TERTIARY TREATMENTS

Prof. Dr. D. A. Aznar Jiménez

Dpto. C. e I. de Materiales e I. Química
UNIVERSIDAD CARLOS III DE MADRID
TERTIARY TREATMENT
•NATURE
•Physical processes.
•Chemical processes.
•Biological processes.

•OBJECTIVES
• Removal of specific substances

•RESULTING FLOWS
•treated aqueous effluent
•sludge
•reusable substances
•Gases
NITROGEN AND PHOSPHOROUS REMOVAL
•MACRONUTRIENTS
hC, H, O
•MESONUTRIENTS
hN, P, S, Ca, Mg, Na, K, Si
•MICRONUTRIENTS
hFe, Cu, Mo, Mn, Zn

[Nutrient] ↓ growth inhibited

•MACRONUTRIENTS
Can be taken from environment (CO2, H2O)
•MESONUTRIENTS
Best option. N (3-10%), P (0,5-1%)
•MICRONUTRIENTS
Very small quantities, total removal very expensive
NITROGEN AND PHOSPHOROUS REMOVAL

ammoniac nitrogen (10-50 mg/L)

Total Kjeldahl Nitrogen (TKN)

Organic nitrogen (5-35 mg/L)

Total nitrogen (Nt)

Nitrites

Oxidised nitrogen (1% Nt)

Nitrates
NITROGEN REMOVAL (I)
•PHYSICO-CHEMICAL METHODS.
•Chlorination breakpoint
Formation of free chlorine
Destruction of
and presence of
organochlorinated
organochlorinated not
and chloramines
Destruction of destroyed
residual Formation of
chlorine with organochlorinated and d
ine e
Residual chlorine (mg/l)

reduction
chloramines b
compounds
om rin
nd c chlo
a l
ee ua

chlorine
residual
Fr esid

Free
r
ine
hlor
lc
idua
re s
ed Breakpoint
bin

Combined

chlorine
residual
o m
C

Added chlorine (mg/l)

Cl2 + H2O → HCl + HOCl Cl 2

= 8 − 10
NH3 + HOCl → NH2Cl + H2O N NH 3
NH2Cl + HOCl → NHCl2 + H2O mg CaCO 3
= 14,3
NHCl2 + HOCl → NCl3 + H2O mg N NH 3
NITROGEN REMOVAL (II)
•PHYSICO-CHEMICAL METHODS.
Air stripping Air, NH3
Wasterwater
Desorption process
NH4+ + OH- → NH3 + H2O
Countercurrent system Sedimentation
Treate
pH ≈ 10 NH3 + H2O NH4+ + OH- Floccul
at. effluen

Qair = 2,5 m3/L

CaO + H2O → Ca(OH)2
Performance ≈ 90%
Calci
ner

Air

Lime sludge

Ca(CO3)2 + ∆ → CaO + CO2

Lime
recovery
NITROGEN REMOVAL (III)
•PHYSICO-CHEMICAL METHODS.
•Ion exchange
Washing Washing
Carbon

INFLUENT Carbon NH3

Air, NH3
Filtration Zeolite
adsorpt stripping
ion exchange
Waste with air Air

EFFLUENT
Waste

Waste Lime
NITROGEN REMOVAL (IV)
•BIOLOGICAL METHODS.

NH 4+ + 2O 2 ⎯Nitrosomas
⎯ ⎯⎯→ 2H + + NO −2 + 1 2 O 2 + H 2 O ⎯Nitrobacte
⎯ ⎯⎯r → NO3−

NO 3 - + 1,08 CH 3 OH + H + Æ 0,065 C 5 H 7 O 2 N + 0,47 N 2 + 0,76 CO 2 + 2,44 H 2 O

•Anoxic conditions (anaerobic)

•Provide organic material BOD5

Age of sludge (days)

NITROGEN REMOVAL (V)
•BIOLOGICAL METHODS.
NITRIFICATION DENITRIFICATION

Carbon source for cellular synthesis Inorganic Organic

Oxidation organic
Energy source for cellular synthesis Oxidation N(NH4)
material
Oxygen source for oxidation
O2 free NO3-
reactions
Medium Aerobic Anaerobic

Microorganisms Aerobic autotrophic Facultative heterotrophic

Associated to oxidised Associated to oxidised
Decrease of the BOD5
NH4+ organic material
Alkalinity consumption Production of alkalinity
Variation of the alkalinity of medium
7 g HCO3-/g NH4+ 4,5 g HCO3-/ g NO3-
Production of biomass 0,16 g SSv / g NH4+ ———

Consumption of free oxygen 4,2 g O2 / g NH4+ ———

Oxygen retrieval ——— 2,85 g O2 / g NO3-

NITROGEN REMOVAL (VI)
Aerobic
Predenitrification Anoxic reactor
Decanter
reactor

Sludge
recirculation Purge

Ludzack-Ettinger Process

Aerobic
Postdenitrification reactor
Anoxic
reactor
Decanter

Sludge
recirculation
Purge
Wuhrman Process
NITROGEN REMOVAL (VII)

Aerobic
Anoxic Aerobic Anoxic Aerobic Anoxic process
process process process process Decanter process Decanter

Sludge
recirculation Sludge

recycle Purge
Purge Aerobic
BARDENPHO Process process RDN Process

Step-feed processes
Aerobic Aerobic Anoxic Aerobic
Anoxic process process process process
Anoxic
process process Decanter

Sludge
recirculation

Step-feed Process Purge

NITROGEN REMOVAL (VIII)
Processes in oxidation channels

Oxidation ditch channel

Orbal
PHOSPHOROUS REMOVAL (I)
•PHYSICAL METHODS : ultrafiltration, reverse osmosis
•CHEMICAL METHODS: precipitation.
Alternatives to addiction of reactants
Aerobic
Primary reactor Secondary Additional
clarifier clarifier clarifier

Sludge

Sludge Recycle Sludge

Purge

¦ Precipitation in the primary clarifier

§ Simultaneous precipitation
¨ Separate precipitation
PHOSPHOROUS REMOVAL (II)
•BIOLOGICAL METHODS.
Anaerobic Aerobic
reactor reactor
Decanter

Sludge recirculation

Purge
A/O Process

Anaerobic Aerobic
decanter reactor
Decanter

Sludge recirculation

EASC Process Purge

NITROGEN AND PHOSPHOROUS REMOVAL
•BIOLOGICAL METHODS.
Anaerobic Anoxic Aerobic
reactor reactor reactor
Decanter

Internal
recirculation

Sludge recirculation
Purge

A2/O Process

Anaerobic Anoxic Aerobic Anoxic Aerobic

reactor reactor reactor reactor reactor Decanter

Sludge recirculation

BARDENPHO Process Purge

NITROGEN AND PHOSPHOROUS REMOVAL
•BIOLOGICAL METHODS.

MAIN BIOLOGICAL METHODS TO REMOVE PHOSPHORUS AND NITROGEN

Method Removes Applied to Sequence Detention Observations
time
N (%) P(%) line (h)
A/O 25 90 Main anaerobic- 2-4 Sludge phosphorous-rich, use
aerobic as fertilizer
PhoStrip 25 95 Auxiliary aerobic- 4-6 Less use of chemicals than in
anaerobic- conventional precipitation
precipitation
Sequencing batch variable variable _____ anaerobic- 3-24 Very versatile process,
reactor (SBR) aerobic-anoxic recommended for small flows
2
A /O 75 90 Main 5-8 Modification of the A/O
process
Bardenpho 80 70 Main anaerobic- 15-20 Recirculation from the 1st
anoxic-aerobic- aerobic step to the anoxic step.
anoxic-aerobic Low production of sludge with
phosphorous.
Orbal 90 30 Main anoxic-aerobic 14-24 Concentric circular channels.
(cyclic) High mineralization
MEMBRANES (I)
PHASE 1 MEMBRANE PHASE 2

Inlet flow
direction

RETAINED PERMEATED

Technique Driving Type of ∅ particle Operation Removes

force barrier (µm) pressure (atm)
Filtration Pressure Inert > 10 1-2 suspended solids
Microfiltration Pressure Inert 0,1-10 1-4 suspended solids,
bacteria, latex, etc.
Ultrafiltration Pressure Inert 0,01-0,1 5-10 Virus, proteins, oil,
colloids, etc.
Nanofiltration Pressure Inert 10-3-10-2 20-40 Colorants, antibiotics,
lactose, etc.
Reverse osmosis Pressure Inert or active 10-4-10-3 30-60 Organic and
inorganic salts
Pervaporation Pressure Inert or active 10-5-10-3 0-1 Separation of solvents

Separation of Pressure or Inert < 10-4 0-1 Separation of gases

gases concentration
Dialysis concentration Inert or active 10-3-10-2 --- Macromolecules,
sales, etc.
Electrodialysis Electric Active 10-3-10-2 --- Deacidification,
potential desalting, etc.
MEMBRANES (II)
REVERSE OSMOSIS : recovery of diluted solutions

[ ]1 < [ ]2 π = 1,12 · T · Σ m
π
P
P > 1,4 + π (Mpa)
Saline water : 4,2-5,6 MPa
Marine water: 7,0-8,4 MPa

[]
MEMBRANES (III)
REVERSE OSMOSIS
Cellulose
Polyamide TFC Polysulfone
acetate
pH 4-7 4-11 2-12 2-12

Tolerance to chlorine Tolerance 0,1 ppm poor poor

Resistance to bacteria None God Good Good

Temperature limit (ºC) 35 38 50-80 70

Rejection (%) 90-80 95-95 97-99,5 90-98

 MEMBRANES (IV)
ELECTRODIALYSIS (ED):
Recovery of concentrated solutions

CONCENTRATE OUTPUT

DILUTE OUTLET
CATHOLYTE OUTLET
A K A K A K A K
ANOLYTE
OUTLET
Λo
+ + + +
M M M M
ANODE CATHOD
+ + M+
M M E
X- X-
X-

X- X- X- X-
D C D C D C D

ANOLYTE INLET CATHOLYTE INLET

DILUTE INPUT
[]
A: anionic membrane CONCENTRATE INPUT
K: cationic membrane
D: dilute compartment
C: concentrate compartment
MEMBRANES (V)
ELECTRO-ELECTRODIALYSIS (EED):
Synthesis of concentrated solutions
∆E = 1,6-2,5 V i = 1000 A·m-2

MOH MB
K HA A
S
S
OH- A-
ANODE
CATHODE
H2O
…… ……
M+
H+

BC AC
200 µm

Saline aqueous solution M+A-

EED cell with 3 compartments with bipolar membranes (BM).

K: monopolar cationic membrane.
A: monopolar anionic membrane.
S: saline compartment.
AC: acid compartment.
BC: basic compartment.
OXIDATION TECHNOLOGIES (I)
z CONVENTIONAL
9 Moderate Temp and P
9 H2O2, Cl2, O3, NaClO, KMnO4, H2O2/Fe2+, …
9 COD > 5000 mg/L
9 Critical variables: pH and Temp
9 Difficult to destroy hydrocarbons and halogenated compounds

z ADVANCED
9 Wet oxidation: High Temp and P
9 Oxidation with supercritical water (T>374 ºC, p>220 atm)
9 Oxidant + UV
9 Electrochemical
9 Solar detoxification
OXIDATION TECHNOLOGIES (II)
Wet oxidation

WASTE TO
BE TREATED EXCHANGER REACTOR AIR or O2
COMPRESSOR

HIGH PRESSURE
PUMP

SEPARATOR N2, CO2,

VAPOUR
OXIDISED LIQUID TO
POST-TREATMENT
OXIDATION TECHNOLOGIES (III)
Wet oxidation
DESTRUCTION EFFICIENCY OF TOXIC CHEMICAL PRODUCTS
PRODUCT TOX. (ºc) TIME (h) Efficacy (%)
Acrolein 275 1 99,96
Acrylonitrile 275 1 99,00
2,4- Dimethylphenol 275 1 99,99
2,4-Dinitrotoluene 275 1 99,74
1,2- diphenylhydrazine 275 1 99,88
Nitrophenol 275 1 99,60
Phenol 275 1 99,80
Formic acid 300 1 99.30
Chloroform 275 1 99,90
Carbon tetrachloride 275 1 99,70
1,2-Dichloroethane 275 1 99,70
n- -Nitrosodimethylamine 275 1 99,60
Hexachlorocyclopentadiene 300 1 99,90
Toluene 275 1 99,70
Dibutyl phthalate 275 1 99,50
Pyrene 275 1 99,95
Policyclic benzene (PCB) 320 2 63,00
DISINFECTION (I)

OBJECTIVE
9Conditioning of consumption water
9Kill pathogens

CLASSIFICATION
9Preoxidation: plant entrance
9Primary disinfection : after filtration
9Secondary disinfection : residual disinfectant
DISINFECTION (II)
DISINFECTANT ADVANTAGES DISADVANTAGES APPLICATION
Effective
Dangerous subproducts
Cheap
pH acid Towards the end: THMS ↓
Chlorine Easy to apply
Does not remove Fe(II) and Secondary disinfectant
Removes NH3
Mn(II)
Primary and secondary disinfectant
Very effective High cost
Without THMS Primary disinfectant
Ozone Before secondary disinfection
Removes organic material Expensive
Oxidant/disinfectant Difficult to apply
Effective virus and bacteria Cannot be used with coloured
Towards the end of the
UV Radiation Without secondary products water, with SS, or high BOD
treatment
Easy to apply Primary disinfectant
Expensive, dangerous
Before filtration
Chlorine dioxide Does not produce THMS subproducts, useless at
Treat with active carbon.
recommended concentrations
Dangerous subproducts
Long residual times Does not remove NH3
Monochloramines At the end of the process
Does not produce THMS Not effective against virus
Only as a secondary disinfectant
Does not produce subproducts
Potassium Removes Fe(II) and Mn (II) Poor disinfectant
Before the filtration
permanganate Easy to apply Does not remove ammonia
Cheap
Partial and accumulated yields (PR, % and AR, %) usually found in the
removal of contaminant load in a effluent treatment plant.

Parameter Primary Secondary Tertiary

treatment treatment treatment

PR AR PR AR PR AR

BOD5 25 25 90 92,5 33 95

SS 72 72 70 91,5 33 95

Phosphorous 12,5 12,5 16,5 25 91,5 94

ADSORPTION
adsorption capacity: amount of
substance that can be adsorbed per
weight or volume unit of adsorbent,

selectivity, tendency that a

substance has to be adsorbed when
in presence of other substances that
can also be adsorbed.

Time

a) b) A Column B Column
Use Use
[B]adsorb [B]adsorb
Regeneration

[B]fluid [B]fluid

Time Time
ADSORPTION WITH ACTIVATED CARBON

 Adsorption system
 Circulation in fixed bed
 Transference of liquid contaminant → solid
 Thermal regeneration of the bed.

REMOVES
 Phenols
 Dyes
 Toxics in general
ABSORPTION / ADSORPTION:

G2 L1 G2 L2
Y2 X1 Y2 X2

Y1 > Y2 Y1 < Y2
X1 < X2 X1 > X2

G1 L2 G1 L1
Y1 X2 Y1 X1

ABSORPTION ADSORPTION
VAPOUR OR AIR STRIPPING

 Desorption system
 Countercurrent flow
Transference of contaminant liquid → gas

REMOVES
 Ammonia
 Solvents (VOCs)
 Volatile substances
GAS WASHING: STRIPPING

 Absorption system
 Bubbling through the liquid
 With or without reaction (neutralization,
oxidation-reduction)
 Transfer of contaminant gas → liquid

REMOVES
 Unpleasant odors

 Solvents (VOCs)
ION EXCHANGE

B+disol B+disol
RES -A +B '
- + +

RES--B++A+

B+disol A+disol B+disol

RES--A++B+→ EXHAUSTION A+disol
RES -B + A →
- + +
RES--B++A+ RES--A++ B+

USE REGENERATION

RES--A+
[B+]RES

TIME
Ionic exchange Columns
Exchange system: anionic,
cationic or mixed
Organic, inorganic and hybrid
resins.
Circulation in fixed bed
Transference de contaminant
liquid → solid

REMOVES
 Metallic ions
 Water softening
 Nitrates
 Ionic organic compounds.
ADJUSTING pH

HOMOGENIZATION

Qacid Qbase

acidic effluent basic effluent

⎛ Qacid ⎞ ⎛ Qbase ⎞
⎜ pH acid ⎟ · ⎜ pH base ⎟
= − log10 ⎝ ⎠ ⎝ ⎠
10 10
pH final
Qacid + Qbase

DOSAGE
OCa CO2

acid effluent basic effluent

 No No Yes
¿Presents medium ¿Needs pH
RAW WATER and coarse solids? adjusting?
¿Presents gas? STRIPPING

Yes Yes
No Gas
PRETREATMENT NEUTRALIZATION

¿Is organic?
No

Yes
Yes
solids SEDIMENTATION ¿Can precipitate? ¿Biodegradable?
No
No Yes
Yes
Oil and
¿Oil and grease? Flotation
Yes grease
solids Filtration ¿Can be filtered?
No
No
Yes
¿Is land available and
Yes lagoon
Is climate warm?
solids Adsorption ¿Can be adsorbed?

No No sludge

Yes
Yes ¿Can be oxidised ¿Are aeration and fast active sludge
oxidation/reduction operation needed? Biological filters
or reduced?

No No sludge

Extraction/ Yes ¿Necesita reducir No ¿Are solids Yes Anaerobic

solids sludge
Evaporation volume? recovered? degradation
No

Wet Oxid/ Yes ¿Need to destroy No

Cinders
incineration residue? TREATED WATER