KajThomsen Phosphorus1298

Recovery of Phosphorus for
Recycling
Kaj Thomsen
CERE, Center for Energy Ressources Engineering
DTU, Technical University of Denmark
Lyngby, Denmark
June 27, 2012 Recovery of Phosphorus for Recycling 2 DTU Chemical Engineering,
Technical University of Denmark
Importance of phosphorus
Phosphorus is found in every cell of all living beings
(ADP/ATP, DNA, bone)
Phosphorus can not be replaced by another compound, it
is a non-renewable resource
Phosphorus is one of the most abundant elements in the
earths crust
The known reserves of high concentration phosphate rock
are being depleted
Lack of phosphorus will cause increase in food prices,
food shortages, geopolitical rifts
Phosphorus has been designated as a strategic mineral
resource by many countries
Peak phosphorus
Hubbert curve by Dana Cordell and Stuart White, Sustainability,
3(2011)2027-2049
Phosphorus as a waste product
Straw and other organic material is increasingly being used for
power and heat generation
Gasification and combustion processes
Much of the phosphorus in the straw ends up in the fly ash
from the combustion
Up to 90% of the fly ash is soluble, inorganic salts
The fly ash cant be deposited in land fills in the European
Union due to its solubility
The fly ash cant be used as a fertilizer due to its content of
cadmium and other heavy metals
This project was started in cooperation with the Danish
company Kommunekemi in order ot solve this waste problem
Soluble salts in fly-ash
Flyash from straw combustion
30 mass % K
2
SO
4
50 mass % KCl
5-10 mass % P
2
O
5
10-15 mass % insoluble
Flyash from sewage sludge or manure combustion
Rich in P
2
O
5
Both contain various metals and other impurities besides
fertilizer material
Fluoride
Aluminum
Iron(III)
Copper(II)
Cadmium (10-15 ppm)
Benefits of recycling phosphorus
The rate of consumption of the limited sources of
phosphate rock in the world can be reduced
The environment benefits from reduced eutrophication
Money and energy is saved on the mining and import of
phosphate products
Indepedence from geopolitical tensions
Thermodynamic modeling of the relevant aqueous salt
systems is required in order to design appropriate
processes for recycling phosphorus
Process simulation
Process design

Previous modeling of similar
systems
Wang et al., Modeling phase equilibria and speciation in mixed-
solvent electrolyte systems, Fluid Phase Equilibria, 222-
223(2004)11-17
System: K
+
, Na
+
, H
2
PO
4
-
, HPO
4
2-
, H
3
PO
4
OLI mixed solvent electrolyte model
Christensen and Thomsen, Modeling of Vapor-Liquid-Solid
Equilibria in Acidic Aqueous Solutions, Ind. Eng. Chem. Res.,
42(2003)4260-4268
System: K
+
, Na
+
, NH
4
+
, Ca
2+
, Cl
-
, H
2
PO
4
-
, HPO
4
2-
, H
3
PO
4
Extended UNIQUAC modeling did not include high pH range
Weber et al., A Solubility Model for Aqueous Solutions
Containing Sodium, Fluoride, and Phosphate Ions, Ind. Eng.
Chem. Res., 39(2000)518-526
System: Na
3
PO
4
, Na
2
HPO
4
, NaF, NaOH
Pitzer model to describe phase equilibria up to 100C
Extended UNIQUAC model
Not a new model but new parameters
Thermodynamic model for solutions containing
electrolytes
Debye-Hckel term for electrostatic interactions
UNIQUAC term for short range interactions
Soave-Redlich-Kwong term for gas phase fugacities
The model is used for calculation of
Speciation equilibrium
Solid-liquid equilibrium
Vapor liquid equilibrium
Liquid-liquid equilibrium
Thermal properties

ex ex ex ex
Combinatorial Residual Extended Debye-Hckel
= + +
G G G G
ln - ln
2
ex
Combinatorial
i i
i i i
i i i
i
z
G
x x q
RT x
| |
u
| |
| |
=
|
|
\ .
\ .

ln
ex
Residual
j
i i ji
i j
G
= x q
RT
u
(
| |
( |
(
\ .

exp
ji ii
ji
u u
= -
T
| |
|
\ .
;
i i i i
i i
j j j j
j j
x r x q

x r x q
| u = =

( )
( )
( )
2

3
4
ln 1
2
E
Extended Debye-Hckel
w w
Ba I
A
G
= x M BaI BaI +
RT
Ba
(
+ (
(

( )
3/ 2
2
1/ 2
0
0
2 ; 1.5
4
A
r
e
A N d Ba
kT
t
tc c
| |
= =
|
\ .
Relative permittivity for pure water is used for all
solutions
The effect of other species on the chemical potentials in the
solution is accounted for by interaction parameters
The hydrogen ion is given fixed parameters, including
interaction parameters with all other species
The hydrogen ion is considered an anchor for the parameters
The properties of all other species are determined relative to
those of the hydrogen ion
The temperature dependence of chemical potentials is
determined by the Gibbs-Helmholtz equation:

( ) ( )
0
0
2
/
ln
at constant pressure
d G RT
d K H
dT dT RT
A
A
= =
Model parameters and standard
state properties
H
2
O, CO
2
, HF, HCl, HNO
3
, H
3
PO
4

H
+
, Na
+
, K
+
, Ca
2+
, Cu
2+
, Cd
2+
, Fe
3+
, Al
3+

F
-
, Cl
-
, SO
4
2-
, HSO
4
-
, NO
3
-
, OH
-
, CO
3
2-
, HCO
3
-
, PO
4
3-
, HPO
4
2-
, H
2
PO
4
-
,

AlO
2-
Adjustable model parameters
UNIQUAC surface area and volume parameters
Interaction parameters for each pair of species
Standard state properties
Aqueous species properties were taken from NIST/NBS tables
Temperature dependent heat capacities of aqueous species
given by three-parameter expression
Pure salt properties were adjusted to the experimental data
Heat capacities of pure salts were determined by Kopps rule
Experimental data
Over 150,000 experimental data on electronic form
More than 350 solute species
Types of data include:
Activity/osmotic coefficient
Enthalpy of mixing
Heat capacity
Degree of dissociation
Gas solubility
Enthalpy of absorption/evaporation
Density
Salt solubility (Solid-liquid equilibrium)
Liquid-liquid equilibrium
Vapor-liquid equilibrium
The databank can be browsed at http://www.cere.dtu.dk/Expertise/
Electrolyte data bank will be presented in the poster session

Determination of parameters
The adjustable parameters were determined using a modified
Marquard routine from Harwell subroutine library and a
Nelder-Mead simplex routine
Sequence of parameter determination:
1. Core system consisting of H
+
, Li
+
,Na
+
, K
+
, Mg
2+
, Ca
2+
, OH
-
, Cl
-
, HCl,
NO
3
-
, HNO
3
, SO
4
2-
, HSO
4
-
based on ca. 27000 experimental data
points. 23 binary and 87 ternary systems.
2. Carbonate species based on ca. 7000 experimental data
3. Phosphate species based on ca. 5000 experimental data
4. Fluorides species based on ca. 2000 experimental data
5. Aluminum species based on ca 1100 experimental data
6. Copper (II) based on ca 1500 experimental data
7. Iron (III) based on ca 1900 experimental data
8. Cadmium based on ca 1000 experimental data
About 200 model parameters and 360 standard state
properties of salts were adjusted based on these data.
0
10
20
30
40
50
60
70
80
90
100
100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
P
2
O
5
Na
2
O
H
2
O
H
3
PO
4
NaOH
NaH
2
PO
4
NaOH3H
2
O
NaOHH
2
O
NaH
2
PO
4
2H
2
O
NaH
2
PO
4
H
2
O
NaH
2
PO
4
H
3
PO
4
Na
2
HPO
4
2NaH
2
PO
4
2H
2
O
Na
2
HPO
4
NaH
2
PO
4
Na
2
HPO
4
Na
3
PO
4
Na
3
PO
4
H
2
O
Na
3
PO
4
8H
2
O
Na
3
PO
4
6H
2
O
Na
3
PO
4
12H
2
O
Na
2
HPO
4
12H
2
O
Na
2
HPO
4
7H
2
O
H
3
PO
4
H
2
O
4(Na
3
PO
4
12H
2
O)H
2
O
2H
3
PO4 = 3H
2
O + P
2
O
5
2H
3
PO
4
H
2
O = 4H
2
O + P
2
O
5
2Na
3
PO
4
= 3Na
2
O + P
2
O
5
2Na
2
HPO
4
12H
2
O = 2Na
2
O + P
2
O
5
+ 25H
2
O
Large number of phosphates
24 solids can form in
the H
3
PO
4
NaOH
H
2
O system
0
5
10
15
20
25
30
35
40
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
m
o
l

H
2
O
/
m
o
l

s
a
l
t

mol Na
2
O/(mol Na
2
O + mol P
2
O
5
)
Experimental
Extended UNIQUAC
Tie lines
Solids composition
NaH
2
PO
4
H
3
PO
4
NaH
2
PO
4
H
2
O
N
a
2
H
P
O
4
2

N
a
H
2
P
O
4
2
H
2
O

N
a
3
P
O
4
1
2
H
2
O

N
a
2
H
P
O
4
2
H
2
O

(4Na
3
PO
4
12H
2
O)NaOH
Na
3
PO
4
H
2
O
40 C
N
a
2
H
P
O
4

N
a
H
2
P
O
4

N
a
2
H
P
O
4
7
H
2
O

NaH
2
PO
4
NaH
2
PO
4
Na
2
HPO
4
Na
3
PO
4
H
3
PO
4
0
10
20
30
40
50
60
70
80
90
100
100
90
80
70
60
50
40
30
20
10
0
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00
Experimental
Extended UNIQUAC
P
2
O
5
Na
2
O
H
2
O
H
3
PO
4
NaH
2
PO
4
NaOH3H
2
O
NaH
2
PO
4
2H
2
O
NaH
2
PO
4
H
2
O
NaH
2
PO
4
H
3
PO
4
Na
2
HPO
4
2NaH
2
PO
4
2H
2
O
Na
3
PO
4
12H
2
O
Na
2
HPO
4
12H
2
O
H
3
PO
4
H
2
O
4(Na
3
PO
4
12H
2
O)NaOH
25C
0
10
20
30
40
50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
m
o
l

H
2
O
/

m
o
l

s
a
l
t

mol K
2
O/(mol K
2
O + mol P
2
O
5
)
Experimental
Extended UNIQUAC
Tie lines
Solids composition
0 C
H
3
PO
4
H
2
O
KH
2
PO
4
H
3
PO
4
KH
2
PO
4
K
2
HPO
4
6H
2
O
K
3
PO
4
7H
2
O
KOH2H
2
O
K
3
PO
4
KH
2
PO
4
K
2
HPO
4
0
10
20
30
40
50
60
70
80
90
100
100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Ravich and Popova, 1942
Platford, 1974
Beremzhanov et al., 1978
Makin, 1957
Bel Madani et al., 1999
Ravich, 1938
Selva, 1947
Extended UNIQUAC, this work
T= 25.0C
NaKHPO
4
5H
2
O
Na
2
HPO
4
7H
2
O
K
2
HPO
4
3H
2
O
Na
2
HPO
4
12H
2
O
K
2
HPO
Na
2
HP
H
2
O

-2
0
2
4
6
8
10
12
14
0
10000
20000
30000
40000
50000
60000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
p
H

m
o
l

H
2
O
/
(
m
o
l

C
a
O

+

m
o
l

P
2
O
5
)

mol CaO/(mol CaO + mol P
2
O
5
)
Experimental
Extended UNIQUAC
Tie lines
pH
25 C
Ca
3
(PO
4
)
2
CaHPO
4
2H
2
O

Ca(H
2
PO
4
)
2
H
2
O

-2
0
2
4
6
8
10
12
14
0
5
10
15
20
25
30
35
40
45
50
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
p
H

m
o
l

H
2
O
/
(
m
o
l

C
a
O

+

m
o
l

P
2
O
5
)

mol CaO/(mol CaO + mol P
2
O
5
)
Experimental
Extended UNIQUAC
Tie lines
pH
25 C
Ca(H
2
PO
4
)
2
H
2
O
CaHPO
4
2H
2
O
0.0E+00
5.0E+08
1.0E+09
1.5E+09
2.0E+09
2.5E+09
3.0E+09
0 0.2 0.4 0.6 0.8 1
m
o
l

H
2
O
/
m
o
l

s
a
l
t

mol Fe
2
O
3
/(mol Fe
2
O
3
+ Mol P
2
O
5
)
Experimental
Extended UNIQUAC model, this work
25C
FePO
4
2H
2
O
Fe
2
(HPO
4
)
3
H
3
PO
4
6H
2
O
Fe(H
2
PO
4
)
3
2H
2
O
0
100
200
300
400
500
600
0 0.05 0.1 0.15 0.2 0.25
m
o
l

H
2
O
/
m
o
l

s
a
l
t

mol Fe
2
O
3
/(mol Fe
2
O
3
+ Mol P
2
O
5
)
Experimental
Extended UNIQUAC
25C
FePO
4
2H
2
O
Fe
2
(HPO
4
)
3
H
3
PO
4
6H
2
O
Fe(H
2
PO
4
)
3
2H
2
O
FePO
4
2H
2
O
Solubility: Ca
3
(PO
4
)
2
> Cu
3
(PO
4
)
2
>
AlPO
4
> FePO
4

0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
N
a
F

m
a
s
s

%

Na
3
PO
4
, mass %
Extended UNIQUAC
Guiot (1967)
Nagorskaya and Novoselova (1935)
Morozova and Rzhechitskii (1977)
Tananaev (1941)
Morrison and Jache (1959)
Payne (1937)
Na
3
PO
4
12H
2
O
2Na
3
PO
4
NaF19H
2
O
NaF
0 C
Systems with data of
questionable quality
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 2 4 6 8 10 12 14
N
a
F

m
a
s
s

%

Na
3
PO
4
, mass %
Extended UNIQUAC
Roslyakova et al. (1979)
Foote and Schairer (1930)
Herting (1996)
Clark (1919)
Carter (1928)
Na
3
PO
4
12H
2
O
2Na
3
PO
4
NaF19H
2
O
NaF
25 C
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
0.0030
0.0035
0.0040
0.0045
0 10 20 30 40 50 60 70 80
M
a
s
s

%

C
a
F
2

Temperature C
Extended UNIQUAC
Experimental
CaF
2
Potassium salts with low
solubility
0
5
10
15
20
25
30
0 2 4 6 8
W
t

%

A
l
2
(
S
O
4
)
3

Wt % K
2
SO
4
Extended UNIQUAC this work
Ts'ai et al., 1936
0C
KAl(SO
4
)
2
12H
2
O
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70
W
t

%

A
l
(
O
H
)
3

wt % KOH

Du et al., 2005
40C
2KOHAl
2
O
3
2H
2
O
Al(OH)
3

Aluminate ion, AlO
2
-
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
8.5 9 9.5 10 10.5 11
A
l
O
2
-

f
r
a
c
t
i
o
n

pH
Al
3+
AlO
2
-
Al
3+
+4OH
-
AlO
2
-
+2H
2
O
Standard state properties for AlO
2
-
A
f
G, kJ/mol A
f
H, kJ/mol
NIST -830.9 -930.9
This work -734.0 -923.0
Salting in of CaSO
4
by AlCl
3
0
5
10
15
20
25
30
35
0 0.2 0.4 0.6 0.8 1 1.2 1.4
W
t

%

A
l
C
l
3

Wt % CaSO
4
Li and Demopoulos, 2006
50C
AlCl
3
6H
2
O
CaSO
4
CaSO
4
2H
2
O
0
200
400
600
800
1000
1200
0 0.2 0.4 0.6 0.8 1
V
a
p
o
r

p
r
e
s
s
u
r
e
,

k
P
a

HF mol fraction
Pxy diagram for HF-H
2
O at 100C
Extended UNIQUAC
Experimental
50
60
70
80
90
100
110
120
0 0.2 0.4 0.6 0.8 1
V
a
p
o
r

p
r
e
s
s
u
r
e
,

k
P
a

HF mol fraction
Pxy diagram for HF-H
2
O at 100C
Extended UNIQUAC
Experimental
Model implementation
The model is implemented in a dynamic link library (DLL-
file)
Multi-phase flash algorithm
The program can be called from programs that have a Visual Basic
interface such as Microsoft Excel
Simulations can be carried out directly in Excel
The excel sheet can be used as an interface to Aspen Plus

The model can be implemented as a user model in Aspen Plus

Conclusion
Phosphate is essential to life on earth no substitutes
Recycling of phosphate is extremely important due to limited
ressources.
Thermodynamic modeling of phase behaviour in systems
containing phosphate enable us to design processes for
producing food grade phosphate from waste such as sewage
sludge
Modelling with current activity coefficient models only possible with
the use of good quality experimental data
Experimental data for solubility in many systems representing
phosphate and its impurities are of low quality
New experimental measurements of solubility and other
properties of these systems are required to improve the
modeling

Acknowledgment
This project was supported by a grant from ForskEL
projekt nr. 2008-1-0111 Working up phosphate from
ashes
The project was carried out in cooperation with
Kommunekemi as, Denmark
Thank you for your attention
0
0.05
0.1
0.15
0.2
0 10 20 30 40 50 60
C
a
S
O
4
s
o
l
u
b
i
l
i
t
y
,

m
o
l
/
k
g

w
a
t
e
r
H
3
PO
4
mol/kg water
Experimental, CaSO4
Experimental, CaSO4H2O
Experimental, CaSO42H2O
Extended UNIQUAC
80 C
CaSO
4
CaSO
4
H
2
O
CaSO
4
2H
2
O
-60
-40
-20
0
20
40
0 20 40 60 80 100
T
e
m
p
e
r
a
t
u
r
e

C
Mass % H
3
PO
4
Experimental
Extended UNIQUAC
H
3
PO
4
H
2
O
H
3
PO
4
Ice
0
1
2
3
4
5
6
0 10 20 30 40 50 60
F
e
F
3

KF
T= 25.0C

Weight%
FeF
3
3H
2
O
FeF
3
2KFH
2
O
KF2H
2
O
FeF
3
3KF3H
2
O
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 10 20 30 40 50 60 70 80 90 100 110 120
s
a
l
t

f
r
a
c
t
i
o
n

Calculated
Experimental
Temperature, C
C
u
S
O
4

N
a
2
S
O
4

CuSO
4
Na
2
SO
4
2H
2
O
CuSO
4
5H
2
O
Na
2
SO
4
10H
2
O
Na
2
SO
4

CuSO
4
3H
2
O

KajThomsen Phosphorus1298

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KajThomsen Phosphorus1298

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