs. Q/Q0 for disinfection with chlorine, unit O&M cost0 = 0.0453$/kgal, Q0 = 1 MGD, displaying a descending curved line with 11 dots.

Figure 7.6 Unit O&M cost/unit O&M cost0 vs. Q/Q0 for disinfection with chlorine, unit O&M cost0 = 0.0453$/kgal, Q0 = 1 MGD.

Unit cost/unit cost0 vs. Q/Q0 for disinfection with ultraviolet, unit capital cost0 = 21.6172$/kgal, Q0 = 1 MGD, with solid line, descending dots, and dashed line. Lines represent Power and Linear trendlines.

Figure 7.7 Unit capital cost/unit capital cost0 vs. Q/Q0 for disinfection with ultraviolet, unit capital cost0 = 21.6172$/kgal, Q0 = 1 MGD.

Table 7.10 Capital cost and operation and maintenance cost of disinfection with ultraviolet at different flow rates.

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

Table 7.11 Unit capital cost and unit operation and maintenance cost of disinfection with ultraviolet at different flow rates.

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

Table 7.12 Unit cost ratio of disinfection with ultraviolet at different flow ratios.

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
Unit cost/unit cost0 vs. Q/Q0 for disinfection with ultraviolet, unit O&M cost0 = 0.010999$/kgal, Q0 = 1 MGD, displaying solid line, ascending dots, and dashed line. Lines represent Power and Linear trendlines.

Figure 7.8 Unit O&M cost/unit O&M cost0 vs. Q/Q0 for disinfection with ultraviolet, unit O&M cost0 = 0.010999$/kgal, Q0 = 1 MGD.

7.3.3 Anammox to Replace Nitrification/Denitrification

7.3.3.1 Nitrogen Forms

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).

Tree diagram with a box labeled Total nitrogen (top) branching to N-salts and Total Kjeldahl nitrogen. N-salts branches to Nitrate and Nitrite. Total Kjeldahl nitrogen branches to total ammonia and Organic N.

Figure 7.9 Nitrogen forms in domestic wastewater.

Total nitrogen is the sum of organic, ammonia, nitrate, nitrite, and gaseous nitrogen. Decomposition of nitrogenous organic matter releases ammonia to solution:

(7.5)images

Nitrifying bacteria will oxidize ammonia to nitrite and nitrate under aerobic conditions as shown in (7.6):

(7.6)images

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:

(7.7)images

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.

7.3.3.2 Nitrification

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.

7.3.3.3 Denitrification

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:

(7.8)images

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).

A box labeled Ammonia-oxidizing bacteria with an arrow curving upward from O2 to water on the left and another 2 arrows curving upward from ammonia to nitrite and from methane to methanol on the right.

Figure 7.10 Schematic of cometabolism in ammonia‐oxidizing bacteria using ammonia and methane, respectively.

Methanol reacts with nitrate as follows:

(7.9)images

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

  • CH3OH = methanol, mg/l
  • DO = dissolved oxygen, mg/l
  • NO2–N = nitrite nitrogen, mg/l
  • NO3–N = nitrate nitrogen, mg/l

Nitrification/denitrification redox pyramid depicted by upward arrows for oxidation (nitrification) from NH4+ to NO–2, to NO3 and downward arrows for reduction (denitrification) from NO3 to NO2–, then to N2.

Figure 7.11 Nitrification/denitrification redox pyramid.

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).

7.3.3.4 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.

Diagram of biological N cycle and nitrate reduction to ammonium, with arrows for partial nitritation from NH4+ to NO2, to NO3, to NO2, to N2 and arrow for planctomycetes anammox from NH4+ to N2.

Figure 7.12 The biological N cycle and nitrate reduction to ammonium.

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.

Image described by caption and surrounding text.

Figure 7.13 Conventional and redesigned sewage treatment schemes with OLAND in the side and mainstream line.

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.

7.4 Design Efficient Reactors

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:

images
(7.12)images

Therefore, the general mole balance equation of accumulation is

where

  • FA = rate of flow of A into the system
  • FA0 = rate of flow of A out the system
  • GA = the generation of other components.

XA is the equivalent of moles of A reacted over moles fed and is usually used as a master variable:

(7.14)images

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:

(7.15)images

Therefore, the master equation could be expressed as follows:

(7.16)images
(7.17)images
(7.18)images
(7.19)images

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:

(7.20)images
(7.21)images

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. images). 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.

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

Table 7.16 Oxidation rate vs. conversion factor.

X 0 0.1 0.2 0.3 0.4 0.6 0.7 0.8
images 0.832 0.74876 0.665531 0.582459 0.499083 0.333148 0.249977 0.166368
images 1.201923 1.335542 1.50256 1.71686 2.003675 3.001673 4.000361 6.010766

Table 7.17 images vs. conversion.

X 0 0.1 0.2 0.3 0.4 0.6 0.7 0.8
images 0.832 0.74876 0.665531 0.582459 0.499083 0.333148 0.249977 0.166368
images 1.201923 1.335542 1.50256 1.71686 2.003675 3.001673 4.000361 6.010766
images 0.072115 0.080133 0.090154 0.103012 0.12022 0.1801 0.240022 0.360646
1/−rA) vs. X displaying an ascending curve with 8 dot markers.

Figure 7.14 images.

FA0/(−rA) vs. X displaying an ascending curve with 8 dot markers.

Figure 7.15 images.

FA0/(−rA) (m3) vs. X displaying an ascending curve labeled VCSTR= 0.28848 m3 with 8 dot markers.

Figure 7.16 CSTR plot.

FA0/(−rA) (m3) vs. X displaying an ascending curve with 8 dot markers. The area below the curve is shaded and labeled VPFR = 0.1169 m3.

Figure 7.17 PFR plot.

Conversion profile of X vs. V (m3) displaying an ascending curve with 5 dot markers.

Figure 7.18 Conversion profile.

Reaction rate profile of –rA (mol/m3• min) vs. V (m3) displaying a descending curve with 4 dot markers.

Figure 7.19 Reaction rate profile.

Table 7.18 Conversion and reaction rate profiles.

X 0 0.2 0.4 0.6 0.8
images 0.832 0.665531 0.499083 0.333148 0.166368
V(m3) 0 0.016093 0.036863 0.066426 0.116948
FA0/(−rA) versus X displaying an ascending curve with 8 dot markers. The areas above and below the curve are labeled VDifference between CSTR and PFR = 0.17158 m3 and VPFR = 0.1169 m3, respectively.

Figure 7.20 Comparison of CSTR and PFR reactor size.

8211;rA vs. X displaying a descending line with dot markers connected to a leftward arrow at the bottom.

Figure 7.21 images.

FA0/(−rA) vs. X displaying an ascending curve with 8 dot markers. The right and bottom left portions of the graph represent CSTR2 and CSTR1, respectively.

Figure 7.22 Two CSTRs in series.

Schematic of 2 PFRs in series illustrated by 2 horizontal cylinders labeled PFR connected by an arrow labeled FA1, X1 = 0.4, with input and output arrows labeled FA0 and FAe, X2 = 0.8, respectively.

Figure 7.23 Two PFRs in series.

FA0/(−rA) (m3) vs. X displaying an ascending curve with 8 dot markers. The left and right portions below the curve represent PFR1 and PFR2, respectively.

Figure 7.24 Two PFRs in series.

Schematic of reactors in series illustrated by 3 cylinders labeled CSTR, PFR, and CSTR connected by arrows labeled X1 = 0.2 and X2 = 0.6, with input and output arrows labeled FA0 and X3 = 0.8, respectively.

Figure 7.25 Reactors in series.

FA0/(−rA) (m3) vs. X displaying an ascending curve with 8 dot markers. The right portion of the graph represents CSTR2, and the middle and left portions below the curve represent PFR and CSTR1, respectively.

Figure 7.26 Reactors in series.

Volume comparison of PFR for 2-MCP, 2,4-DCP, and 2,4,6-TCP depicted by ascending solid, dash-dot, and dashed curves, respectively, with dot markers.

Figure 7.27 Volume comparison of PFR for 2‐MCP, 2,4‐DCP, and 2,4,6‐TCP.

FA0/(−rA) (m3) vs. X displaying 2 ascending curves with dot markers. The area between the 2 curves is labeled VDifference between 2,4−DCP and 2−MCP = 0.0797 m3 and the area below is labeled V2−MCP = 0.1169 m3.

Figure 7.28 Volume comparison of PFR for 2‐MCP and 2,4‐DCP.

FA0/(−rA) (m3) vs. X displaying 2 ascending curves with dot markers. The area between the 2 curves is labeled VDifference between 2,4−TCP and 2,4−DCP = 1.1434 m3 and the area below is labeled V2,4−DCP = 0.1966 m3.

Figure 7.29 Volume comparison of PFR for 2,4‐DCP and 2,4,6‐TCP.

7.4.1 Cost of Different Volume Reactors

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.

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
ln (price) vs. ln (volume) displaying an ascending line (trend line) along with 6 dot markers (original data).

Figure 7.30 ln (price) vs. ln (volume).

7.5 Exercise

7.5.1 Questions

  1. What is the mass balance master equation for unsteady vs. steady reactors, respectively?
  2. What are the design equations for batch, CSTR, and PFR, respectively?
  3. Why reactor volume for PFR is much smaller than that of CSTR for a given conversion factor?
  4. Explain the principle involved in selecting different combinations of CSTR and PFR.
  5. Mass balance, stoichiometry, and kinetics are considered as three pillars of reactor design in chemical reactors. In water and WWTP, the product is water. How would you apply these three pillars to design a reactor to produce the maximum amount of treated water?
  6. For pentachlorophenol, what is the PFR volume required to achieve 100 conversions if all the other reaction conditions remain the same as Tang and Huang (1996a)? Why or why not?

7.5.2 Calculation

  1. A continuous‐flow reactor will convert A to B at constant temperature. If CA = 0.02CA0, FA0 = 5 mol/h, v = 10 l/h, CA0 = 0.5 mol/l, and the entering volumetric flow rate v is 10 l/h, for a constant volumetric flow rate, v = v0 = 50 l/h, FA0 = CA0v0, and CA0 = FA0/v0 = (5 mol/h)/(10 l/h) = 0.5 mol/l. If the required CSTR volumes are 99, 2 750, and 66 000, respectively, when the reaction has zero, first, and second order, (i) find the corresponding reaction rate constants. And what is the corresponding reactor volume of PFRs?
  2. Fenton process requires optimal pH of 3.5 in oxidizing organic pollutants such as chlorophenols. As a result, strong acid such as HCl or H2SO4 has to be added. In addition, the Fenton process requires oxidant H2O2 and catalyst such as FeSO4, if a vacuum UV reactor is used to oxidize chlorophenols, please answer the following design questions:
    1. How large is the reactor volume required to oxidize 1 mg/l mono‐chlorophenol to 0.01 mg/l at a flow rate of 1 MGD?
    2. How much capital and O&M costs could be saved if VUV replaces the Fenton process for the same flow rate?
  3. If a Pfaudler reactor is designed for the aforementioned problem, what is the capital cost of the Pfaudler reactor?

7.5.3 Project

7.5.3.1 Xiongan Project

  1. On‐site WWTP could play a significant role since Xiongan has many villages or satellite cities. For on‐site WWT, what type of wastewater treatment reactor would you recommend?
  2. As the Xiongan district expands with WW generated from one million people in 1 year and two million people in 5 years, would you still recommend on‐site WWTP only? What are the advantages of centralized WWTP?
  3. How much sludge and methanol could be saved if your new WWTP adopted anammox annually when OLAND was used in the side and mainstream line, respectively?
  4. What would be the O&M cost saving over a life cycle of 50 years when OLAND is used in the side and mainstream line, respectively?
  5. What would be the O&M cost saving over a life cycle of 50 years when UV disinfection is to replace chlorination?

7.5.3.2 Proposal Project

  1. Make an appointment with the WWTP manager of your local town, and get data on methanol consumption and sludge produced annually. After you have analyzed the WWTP processes, please do the following:
    1. Develop an alternative using anammox and quantify monetary saving by eliminating methanol for nitrification/denitrification for over 50 years. Assuming flow rate is 120 MGD average daily flow; inflow total is 40 mg/l as nitrogen. Forty percent of the load would be removed after AS process. The side stream anammox is being proposed to retrofit the plant. Quantify the monetary saving by eliminating methanol for nitrification/denitrification by using side stream anammox over 50 years. Assume that 0.49 gal of methanol is needed for every pound of nitrogen removed in the conventional nitrification/denitrification process.
    2. Design an alternative using UV disinfection to replace chlorination for this 120 MGD. Following the examples used in the chapter, estimate the capital and O&M costs for both UV disinfection and chlorination over 50 year design life expectancy.

References

  1. Dapena‐Mora, A., Fernandez, I., Campos, J.L. et al. (2007). Evaluation of activity and inhibition effects on anammox process by batch tests based on the nitrogen gas production. Enzyme and Microbial Technology 40: 859–865.
  2. Egli, K., Fanger, U., Alvarez, P. et al. (2001). Enrichment and characterization of an anammox bacterium from a rotating biological contactor treating ammonium‐rich leachate. Archives of Microbiology 175: 198–207.
  3. Lackner, S., Gilbert, E.M., Vlaeminck, S.E. et al. (2014). Full‐scale partial nitritation/anammox experiences – An application survey. Water Research, 55: 292–303.
  4. Levenspiel, O. (1999). Chemical Reaction Engineering, 3e. New York: Wiley.
  5. Rosenwinkel, K.‐H. and Cornelius, A. (2005). Deammonification in the moving‐bed process for the treatment of wastewater with high ammonia content. Chemical Engineering and Technology 28: 49–52.
  6. Siegrist, H., Salzgeber, D., Eugster, J., and Joss, A. (2008). Anammox brings WWTP closer to energy autarky due to increased biogas production and reduced aeration energy for N‐removal. Water Science and Technology 57: 383–388.
  7. Strous, M., Heijnen, J.J., Kuenen, J.G., and Jetten, M.S.M. (1998). The sequencing batch reactor as a powerful tool for the study of slowly growing anaerobic ammonium‐oxidizing microorganisms. Applied Microbiology and Biotechnology 50: 589–596.
  8. Strous, M., Kuenen, J.G., and Jetten, M.S.M. (1999). Key physiology of anaerobic ammonium oxidation. Applied Environmental Microbiology 65: 3248–3250.
  9. Tang, W.Z. and Huang, C.P. (1996a). Effect of chlorine content of chlorinated phenols on their oxidation kinetics by Fenton’s reagent. Chemosphere 8: 1621–1635.
  10. Tang, W.Z. and Huang, C.P. (1996b). Oxidation kinetics and mechanisms of 2,4‐dichlorophenol by Fenton’s reagent. Environmental Technology 17: 1371–1378.
  11. Van Loosdrecht, M.C.M. and Salem, S. (2006). Biological treatment of sludge digester liquids. Water Science and Technology 53: 11.
  12. Wett, B., Hell, M., Nyhuis, G. et al. (2010). Syntrophy of aerobic and anaerobic ammonia oxidisers. Water Science and Technology 61: 1915–1922.
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