1 生物反應器之基質降解動力學 kinetics of substrate degradation in biological reactors...

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生物反應器之基質降解動力學Kinetics of Substrate Degradation in

Biological Reactors

主講人 :黃汝賢國立成功大學環境工程學系

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Papers Submitted to:

Biotechnol. Bioeng. (USA)

J. Envir. Eng. (ASCE). (USA)

Water Envir. Res. (USA)

Water Res. (Great Britain)

J. Chem. Technol. Biotechnol. (Great Britain)

4

Biological Wastewater Treatment

Objectives of biological treatment

Roles of microorganisms

Nutritional requirements for microbial growth

5

Biological Treatment Processes

Aerobic

Anoxic

Anaerobic

Combined

6

Kinetics of Substrate Utilization

Monod-type Grau

Haldane Modified Grau (Huang)

SKkXS

dtdS

s

is KSSK

kXSdtdS

2 /

0SkXS

dtdS

0

n

SSSkX

dtdS

7

Estimation of Biokinetic Constants

Batch

Chemostat

CSTR with sludge return

8

Part 1. Process Kinetics of UASB Reactors Treating Inhibitory Substrate

9

E f f lu e n t

G a s

4

# 6

# 5

# 4

23 35 5

# 3P

P 1

T h e r m o m e te r

# 2

# 1

PI n f lu e n t

1 . T h e r m i s to r2 . B i o r e a c t o r3 . O u t e r - w a te r j a c k e t4 . G a s - l i q u id - s o l id s s e p a r a t o r5 . R e c y c le

Schematic diagram of UASB reactor

Process Kinetics of UASB Reactors

10

Kinetic Model

pro ducts En dVFAsPh eno lsM eth an o g enAcid o g en s

dr

dS

rdr

SdD ff

f1

2

12

1

2 iffs

ff

K/SSK

SXkf

2111

111

01 dr

dS f a t r = 0

111

111 fb

wff SS

L

D

dr

dSD a t r = R

22

222

2

22

2

2

fs

fffff SK

SXkf

dr

dS

rdr

SdD

iffs

ff

K/SSK

SXkf

2111

111

02 dr

dS f a t r = 0

222

222 fb

wff SS

L

D

dr

dSD a t r = R

ibbs

b

x

bin

K/SSK

Skf

M

SSQ2

111

111

11 1

22

222

211

bs

b

x

bbin

SK

Sfk

M

SSSQ


11

Time course of phenol utilization in a suspended- growth batch reactor (mixed culture).

Time (h)

0 50 100 150 200 250 300 350

Phe

nol (

mg/

L)

0

200

400

600

800

1000

1200 Disrupted-granule culture for phenolExperimental

Calculated

X = 1165 mg VSS/Lk = 0.86 mg phenol/mg VSS-dKs = 63.6 mg phenol/L

Ki = 56.7 mg phenol/L


12

Time course of acetate utilization in a suspended- growth batch reactor (enrichment culture).


13

Operating conditions and performance of UASB reactors

Test Recycle Sin Volumetric Xb COD removalrun us Q ratio (mg phenol loading lower middle upper Biomass soluble total

(m/h) (L/d) (-) /L) (kg COD/m3-d) (mg VSS/L) (g VSS) (%)A1 0.5 5.0 7.7 335 1.06 41190 19850 43.0 97.1 93.4B1 1.0 5.0 16.3 335 1.06 52020 18520 53.8 96.6 91.9C1 2.0 5.0 33.6 335 1.06 39590 18680 14420 48.2 97.8 93.9D1 4.0 5.0 68.1 335 1.06 27300 20300 12710 34.4 97.8 91.7A2 0.5 5.0 7.7 1050 3.31 42770 29260 50.0 97.6 96.8B2 1.0 5.0 16.3 1050 3.31 53480 30120 64.4 96.6 95.8C2 2.0 5.0 33.6 1050 3.31 41300 26810 18130 56.1 97.0 96.3D2 4.0 5.0 68.1 1050 3.31 32130 26600 14840 53.3 97.0 96.3A3 0.5 10.0 3.3 1595 10.05 50320 44860 40520 78.8 88.8 82.7B3 1.0 10.0 7.6 1690 10.66 57190 47600 42350 88.1 98.1 96.9C3 2.0 10.0 16.3 1690 10.66 52460 46260 45220 92.7 98.1 97.1D3 4.0 10.0 33.6 1690 10.66 63100 53650 49480 113.4 98.0 96.7


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Experimental results of f values in UASB reactors

Test Volumetric loading frun (kg COD/m3-d) lower middle upperA1 1.06 0.76 a 0.56B1 1.06 0.76 a 0.62C1 1.06 0.83 0.84 a 0.58D1 1.06 0.83 0.81 a 0.50A2 3.31 0.60 a 0.65B2 3.31 0.79 a 0.61C2 3.31 0.45 0.57 a 0.52D2 3.31 0.58 0.70 a 0.51A3 10.05 0.32 0.21 a 0.24B3 10.66 0.29 0.28 a 0.22C3 10.66 0.30 0.27 a 0.25D3 10.66 0.29 0.23 a 0.25a Sampling port is near the one-half height of sludge bed.


15

Biological and physical parameters used in model simulation

Parameter Values Remarksk1 1.28 d-1 Determined in this studyKs1 63.6 mg phenol/L Determined in this studyKi 56.7 mg phenol/L Determined in this studyk2 5.25 d-1 Determined in this studyKs2 144 mg acetate/L Determined in this studyf variable Table 3Xf variable Table 4Mx variable Table 2dj and Fj variable Determined in this studyDw1 1.0610-4 m2/d Jih and Huang (1994)Dw2 1.3710-4 m2/d Huang and Jih (1997)Df1 8.4810-5 m2/d Williamson and McCarty (1976)Df2 1.0910-5 m2/d Williamson and McCarty (1976)Li variable Calculated by Eq. (8) 2.23 mg acetate/mg phenol based on COD-equivalent variable 1-Xb/Xf

7.2410-7 m2/s water at 35℃


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Calculated phenol, VFAs, and COD concentrations in the effluent vs. experimental results

Volumetric Phenol VFAs CODTest loading us exp. cal. exp. cal. exp. cal.run (kg COD/m3-d) (m/h) (mg phenol/L) (mg acetate/L) (mg COD/L)A1 1.06 0.5 0.5 8.4 10 0.6 23 20.7B1 1.06 1.0 1.0 7.0 15 0.7 27 17.4C1 1.06 2.0 0.4 9.9 8 0.6 18 24.3D1 1.06 4.0 0.2 11.9 12 0.7 18 29.2A2 3.31 0.5 0.8 28.9 28 1.8 60 70.9B2 3.31 1.0 0.9 24.1 30 1.8 86 59.5C2 3.31 2.0 0.7 17.2 38 2.4 76 43.7D2 3.31 4.0 0.7 21.3 36 2.4 76 53.3A3 10.05 0.5 180 40.4 150 67.7 426 168.5B3 10.66 1.0 5.4 32.8 58 61.6 76 143.8C3 10.66 2.0 1.2 33.8 69 55.8 78 140.0D3 10.66 4.0 0.8 23.3 75 48.6 83 107.0


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Part 2. Effect of Addition of Rhodobacter Sp. to Activated-Sludge Reactors Treating Piggery Wastewater

18

Schematic of purple nonsulfur bacteria-supplemented activated-sludge reactors.

Addition of Rhodobacter Sp. to Activated-Sludge Reactors

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00 S

SSkX

SS

SSkX

dt

dS n

n

n

u

≒ ( 1 )

00 S

SSkX

SS

SSkX

dt

dS n

n

n

u

≒ ( 1 )

nn

u S

SSkX

dt

dS

0( 2 )

Xkdt

dSY

dt

dXd

uT

g

( 3 )

nnn f

S

Sk

S

SSk

XV

)SS(Q

00

0 ( 4 )

w h e r e

f = S n / S 0 ( 5 )

F / M = Q S 0 / X V ( 6 )

R = 1 – S / S 0 ( 7 )

Kinetic ModelAddition of Rhodobacter Sp. to Activated-Sludge Reactors

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( 1 – f – R ) n / R = ( F / M ) / k ( 8 )

dTdTc

kRYkXV

)SS(QY

F/M1 0 ( 9 )

F / M = ( 1 + k d c ) / Y T R

c ( 1 0 )

n

cT

cd

kY

kfR

1

11

( 1 1 )

baRbXV

SSQac

F/MSOUR 0 ( 1 2 )

bkY

kfabRfakc

T

d

n

1

c

cn 11M/F1SOUR ( 1 3 )


21

Time course of soluble COD conversion in batch-type activated-sludge reactors.

Time (h)

0 2 4 6 8 10 12 14

So

lub

le C

OD

(m

g/L

)

100

150

200

250

300

350

MLVSS = 2287 mg/L

PNB dosage

0 mg/L

11 mg/L

22 mg/L44 mg/L88 mg/L


22

Time course of Bchl. a decay in continuous- flow activated-sludge reactors.

0 1 2 3 4 5 6 7B

chl.a

(n

g/m

g-V

SS

)0

10

20

30

40

k1 = 0.22 d-1

Time (d)

0 1 2 3 4 5 6 7

Bch

l.a (

ng

/mg

-VS

S)

0

10

20

30

40

k1 = 0.32 d-1

Light

Dark


23

Calculated and experimental COD removal efficiencies at different F/M ratios.

F/M (kg COD /kg MLVSS-d)

0.0 0.2 0.4 0.6 0.8 1.0 1.2

CO

D r

emov

al (

%)

40

50

60

70

80

90

100

CASR, ExperimentalRASR, ExperimentalCASR, Eq. (8), k = 0.63 d-1, f = 0.038RASR, Eq. (8), k = 0.88 d-1, f = 0.025


24

Variations in TKN removal efficiency with different F/M ratios.

F/M (kg COD /kg MLVSS-d)

0.0 0.2 0.4 0.6 0.8 1.0 1.2

TK

N r

emov

al (

%)

50

60

70

80

90

100

R2 = 0.83

R2 = 0.88

CASR, ExperimentalRASR, Experimental


25

Calculated and experimental SOURs at different F/M ratios.


26

Parametric sensitivity. (k = 0.88 d-1, f = 0.025, n = 0.50, and F/M = 0.50 kg COD/kg MLVSS-d)

R/R0 (%)

P/P0 (%)-100 -50 0 50 100

-50

-25

0

25

50

n

F/M

k

f


27

Parametric sensitivity. (k = 0.88 d-1, f = 0.025, n = 0.50, a = 0.60 kg O2/kg COD, and b = 0.10 d-1)

-100 -50 0 50 100

-100

-50

0

50

100

P/P0 (%)

SOUR/SOUR0 (%)

n

f

a, k

b


28

Part 3. Nitrification-Denitrification Kinetics Incorporating Distributed Fractions of Nitrosomonas, Nitrobacter, Nitrate Reducer and Nitrite Reducer

29

Anoxicreactor

Aerobicreactor

Settler

Mixed liquor recycle

Sludge return

Influent Effluent

Excess sludge

Schematic of the single-sludge nitrogen removal system.

Nitrification-Denitrification Kinetics Incorporating Distributed Fractions of Bacterial Species

30

Assumptions of Model Formulation

1.Nitrification and biosynthesis of nitrifiers occur in the aerobic reactor only.

2.Denitrification and biosynthesis of denitrifiers occur in the anoxic reactor only.

3.Both nitrification and denitrification are regarded as sequential biochemical reactions.

4.Both the oxidation of NH4+-N and NO2

--N follow Monod-type kinetics; the reduction of NO3

--N follows zero-order kinetics, while the reduction of NO2--N

follows Monod-type kinetics.

5.No microbial activity occurs in the settler; that is, the soluble nitrogen content in the settler and the effluent are the same as that in the aerobic reactor.

6.Nitrogen assimilation by Nitrosomonas, Nitrobacter, nitrate reducer or nitrite reducer is 0.124 g N/g VSS, according to the chemical formula of microbial cells C5H7O2N.


31

NH4+-N, NO2

--N, and NO3--N in anoxic reactor

The mass balance for NH4+-N, NO2

--N, and NO3--N entering and leaving the anoxic

reactor can be expressed as

Q Ck0 + (Qs + Qm) Ck2 – (Q + Qs + Qm) Ck1 – V1rs = 0 (1)

(Qs + Qm) Cni2 – (Q + Qs + Qm) Cni1 + V1rdn1 – V1rdn2 = 0 (2)

(Qs + Qm) Cna2 – (Q + Qs + Qm) Cna1 – V1rdn1 = 0 (3)

NH4+-N, NO2

--N, and NO3--N in aerobic reactor

The mass balance for NH4+-N, NO2

--N, and NO3--N entering and leaving the aerobic

reactor can be expressed as

(Q + Qs + Qm)Ck1 – (Q + Qs + Qm) Ck2 – V2rs – V2rn1 = 0 (4)

(Q + Qs + Qm) Cni1 – (Q + Qs + Qm) Cni2 + V2rn1 – V2rn2 = 0 (5)

(Q + Qs + Qm) Cna1 – (Q + Qs + Qm) Cna2 + V2rn2 = 0 (6)

Kinetic Model


32

N i t r i f i c a t i o n a n d d e n i t r i f i c a t i o n r a t e s a n d N H 4+ - N u p t a k e r a t e

21

1211

kn,s

nknn CK

XfCkr

( 7 )

22

2222

nin,s

nninn CK

XfCkr

( 8 )

Xfkr dndndn 111 ( 9 )

12

2122

nidn,s

dnnidndn CK

XfCkr

( 1 0 )

r s = 0 . 1 2 4 X / c ( 1 1 )

w h e r e

21

2211

VV

VXVXX


33

Operating conditions and main results of the single-sludge nitrogen removal system a

HRT MLVSS COD Nitrogen removal

Run Qanoxicreactor

aerobicreactor

Rs Rmanoxicreactor

aerobicreactor

c influent

anoxicreactor

aerobicreactor

NH4+-N TN

CODexp/TNexp

Alkcal/Alkexp

(L/d) (h) (-) (-) (mg/L) (mg/L) (d)

1 15 8.0 19.2 1 0 597 615 10.3 220 40 26 98.9 56.9 3.9 1.07

2 15 8.0 19.2 1 2 687 643 12.1 330 25 25 98.3 75.4 5.2 1.02

3 30 4.0 9.6 1 1 1295 1335 9.4 395 67 40 95.0 65.4 4.2 0.98

4 30 4.0 9.6 1 2 1425 1443 10.0 430 73 52 93.4 70.7 4.1 1.05

5 50 2.4 5.8 1 0 2015 2100 10.5 300 54 27 92.1 49.6 4.5 1.01

6 50 2.4 5.8 1 1 2045 2060 10.0 320 44 23 91.0 49.0 4.3 1.06

7 50 2.4 5.8 1 2 2015 2050 11.0 450 74 30 90.7 41.4 4.2 0.98

8 60 2.0 4.8 1 1 2220 2380 10.0 240 37 33 86.3 43.5 4.1 0.93a Influent: NH4

+-N = 120 mg/L, COD = 220 – 450 mg/L.


34

Enrichment culture for nitrite

0 1 2 3 40

2

4

6

8

10

12

14

16

18

20

Xn2 = 172 mg VSS/L

kn2 = 2.27 mg NO2--N/mg VSS-d

Ks,n2 = 12.7 mg NO2--N/L

Time (h)

NO

2- -N

(m

g/L)

Time course of the oxidation of NO2--N in a suspended-

growth batch reactor.


35

Time course of the oxidation of NH4+-N in a suspended-


0 1 2 30

10

20

30

40

50

60

Xn1 = Xn - Xn2 = 307 mg VSS/L

Xn2 = Xnfn2 = 420 x 0.27 = 113 mg/L

kn1 = 1.73 mg NH4+-N/mg VSS-d

Ks,n1 = 1.71 mg NH4+-N/L

Equivalent to enrichment culture for ammonia

Time (h)

NH

4+-N

(m

g/L)


36

Time course of the reduction of NO2--N in a suspended-


Time (h)

0 1 2

NO

2- -

N (

mg/

L)

0

5

10

15

20

25

Enrichment culture for nitrite

Xdn2 = 375 mg VSS/L

kdn2 = 0.74mg NO2--N/mg VSS-d

Ks,dn2 = 0.14 mg NO2--N/L


37

0 1 2 30

10

20

30

40

50

60

Time (h)

Xdn1 = Xdn - Xdn2 = 181 mg VSS/L

Xdn2 = Xdnfdn2 = 585 x 0.69 = 404 mg VSS/L

kdn1 = 3.56 mg NO3--N/mg VSS-d

NO

3- -N

(m

g/L)

Equivalent to enrichment culture for nitrate

Time course of the reduction of NO3--N in a suspended-



38

Distributed fractions of Nitrosomonas (fn1), Nitrobacter (fn2),nitrate reducer (fdn1), and nitrite reducer (fdn2) in the single-sludge nitrogen removal system

HRT

Run Qanoxicreactor

aerobicreactor

Rs Rm fn1 fn2 fdn1 fdn2

(L/d) (h) (-) (-)

1 15 8.0 19.2 1 0 0.34 0.19 0.08 0.35

2 15 8.0 19.2 1 2 0.25 0.18 0.11 0.47

3 30 4.0 9.6 1 1 0.29 0.23 0.07 0.39

4 30 4.0 9.6 1 2 0.33 0.16 0.08 0.38

5 50 2.4 5.8 1 0 0.32 0.31 0.11 0.34

6 50 2.4 5.8 1 1 0.31 0.30 0.09 0.35

7 50 2.4 5.8 1 2 0.30 0.25 0.06 0.32

8 60 2.0 4.8 1 1 0.14 0.23 0.14 0.32

Avg. 0.29 0.23 0.09 0.37


39

Biological parameters in model simulation

kn1

(d-1)Ks,n1

(mg/L)kn2

(d-1)Ks,n2

(mg/L)kdn1

(d-1)kdn2

(d-1)Ks,dn2

(mg/L)fn1

(-)fn2

(-)fdn1

(-)fdn2

(-)

1.73 1.71 2.27 12.7 3.56 0.74 0.14 Table 2 Table 2 Table 2 Table 2


40

Calculated residual concentrations of NH4+-N, NO2

--N, NO3--N in

the anoxic and aerobic reactors vs. experimental results

HRT Anoxic reactor Aerobic reactoranoxic aerobic NH4

+-N NO2--N NO3

--N NH4+-N NO2

--N NO3--N

Run Q reactor reactor Rs Rm exp. calc. exp. calc. exp. calc. exp. calc. exp. calc. exp. calc.(L/d) (h) (-) (-) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

1 15 8.0 19.2 1 0 56.4 59.3 0.7 4.3 3.4 ~ 0 1.3 1.1 9.2 10.9 41.2 48.7

2 15 8.0 19.2 1 2 29.4 30.7 0.6 8.3 6.5 ~ 0 2.1 1.6 0.1 11.0 27.3 24.9

3 30 4.0 9.6 1 1 42.7 39.8 0.1 2.7 3.0 9.4 6.0 1.2 0.4 6.8 35.1 41.5

4 30 4.0 9.6 1 2 33.6 29.9 0.4 9.1 3.9 6.3 7.9 0.9 0.9 11.5 26.4 31.2

5 50 2.4 5.8 1 0 61.0 59.4 1.1 4.6 1.3 ~ 0 9.5 1.1 3.2 5.7 47.8 56.1

6 50 2.4 5.8 1 1 42.1 40.0 9.1 9.0 8.5 12.0 10.8 1.2 0.9 6.8 49.5 50.9

7 50 2.4 5.8 1 2 36.5 30.4 6.0 4.6 25.1 31.7 11.2 1.3 0.1 7.2 59.0 56.8

8 60 2.0 4.8 1 1 49.6 47.5 10.4 20.5 8.5 ~ 0 16.5 12.4 5.2 12.8 46.1 40.8


41

Calculated NH4+-N removal efficiency vs. experimental NH4

+-N

removal efficiency in the single-sludge nitrogen removal system.

Experimental NH4+-N removal efficiency (%)

60 65 70 75 80 85 90 95 100

Cal

cula

ted

NH

4+-N

rem

oval

effi

cien

cy (

%)

60

65

70

75

80

85

90

95

100

+ 10% dev.

- 10% dev.

% dev. of removal efficiency=(Calc. - Exp.)/Exp. x 100%


42

Calculated TN removal efficiency vs. experimental TN removal efficiency in the single-sludge nitrogen removal system.

Experimental TN removal efficiency (%)

30 35 40 45 50 55 60 65 70 75 80

Cal

cula

ted

TN

rem

oval

effi

cien

cy (

%)

30

35

40

45

50

55

60

65

70

75

80

+ 15% dev.

- 15% dev.

% dev. of removal efficiency=(Calc. - Exp.)/Exp. x 100%


1 生物反應器之基質降解動力學 kinetics of substrate degradation in biological reactors...

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