we deliver phosphorus made in europe
TRANSCRIPT
We deliver Phosphorus made in
Europe
Recovery of Phosphorus from Sewage Sludge and Subsequent Purification Using Reactive Extraction17th SFGP Congress, 15-17.10.19, Nantes, France
Pfennig A., Shariff Z.A., Fraikin L., Léonard A.
PEPs - Department of Chemical Engineering, Université of Liège
agenda
• introduction
• PULSE process concept
• process development
– SLE modelling
– cascaded option tree
• experimental results
• demonstrator
• summary
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 2
introduction
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 3
• essential element for all forms of life & finite resource
• more than 80% P produced used in agriculture
rock phosphate
EU sourcing (domestic production + imports) of phosphate rock, average 2010-2014 (Eurostat COMEXT database, 2016)
introduction: EU crictical
materials
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 4
introduction : fraction of P-
loss in waste for EU-27
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 5
Kimo C. etal., 2016. Phosphorus flows and balances of the European Union Member States, Science of The Total Environment, Volume 542, Part B
introduction : P recycling
• P-recovery potential from sewage sludge for EU > 25%
• German legislation (2017) – either recovery of P > 50% or reduction of P in sewage sludge to <2% by 2029
• new EU fertilizer regulation: certain types recycled P allowed to be used in fertilizers (published June 2019)
– first EU product legislation to confer “End of Waste” status
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 6
introduction: Phos4You project
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 7
• accelerate the exploitation of P
recovery in sewage and close the
gap between P-recovery and
recycling.
• 12 partners from 6 EU member
states and Switzerland
• demonstrate 7 P-recovery
technologies
• ULiège: demonstrate PULSE
process and LCA for all the
technologies
introduction : Phos4You
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 8
demonstrator country source process
EuPhoRe GmbHGermany (digested)
sludgepyrolysis followed by incineration
Lippeverband with REMONDIS Aqua
Germany sewage sludge ashes
chemical leachingfollowed by ion-exchange
PULSE process, ULiégeBelgium dried sludge chemical leaching,
reactive extraction, precipitation
IRSTEA and VéoliaFrance sewage sludge bio-acidification, ion-
exchange, precipitation
Veolia with CIT and GCU France wastewater precipitation
GCU Scotland wastewater P uptake by algae
ERI and Veolia Scotland wastewater adsorption of P
CIT: Cork Institute of Technology; GCU: Glasgow Caledonian University; ERI: Environmental Research Institute
PULSE (Phosphorus University of
Liege Sludge Extraction) process
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 9
acid
organicsolventbase/Ca
drying leaching separation
reactiveextraction
re-extractionCaP
solid waste
metals
precipitation
dewateredsludge
wastewater
re-extraction agent/NH3
P + impurities
PULSE process development
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 10
PULSE process concept – based
on PASCH process (TU Aachen)
design and construction of PULSE
demonstrator
• experiments to evaluate
process option/parameters
• modelling tool development &
validation
cascaded option trees evaluation –
final PULSE process
PUSLE demonstrator operation
inputs from quality assesment &
LCA
optimization with lab experiments
& modelling
scale up design of PULSE
technology
modelling: Solid-Liquid-Liquid
Equilibrium
• aqueous phase speciation:
– mass balance
– law of mass action
– charge balance
• solid precipitation:
– saturation index
• activities instead of concentration to account for ionic
interactions
• efficiency of reactive extraction with organic solvents
– determination of extraction parameters by data fitting
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 11
modelling: SLE & speciation
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 12
-1 0 1 2 3 4 5 6 7 8 91E-6
1E-5
1E-4
0.001
0.01
0.1
1
CaHPO4
FeCl4-
FeHPOFe2+
PO4
3-
CaHPO4(S)
AlPO4(S)
FePO4(S)
CaH2PO
4+
FeH2PO
4
2+
H3PO
4
H2PO
4-
HPO4
2-
FeH2PO
4+
Ca2+
Cl-
Al3+
Fe3+
concentr
ation m
ol/l
pH
modelling tool: non-linear data
fitting
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 13
1 100.0
0.2
0.4
0.6
0.8
1.0
degre
e o
f iron e
xtr
action
usin
g A
336+
TB
P
Cl- concentration mol/L
model
measured
fitted parameter log Kext
= 3.2
cascaded option tree: drying
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 14
P-recovery
from sludge
drying
conditions
- dewatered sludge 0 0 0 -
+ convective air drying + 0 0 0 0
slow drying (no air) + 0 0 0
extraction compatibility
filtrability
P leaching
operation cost
transport/handling/storage
not evaluated
Bednarz, A. et al. 2014. Use of Cascaded Option Trees in Chemical-Engineering Process Development. Chem. Ing. Tech. 86, 611-620
- not feasible
0 acceptable
+ good
sludge drying
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 15
dried sludge (>95% DM)
dewatered sludge (20-22% DM)
• biologically unstable – storage / transportation issues
• pasty – requires 2 -3 times more water/acid for leaching (0.06€/mol acid)
• difficult to filter at low pH
• stable solid – easier storage / transportation• mineral like – less water / acid for required
for leaching (drying cost = 0.1 – 0.21 €/kg dewatered sludge)
• easier to filter
P leaching- wet/dry sludge
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 16
0.0 0.2 0.4 0.6 0.8 1.00.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
rapid convective drier with air circulation (65 - 98% DM)
wet sludge (2 - 21% DM)
slow drying 80 -100°C (>98% DM)
oven dried without air circulation 105°C (>98% DM)
deg
ree o
f P
le
ach
ing
pH
P leaching- different acids and pH
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 17
-1 0 1 2 3 4 5 60.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
degre
e o
f P
leachin
g
equilibrium pH
HCl
H2SO
4
HNO3
HCl+HNO3
HCl+H2SO
4
HNO3+H
2SO
4
H3PO
4
model
P leaching- organic & inorganic P
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 18
*According to The standards, measurements, and testing (SMT) procedure for phosphorus fractionation in freshwater sediments, developed within the framework of SMT Program of the EC
32.43%
67.57%
in organic fraction of P
organic fraction of P
sludge leach liquor
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 19
P Fe K Mg Ca Al Mn Zn Na Cr Cu Ni Co Pb Cd0.1
1
10
100
1000
10000
ce
nce
ntr
atio
n (
mg
/L)
in le
ach
liq
uor H2SO4
HCl
reactive extraction with HCl
conc. 1mol/L
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 20
D2E
PHA
TBP
D2E
PHA-T
BP
A33
6
A33
6-D2E
PHA
A33
6-TBP
A33
6-D2E
PHA-T
BP
0
20
40
60
80
100
pe
rce
nta
ge
of
extr
actio
n
P
Ca
Cd
Cu
Pb
Zn
Fe
mixing
settling
Fe extraction with A336-TBP at
varying Cl- concentrations
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 21
Alamine 336:
𝐹𝑒𝐶𝑙4−+ 𝑅3𝑁𝐻
+𝐶𝑙−= 𝐹𝑒𝐶𝑙4𝑅3𝑁𝐻+ 𝐶𝑙−
TBP:
𝐹𝑒𝐶𝑙4−+ 𝑇𝐵𝑃= 𝐹𝑒𝐶𝑙4𝑇𝐵𝑃
0 1 2 3 4 5 6 7 8 9 10 110.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0degre
e o
f iron e
xtr
action
Cl- concentration mol/L
10%Al336
+10%TBP
(O:A=1)
10%Al336
+10%TBP
(O:A=2)
15%Al336
+15%TBP
+1%Exxal
(O:A=1)
15%Al336
+15%TBP
+1%Exxal
+H2O2
(O:A=1)
0.0
0.2
0.4
0.6
0.8
1.0
degre
e o
f iron e
xtr
action
Fe extraction with different extractant
concentrations and with H2O2
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 22
Fe extraction extraction with
and without H2O2
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 23
before
extraction
after
extraction
0
1
2
3
4
5
no H2O
2
Fe2+
Fe3+
tota
l iron c
oncentr
ation g
/L
before
extraction
after
extraction
with H2O
2
Fe3+
Fe2+
reactive extraction of Fe with
A336 + TBP
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 24
1 2 3 4 5 6 70.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
extraction without H2O
2
extraction with H2O
2
deg
ree o
f iron
extr
actio
n
Cl- mol/L
Alamine 336:
𝐹𝑒𝐶𝑙4−+ 𝑅3𝑁𝐻
+𝐶𝑙−= 𝐹𝑒𝐶𝑙4𝑅3𝑁𝐻+ 𝐶𝑙−
TBP:
𝐹𝑒𝐶𝑙4−+ 𝑇𝐵𝑃= 𝐹𝑒𝐶𝑙4𝑇𝐵𝑃
re-generation of solvent
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 25
after centrifugation
before mixing
during mixing
phase separation
organic solvent + metals
aqueous phase(NH3 + NH3HCO3)
regenerated organic solvent
aqueous phase + metal precipitates
2 stage extraction before
precipitation of product
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 26
P Fe0
1
2
3
4
5
after
2nd
extr
action
after
1st extr
action
co
nce
ntr
atio
n g
/L
raw
liq
uor
PULSE product
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 27
Comp. PULSE Legislativelimit
P2O5 29.2% > 3 %
CaO 21.7 % > 1.5 %
Total C 6 % -
Al2O3 2.61 % -
MgO 1.84 % > 1.5 %
Fe 0.325 % -
Mn 10800ppm -
Cr 1530 ppm -
Cu 294 ppm 600 ppm
Ni 51.6 ppm 120 ppm
Pb 38,8 ppm 150 ppm
Zn 8.97 ppm -
Cd 0.735ppm 60 ppm
Hg 0.054 ppm 2 ppm
leaching of dried sludge
filtration
metal removal by reactive extraction
CaP precipitation with NaOH (pH = 6 - 7)
P recovery potential
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 28
dried sludge leaching reactive
extraction
precipitation0
20
40
60
80
100
13
7 g
/kg
23
g/k
g
P r
eco
very
po
ten
tial
inorganic P
organic P
total P recovery
summary
• no significant difference between P leaching from wet or dry sludge
• P leaching depends only on pH and not on the type of acid
• extraction of metals at low pH only achieved with Alamine 336
• metals concentration in product is within the limits set by the EU fertilizer regulations except in case of Cr
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 29
further work
• lab scale optimization
• construction of demonstrator – 100kg/day
of dewatered sludge capacity
• operation of demonstrator in Belgium,
Germany, Ireland and Scotland
• LCA and scale up design
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 30
further work: PULSE demonstrator
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 31
drying +
crushing
leaching+
filtration
reactive extraction
precipitation + filtration
acknowledgements
• financing– Interreg North-West Europe
– SPW Région Wallonne
• analytics– Faculty of Bioscience Engineering, Ghent University,
Belgium
– Prayon S.A., Belgium
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 32
16th October 2019, Nantes | 17th
SFGP | Andreas Pfennig | PEPs -
ULiège | Slide n°
33
Recovery of Phosphorus from Sewage Sludge and Subsequent Purification Using Reactive Extraction17th SFGP Congress, 15-17.10.19, Nantes, France
Pfennig A., Shariff Z.A., Fraikin L., Léonard A.
PEPs - Department of Chemical Engineering, Université of Liège
references
• Kimo C. van Dijk, Jan Peter Lesschen, Oene Oenema, 2016. Phosphorus flows and balances of the European Union Member States, Science of The Total Environment, Volume 542, Part B
• http://www.nweurope.eu/projects/project-search/phos4you-phosphorus-recovery-from-waste-water-for-your-life/
• Doetsch, P., Pinnekamp, Johannes, Montag, D., Rath, W., Grömping, M., 2010. Rückgewinnung von Pflanzennährstoffen, insbesondere Phosphor aus der Asche von Klärschlamm (Abschlussbericht PASCH). Institut für Siedlungswasserwirtschaft der RWTH Aachen, Aachen.
• Bednarz, A., Rüngeler, B., Pfennig, A., 2014. Use of Cascaded Option Trees in Chemical-Engineering Process Development. Chem. Ing. Tech. 86, 611-620.
• EC, 2019. Proposal for a REGULATION OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL laying down rules on the making available on the market of CE marked fertilizing products and amending Regulations (EC) No 1069/2009 and (EC) No 1107/2009.
16th October 2019, Nantes | 17th SFGP | Andreas Pfennig | PEPs - ULiège | Slide n° 34