Post on 19-Apr-2020
Removal of Endocrine Disrupting Compounds from Urban Waste
Water using a novel process combining PAC (Powder Activated
Carbon) and ballasted clarification
➢ Actiflo® Carb
▪ Process descriptions
▪ Applications
▪ References
➢ Micropollutants within urban waste water
▪ A wide range of pollutants and concentration
▪ Typical performance data of biological waste water plants
➢ Micropollutants removal with Actiflo® Carb
▪ Process descriptions
▪ First References
▪ Perspectives using Frogbox®
2
Agenda
Actiflo® Carb
Proces description, usages and
references
o Ballasted clarification:o Short floculation time
o High clarification rate : 40 to 60 m/h (waste water)
o Benefits of recirculated PACo Constant availability of PAC for adsorption
o Continuous removal
1
2
3 4
5
67
1 = New PAC2 = PAC reactor3 = Coagulation4 = Flocculation 5 = Clarifier6 = Cycloning PAC removal7 = PAC recirculation
PAC under microscope
Process descriptive
• Natural Organic Matter
• Disinfection By Products
• Pesticides (atrazine, metaldehyde, DEA...)
Drinking water
• Endocrine Disruptors (hormones...)
• Drugs residues (antibiotic, anti-inflammatory, anti-epilectic...)
• Biocides
Waste water
Any pollutants with an affinity with PAC
Over 12 years of experiences
Applications
Corporate Municipal Marketing - September 2016 6
Parker WSD, CO, (38 MLD)
Indianapolis, IN, (91 MLD) Medias, Romania
(16 MLD)
Huntsman, China, (1 MLD)
Harpeth VUD, Nashville, TN,
(90 MLD)
Rexam Plastic, China,
(0.2 MLD)Guangzhou,LGInd.Park China,
(36 MLD)
Beash Dam, Saudi Arabia
(31 MLD) Rizal Prov. Gr. Manila Philippines (77 MLD)
Drinking Water (40 Ref / (total 1,138 MLD)Municipal Wastewater ( 5 Ref. / (total 446 MLD)Industrial Water & WW ( 6 Ref./ (total 76 MLD))
DSM NUTRITIONAL, F (2.5 MLD)
Tongxiang, China(66 MLD)
Fuyang, China(250 MLD)
Jiaxing, China(2x50 MLD)
Design & Build
Solutions
France30 Refs
(680 MLD)USA
4 Refs(236 MLD)
China12 Refs
(619 MLD)
A world wide extension
Actiflo® Carb – Drinking water plants in operation
Surface water with colour and Algae
TOC 3 to 6 mg/l & pesticides (50 to 75% removal)
µ Coagulation
Geosmin & MIB Tests Results
Geosmin (in) Geosmin (out)
MIB (in) MIB (out)
Ge
osm
in
(mg
/l)
MIB
(m
g/l
)
IN (ppb) Out (ppb)
Removal (%)
Atrazine 0.36 0.05 86
DEA 0.26 < LQ > 93
DEDIA 0.37 0.03 92
Isoproturone 0.40 < LQ > 98
Acetochlorine 0.77 < LQ > 94
Bentazone 0.37 0.04 89
Glyphosate 0.23 < LQ > 68
Acetochlorine 0.22 < LQ > 68
Actiflo® Carb – Moses Indianapolis
Actiflo® Carb
for pesticides removal
Pesticide Removal : testing under “live” conditions
10
o Dosing of pesticides in the raw water (reservoir) to simulate peaks of concentrations
o Target concentration in the raw water: 0.3 µg/L
Compounds Inlet T +1h
Outlet T + 1h
% removal Outlet T + 24h
% removal
[mg/L] [mg/L] [%] [mg/L] [%]
Atrazine 0.39 n.d. >95 n.d. >95
DEA 0.34 n.d. >94 n.d. >94
DEDIA 0.36 n.d. >94 n.d. >94
Isoproturon 0.66 n.d. >97 n.d. >97
Acetochlore 0.81 n.d. >97 0.24 70.4
Bentazone 0.27 n.d. >92 0.03 89.0
Glyphosate 0.35 n.d. >77 n.d. >77
AMPA 0.46 n.d. >82 n.d. >82
Eff. Removal > 77 to 97%n.d.: below detection level
Pesticides removal
Spiking program
• Pesticide spiking changed each day (up to 1.5 µg/L)• Metaldehyde, carbetamide, metazachlor and propyzamide
• Main conditions target for each week
12
Inlet Load, PAC dosing
Target: Test upper limits of Actiflo®Carb process
Actiflo® carb (most recent tests)
Trials in 2015 for Metaldehydes removal: North Mymms WTW with Affinity Water – DTP support of VWT (UK) for Metaldehyde (CH3CHO)4
Particularly challenging compound for traditional technologies eg GAC LogKow < 0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
15/4/15 9:10 16/4/15 9:20 16/4/15 14:00 16/4/15 16:00 17/4/15 11:00
Met
alde
hyde
con
cent
rati
on (µ
g/L)
Date
North Mymms phase II - Actiflo®Carb - Metaldehyde concentrationWeek 1
Raw Water Inlet Actiflo® Carb Outlet Actiflo® Carb
0.0090.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
28/4/15 13:10 28/4/15 14:45 29/4/15 15:15 30/4/15 12:15 30/4/15 14:00 1/5/15 12:00 10/5/15 13:10
Conc
entr
atio
n (µ
g/L)
Date
North Mymms phase II - Actiflo® Carb - Total Pesticide concentrationWeek 3
Raw water Inlet Actiflo® Carb Outlet Actiflo® Carb
0.031
2018 America’s Sales Meeting 7
Micropollutants in urban waste water
Pharma residuals during 2010 - 2011
15
N
FRANCE
Paris
Marne
Seine
STEP
Marne Aval
75 000 m3.j-1
STEP - Seine Amont
600 000 m3.j-1
STEP - Seine Centre
240 000 m3.j-1
STEP - Seine Aval
1 700 000 m3.j-1
10 km
STEP - Seine Grésillons
100 000 m3.j-1
Sites de prélèvement en Seine
Stations d’épuration du SIAAP
Déversoirs d’orages SIAAP
1
23
4
5
6
7
1
2
Oise
Pharma residuals during 2010 - 2011
16
Co
nce
ntr
atio
n m
édia
ne
(ng.
l-1)
Fréqu
ence d
e détectio
n (%
)
1
10
100
1000
Sufa
chlo
rpyr
idazi
ne
Sulfa
méra
zin
e
Sulfa
méth
oxa
zole
Ery
thro
myc
ine
Spiram
ycin
e R
oxith
rom
yci
ne
Trim
éth
oprim
e A
mpic
illin
e A
moxi
cilli
ne
Oxy
tétr
acy
clin
e C
hlo
rtétr
acyc
line
Tétr
acy
clin
e A
cid
e o
xolin
ique
Cip
rofloxa
cine
Norf
loxacin
e O
floxaci
ne
Para
ceta
mol
Acid
e acé
tyls
alic
yliq
ue
Acid
e s
alic
yliq
ue
Nefo
pam
Dic
lofe
nac
Ibupro
fène
2-h
ydro
xy
ibupro
fen
Kéto
pro
fène
Napro
xène
Carb
am
azépin
e P
rim
idone
Beza
fibra
te F
enofib
rate
Clo
fibra
te G
em
fibro
zil
Acebuto
lol
Méto
pro
lol
Pro
pra
nolo
l S
ota
lol
Bro
mazepam
Dia
zepam
Flu
oxetine
Acid
e d
iatr
izoïq
ue
Co
ncen
trati
on
(n
g/L
)
0
10
20
30
40
50
60
70
80
90
100
Occu
ren
ce (
%)
Max =1200 ng/L
Antibiotiques Analgésiques Anti-épileptiques Hypolipémiants Bétabloquants Antidépresseurs
Produit de
contraste
Overview of some molecules across Paris
17
Flux (g.j-1) Campagne du 20 octobre 2011 (Q Austerlitz = 160 m3.s-1)dfhs
0
1000
2000
3000
4000
5000
6000
7000
8000
Sulfa
mét
hoxa
zole
Spira
micine
Acé
tam
inop
hène
- Par
acet
amol
2-h
ydro
xy ib
upro
fen
Két
opro
fen
Car
bam
azép
ine
Mét
ropr
olol
Sot
alol
Flu
x (
en
g/j
ou
r)
Choisy Bougival Triel
Gradient spatial marqué entre l’amont et l’aval de l’agglomération parisienne
dfhs
0
1000
2000
3000
4000
5000
6000
7000
8000
Sulfa
mét
hoxa
zole
Spira
micine
Acé
tam
inop
hène
- Par
acet
amol
2-h
ydro
xy ib
upro
fen
Két
opro
fen
Car
bam
azép
ine
Mét
ropr
olol
Sot
alol
Flu
x (
en
g/jo
ur)
Choisy Bougival Triel
The context: typical WwTW performances
18
Verschiedene Quellen (1996-2010) aus Beier, S. et al. 2010
20 à 40% removal
depending on molecules
Hospitals
Inlet
Outlet
Rivers
Drinking water
12 months operational study with SIAAP*
• Organisation & scientific plan
– To operate on a real plant
– 138 micropolluants analysed
WwTW Seine Aval (Achères) 6 million
Pop. eq. – removal C/N/P
Sand and
grease catcherScreening
Seine river
Sewer
Settling
Pré-treatment
Treated water
Primary treatment
Carbon biological treatment (activated sludge)
Phisico-chemical
lamellar settling
Activated sludge tank Secondary settling
Total nitrification
Air
Nitrogen biological treatment (bioflters)
Denitrification
Daily monitoring
TSS, DOC, BOD, DOC, TKN, NO3, NO2, Pt, P-
PO4, Colour , Turbidity, Abs. UV 254 nm
Pharmaceutical and Hormones
Antibiotiques (humains et vétérinaires),
analgésiques, bétabloquants, hypolipémiants,
antidépresseurs, antiépileptiques, diurétiques,
antifongiques, hormones
Other micropollutants
HAP, solvants chlorés, Alkylphénols,
herbicides/insecticides, acides perfluorés,
bisphénol A, Métaux
MEDICAMENTS HUMAINS MEDICAMENTS VETERINAIRES HORMONES DIVERS
Naphtalène Alachlore Metronidazole Florfenicol α oestradiol PFOA
Acénaphtylène Atrazine Trimethoprim Sulfanilamide β oestradiol PFOS
Acenaphtène Chlorfenvinphos Sulfamethoxazole Dicyclanile Estrone Bisphénol A
Fluorene Diuron Ofloxacine Sulfadiazine Estriol
Phenanthrene Isoproturon Ciprofloxacine Sulfathiazole Norethindrone
Anthracene Pentachlorophénol Roxithromycine Marbofloxacine Androstenedione
Fluoranthene Simazine Paracétamol Ampicilline Gestodène
Pyrène Trifluraline Kétoprofene Norfloxacin Testosterone
Benzo[a]anthracene HCH alpha Diclofenac Tétracycline Levonorgestrel
Chrysène HCH béta Ibuprofène Oxytetracycline Progesterone
Benzo[b]fluoranthène HCH gamma Naproxen Sulfabenzamide
Benzo[k]fluoranthène HCH delta Acide salicylique Danofloxacine
Benzo[a]pyrène Chlopyrifos Aténolol Enrofloxacine
Indeno[1,2,3-cd]pyrène Aldrine Propranolol Orbifloxacine
Dibenz[a,h]anthracène Isodrine Fenofibrate Difloxacin
Benzo[ghi]perylène Endosulfan alpha Bezafibrate Sulfadimethoxine
1,2,4-trichlorobenzène DDE pp Fluvoxamine Chlortetracycline
Hexachlorobutadiène Dieldrin Oxazepam Penicilline G
Hexachlorobenzène Endrin Lorazepam Tylosine Tartrate
BPA DDD pp Carbamazepine Erythromycine
Nonylphénol DDT op Furosemide Monensin
4-nonylphénol Endosulfan béta Econazole Narasin
Octylphénol DDT pp Sulfameter
Para-ter-octylphénol Sulfadimerazine
LISTE DCE
Micropolluants organiques
HAP Herbicides / insecticides Antibiotiques Bétabloquants Antidépresseurs / anxiolytiques Diurétique HormonesSolvants chlorés Alkylphénols Analgésiques Hypolipémians Antiépyleptique Antifongique Perfluorés
Often found Seldom foundAlways
found
Micropollutants analysed
Box plot final effluent quality
SO4Cl F AOXSr Fe Mn Zn Ba Al
1
10
100
1000
10000
Co
ncen
trati
on
s (
un
ités l
og
)
Minimum/Maximum
Ni V Cu Co Sb Cr Pb Ag Cd0,001
0,01
0,1
1
10
Co
ncen
trati
on
s (
un
ités l
og
)
Résultats métaux
(4 campagnes – 2
configurations, 11 campagnes
en attente de résultats)
Faible variabilité des
concentrations et ordres de
grandeur conformes aux
suivis RSDE des usines du
SIAAP
mg/
L
µg/L
µg/L
0,1
1
10
100
1000
10000
0,1
1
10
100
1000
10000
Minimum/Maxi…
Box plot organic micropollutants
0,1
1
10
100
1000
10000
Co
nce
ntr
atio
ns
(un
ité
s lo
g)D
iclo
fen
ac
Ké
top
rofe
ne
Par
acé
tam
ol
Nap
roxe
n
Ibu
pro
fèn
e
Ofl
oxa
cin
e
Sulf
ame
tho
xazo
le
Trim
eth
op
rim
Cip
rofl
oxa
cin
e
Ro
xith
rom
ycin
e
Me
tro
nid
azo
le
Até
no
lol
Pro
pra
no
lol
Oxa
zep
am
Lora
zep
am
Car
bam
aze
pin
e
Be
zafi
bra
te
No
rflo
xaci
ne
Eryt
hro
myc
ine
Sulf
adia
zin
e
Estr
on
e
Bis
ph
én
ol A
PFO
S3
PFO
AP
ara
-ter-
octy
ph
én
ol
Diu
ron
Atr
azin
e
Analgésiques
Ab humains
Bêtabloquants
Anti-déprésseurs
Antiépileptiques
Hypolipémiants
Ab vétérinaires
Hormones
Bisphénol A
Perfluorés
DCE - herbicides
ng/l
Plus forte variabilité des concentrations
Actiflo® Carb
Micropollutants removal
o Avranches (France) – Pilot trials
o 18 months Actiflo Carb (2010 – 2012)
o PAC alone and combined with O3
o Industrial prototype – Cham (Lucerne, CH)
o 6 months trials in 2011 in cooperation with :
o Industrial unit 50 to 100 m3/h
o Industrial prototype – Milwaukee (USA)
o 4 months trials in 2011
o Industrial unit 50 to 100 m3/h
o Aachen (Germany) – Pilot trialso 6 months trials - RWTH Aachen
Over 10 pilot plants trials since 2010
0
20
40
60
80
100
120
Elim
inat
ion
%
Norit SAE Super PICA AFP23 CSC HPC HZ 1050
Average 55%Average 69% Average 69%
1. Analyses by Eawag (2011)
o CAP dose 10 ppm, CAP concentration in reactor 1 – 2 g/l
o Contact time 10 mn
Re
mo
val[
%]
Various PAC tested (Norit, Jacobi, Calgon, etc…)
➢ Actiflo® Carb : micropollutants removal
Micropollutants removal
26
Micropolluants
Abattement en %Sites et quantités de CAP
Aachen Achères Avranches Bruxelles Lucerne
10 ppm 20 ppm 30 ppm 5 ppm 10 ppm 15 ppm 20 ppm 20 ppm + O3 15-20 ppm 10 ppm
Atenolol / / / 38 47 67 90 92 / 76Metoprolol 88 91 95 / / / 69 76 82 85Propanolol / / / 75 88 95 / / 88 /
Clarithromycine 37 70 63 / / / / / 79 76Sulfamethoxazole 28 68 74 28 39 39 77 88 69 45
trimethoprim / / / 68 72 80 / / 79 95Diclofenac 57 89 91 38 45 60 82 97 71 65Bezafibrate / / / 20 15 30 / / 31 78
Carbamazepine 83 94 96 40 60 72 98 99 82 76
0,1
1
10
100
1000
10000
• Inlet quality : Pharma residues and hormones
0,1
Co
nce
ntr
ati
on
s n
g.l
-1
Analgésiques Antibiotiques
1
10
100
1 000
10 000
Analysis results over 24 campaigns of sampling
0
20
40
60
80
100Analgésiques Antibiotiques
Ab
att
em
en
ts (
%)
0
20
40
60
80
100
Average removal over 33 molecules :
> 70% for 5 molecules, [40 – 70%] for 11 molécules and < 40% for 9 molécules
Median removal
Synthesis over 6 molecules (cumulative concentration)
0
10
20
30
40
50
60
70
80
90
100
60-5-0 XX-10-0 40-15-0
ab
att
em
en
t m
oyen
(%
)
Vs PAC dose rate
Molecules of
reference
Diclofenac
Ibuprofene
Sulfamethoxazole
Atenolol
Propanolol
Carbamazepine
Mass removal
Actiflo® Carb
“hard” COD removal
Municipal wastewater
China Zhejiang Fuyang TertiaryActiflo Carb operation as needed to reduce refractory COD from nearby
paper mill
Industrial wastewater
ChinaShandon
gHuntsman, Qingdao HPI / CPI
Tertiary; removal of refractory COD from WW with dye chemicals used
in textile industry; very high COD up to > 900 mg/l
Industrial wastewater France
haut-rhin
DSM NutritionalProducts France, Village-
Neuf (close to Basel, Switzerland)
PharmaTertiary treatment after AS for TSS &
refractory TOC/COD removal; and pharma micropoll removal
Industrial wastewater
Italy SICRaffineria di Milazzo,
Milazzo (Sicily)HPI / CPI
Secondary clarification of MBBR effluent with Actiflo Carb; removal of refractory COD up to 200 mg/l;
reuse for fire protection water system
Actiflo® Carb for industrial effluents (« Hard COD »)
DSM references : Mulhouse, France
Date Débit alim Vitesse MES alim COT alimDosagepolymère
Dosage FeCl3
Dosage CAP
Type CAP pH rejet MES rejet COT rejet
m3/h m/h mg/l mg/l mg/l mg/l g/l upH mg/l mg/l
21/04/2015 60 30 500 40 0,7 100 _ _ 7,0 7
22/04/2015 35 12 240 30 0,7 100 _ _ 7,4 9
22/05/2015 65 32 65 140 1,5 250 1 HCAP2 6,9 19 15
08/06/2015 65 32 30 1,5 250 1 HCAP2 6,5 21
09/06/2015 65 32 15 1,5 350 1 HCAP2 6,4 25
22/06/2015 70 35 250 140 1,5 350 1 CPL 6,9 14 25
23/06/2015 70 35 140 150 1,5 350 1 CPL 6,8 13 30
29/06/2015 70 35 120 200 1,5 550 1,7 CPL 6,3 12 25
Taux de sable réglé à 7-10 g/L
Synthèse des essais de mise en route
DSM : results (Commissioning)
Messages to take home
➢ TOC & Colour Removal
▪ TOC < 2 ppm
▪ When used in combination with upstream clarification UVT > 90 / 92%
➢ Taste & Odour Removal
➢ Pesticides Removal
➢ Algal Toxins removal
➢ THM Removal when using Actiflo Carb; Filtraflo Carb or Opacarb MF
▪ THMs are formed by the reaction of free chlorine with natural organic matter (NOM), man-made organic
matter or bromide
▪ The NOM responsible for THMs consists of humic and fulvic acids produced by decaying organic matter
▪ Chloroform is typically found at higher concentrations in potable water than any other THM.
▪ THM5 < 100 ppb and generally below 50 ppb
These processes deliver :
35
Many thanks for your attention
We welcome your questions
36