We deliver Phosphorus made in Europe

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.

[email protected]

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


• 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


introduction : fraction of P-

loss in waste for EU-27


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


introduction: Phos4You project


• 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


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


acid

organicsolventbase/Ca

drying leaching separation

reactiveextraction

re-extractionCaP

solid waste

metals

precipitation

dewateredsludge

wastewater

re-extraction agent/NH3

P + impurities

PULSE process development


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


modelling: SLE & speciation


-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


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


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


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


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


-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


*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


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


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


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


Fe extraction extraction with

and without H2O2


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


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


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


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


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


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


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


further work: PULSE demonstrator


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°

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.

[email protected]

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.


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