Transcript Novosol - Solvay Plastics

A STABILIZATION PROCESS OF
MINERAL RESIDUE
CONTAMINATED WITH HEAVY
METALS AND ORGANIC
COMPOUNDS
G. Depelsenaire – SOLVAY
5 avril 2006 - 0
[ Presentation Outline ]
1. The Novosol® process
2. Potential applications
3. Process R&D
3.1. The process as applied to fly ash
3.2. The process as applied to polluted river or port sediments
5 avril 2006 - 1
1. THE PROCESS
TWO-STEP STABILIZATION OF MINERAL RESIDUE
CONTAMINATED WITH HEAVY METALS AND ORGANIC
COMPOUNDS
Step A HEAVY METAL STABILIZATION
by binding to a calcium phosphate ( [Ca3(PO4)2]xH2O ) matrix
formed by adding H3PO4
Step B ORGANIC COMPOUND DESTRUCTION
by calcination (650°C - 900°C)
H3PO4
Contaminated
mineral
residue
Calcium
phosphate
formation
Step A
Calories
Organic
compound
destruction
Usable
stabilized
mineral
residue
Step B
5 avril 2006 - 2
2. POTENTIAL APPLICATIONS

Potential applications
 Port and waterway dredging sediments
 Fly ash from municipal waste incinerators
 Automotive shredder residue
 Contaminated soil
 Industrial sludge
 ...
Among these, the following have been so far
treated in industrial pilot facilities:
 Fly ash from municipal waste incinerators
 River sediments
5 avril 2006 - 3
3. NOVOSOL® PROCESS R&D
 Research program
- Began in 1993, with the Université Libre de Bruxelles
(ULB – Professor DERIE)
- Continued uninterruptedly since then, in partnership with several
research institutes:
* Ecole des Mines d’Albi (F)
* Laboratoire des matériaux et de la durabilité des constructions à
Toulouse (F)
* BRGM – Orléans (F)
* Ecole Centrale de Lille (F)
* NJIT (USA)
* Laboratoire Central des Ponts et Chaussées – Nantes (F)
* EUROVIA (F)
* Ecole Nationale de Travaux Publics de l’Etat – Lyon (F)
* EEDEMS – Lyon (F)
5 avril 2006 - 4
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.1. Patents
 Europe
- EP 0883585 B1
- EP 0899000 B1
(Jan. 12, 2000)
(Nov. 3, 2004)
 USA
- 6 132 355
- 6 254 846
(Oct. 17, 2000)
(Jul. 3, 2001)
5 avril 2006 - 5
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
The REVASOL program: value recovery from flue gas scrubbing residue
produced by the sodium bicarbonate-based Neutrec® dry process
Flue gas process
Sodium
Activated
bicarbonate carbon
Waste
Furnace +
boiler
Raw flue
gasses
Filtration
Filtration
Dust-free gasses
Fly ash
Processed gasses
Sodium-rich residue
REVASOL pilot plant – Dombasle 1999 - 2003
Water
Scrubbing
-------------------------------------
H3PO4
Calories
NOVOSOL
Dioxin-free, furan-free
solid residue
Incorporation in road-building materials
Scrubber
solution
Chemical treatment
Ultimate wastes
Grade I landfill site
Concentrated
dioxin-free, furan-free
standardized brine
Sodium carbonate production
5 avril 2006 - 6
Stack
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
REVASOL program – Development of partnership studies
 ADEME - Agence De l'Environnement et de la Maîtrise de l'Energie - Angers
 BERTIN Technologies - Tarnos
 BRGM - Bureau de recherches Géologiques et Minières - Orléans
 EMAC - Ecole des Mines d'Albi/Carmaux - Albi
 LCPC - Laboratoires Central des Ponts et Chaussées - Nantes
 Ets. Jean LEFEBVRE - Metz - Dourdan
 LMDC - Laboratoires des Matériaux et de la Durabilité des Constructions INSA - Toulouse
 POLDEN - INSA - Lyon
5 avril 2006 - 7
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
REVASOL program – Pilot plant process development
 Carried out by BERTIN in 1998
 Built by SOLVAY at its Dombasle (Nancy) research centre in 1999
 Operated by Solvay
 Process developed in 2000
 20 metric tons of fly ash treated in the first half of 2001
5 avril 2006 - 8
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
REVASOL program – Assessment of value recovery strategies
 Studies carried out by different research teams from 1998 to 2001
 Selected strategies:
 Incorporation in concrete
 Incorporation in road-building materials
 Tested strategy: road construction (in juin 2002)
 Construction of a ‘test road’ (100 m2) and a ‘control road’ (100
m2) at Dombasle. Their leachates can be collected on impermeable
membranes and continuously monitored.
 Construction of mini pilot units (4 m2) for running accelerated
aging tests on road-building materials. Their leachates, also collected
on impermeable membranes, have been monitored until June 2003
5 avril 2006 - 9
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
Test road at Dombasle: placement of the sand-gravel aggregate base course
containing 12% treated fly ash (June 2002)
5 avril 2006 - 10
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
Test road at Dombasle: placement of the sand-gravel aggregate base course
containing 12% treated fly ash (June 2002)
5 avril 2006 - 11
3.1. THE NOVOSOL® PROCESS AS APPLIED TO FLY ASH
3.1.2. Study of process and value recovery from products
Quality of the leach water collected beneath the ‘test’ road
After
1 week
1
Tank
02.07.02
pH
µ
Conductivity
P mg/l S/cm
ClSO4 mg/l
id
As
id
Cd
id
Cr (total)
id
Ni
id
Cu
id
Ag
id
Pb
id
Zn
6.200
14.385
0.690
4.010
811.000
< 0.001
< 0.005
0.080
< 0.050
< 0.050
< 0.001
< 0.050
< 0.050
After
After
After
After
1 month 4 months 12 months 40 months
5
4
3
2
Tank
Tank
Tank
Tank
24.01.06
18.07.02 18.10.02 09.07.03
8.6 **
7.400
7.053 3080.000
0.160
0.260
1.959 8080.000
763.000 446.000
< 0.001
< 0.001
< 0.050
< 0.050
0.210
0.160
< 0.050
< 0.050
< 0.050
< 0.050
< 0.001
< 0.001
< 0.050
< 0.050
< 0.050
< 0.050
10.6500
7.600
3000.000 9830.0000
NM***
NM***
656.000 3169.0000
573.000 734.0000
< 0.0010
< 0.001
< 0.0005
NM***
0.1100
0.100
< 0.0050
NM***
0.0090
NM***
< 0.0010
< 0.001
< 0.0050
NM***
0.0100
NM***
SEQ*/Ground
water,
drinking water
production,
acceptable
quality
8.5 – 9
400 – 2300
250.000
250.000
0.010
0.005
0.050
0.020
0.200
0.020
0.010
5.000
* cas de percolation contaminée par de la chaux répandue sur la route
de la Qualité des eaux (France – Agences de l’eau)
* SEQ = Système d’Evaluation
** Percolating water was contaminated by lime spilt on the road
*** Not measured
5 avril 2006 - 12
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.1. Patents
 Patent applied for in October 2000 for processing port and waterway dredging
sediments
*
European patent EP 1 341 728 B1
(Nov. 23, 2005)
 Patent applied for in October 2002 due to technological advances –
“NOVOSOL–Foam”
5 avril 2006 - 13
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.2. Novosol foam
Process operating chart
H3PO4
Sediments/Soil
cont. 50% H2O
Maturation
and drying
bed
Site A
- Interim storage makes for:
Interim
storage
* Fast completion of the phosphatation & drying phase
* Extra time for planning the calcination & value recovery phase
* Extra time for selecting the best fuel for the calciner
Value recovery from
stabilized materials
Calcination
Value recovered as
calories for drying or
electricity generation
Site B
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3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
European classification of contaminated sediments
17 05 05 * Dredging sludges containing hazardous substances
Heavy metal levels above which sediments are considered hazardous
in mg/kg
dry matter
As
Cd
Cr
Hg
Cu
Ni
Pb
Zn
FRANCE
GEODE
50.00
2.40
180.00
0.80
90.00
74.00
200.00
552.00
THE NETHERLANDS –
FLANDERS
KLASSE 4
173.8
6.0
268.6
0.8
126.4
173.8
221.2
1058.6
BELGIQUE
WALLONIA
50.0
6.0
200.0
1.5
150.0
75.0
250.0
1200.0
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3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Process demonstration in pilot units

Laboratory research
Research and doctoral dissertation agreements with:
- Ecole des Mines (Albi-Carmaux, France)
- Ecole Centrale (Lille, France)
- Ecole Nationale des Travaux Publics (Lyon, France)
- Université P. Sabatier (Toulouse, France)
5 avril 2006 - 16
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
 Phosphatation mini pilot unit
(Capacity: 400 l/h of sediments containing 50% H2O)
5 avril 2006 - 17
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Industrial-scale phosphation pilot unit
(designed and realized by Bertin Technologies)
Capacity:
400 l/h of sediments containing
50% H2O
5 avril 2006 - 18
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Industrial-scale phosphatation and drying demonstration pilot unit at Farciennes (B)
5 avril 2006 - 19
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Mobile industrial-scale
calcination pilot unit
(designed and realized by
Bertin Technologies)
Capacity: 20 t / month of
processed sediments
5 avril 2006 - 20
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Mobile industrial-scale calcination pilot unit – General view
5 avril 2006 - 21
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Stabilizing performances of the NOVOSOL® process when applied to river
sediments in pilot units – Leaching with 0.5M acetic acid
As
Cd
Cr
Hg
Cu
Ni
Pb
Zn
TOTAL
Evolution ratio of metals in the
mineral matrix
Metal leaching ratio
Raw sediments
Phosphated sediments
Leaching
Leaching
CH3COOH
CH3COOH
Composition
Composition
0.5 M
0.5 M
mg/kg
mg/kg
L/S=20
L/S=20
dry matter
dry matter
mg/kg
mg/kg
dry matter
dry matter
7.82
1.200
6.94
4.70
11.50
0.068
11.50
< 0.20
131.00
2.500
129.00
< 0.20
0.89
< 0.001
0.86
0.16
100.00
< 0.500
102.00
< 0.20
105.00
18.000
106.00
14.90
680.00
40.000
700.00
< 0.60
3590.00
900.000
3530.00
212.00
4626.21
962.270
4586.30
232.96
Calcinated sediments
Leaching
CH3COOH
Composition
0.5 M
mg/kg
L/S=20
dry matter
mg/kg
dry matter
13.00
4.70
13.00
0.23
175.00
0.48
0.35
< 0.10
163.00
0.34
165.00
1.45
981.00
0.98
4290.00
109.70
5800.35
117.89
100 %
99.14%
125%
20.8 %
5.08 %
2.03 %
5 avril 2006 - 22
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Stabilizing performances of the NOVOSOL® process when applied to river
sediments in pilot units – Leaching with water
As
Cd
Cr
Hg
Cu
Ni
Pb
Zn
Metal leaching ratio
Raw sediments
Leaching
H2O
Composition
mg/kg
L/S=10
mg/kg
dry matter
dry matter
7.82
0.1670
11.50
0.0250
131.00
0.0400
0.89
0.0006
100.00
0.1200
105.00
0.2600
680.00
0.3400
3590.00
0.4900
0.03 %
Phosphated sediments
Leaching
H2O
Composition
mg/kg
L/S=10
mg/kg
dry matter
dry matter
6.94
0.5980
11.50
0.0450
129.00
0.0300
0.86
0.0008
102.00
0.1500
106.00
0.4900
700.00
0.6500
3530.00
0.4500
0.05 %
Calcinated sediments
Leaching
H2O
Composition
mg/kg
L/S=10
mg/kg
dry matter
dry matter
13.00
0.1980
13.00
0.0450
175.00
4.0300
0.35
0.0004
163.00
0.2900
165.00
0.0800
981.00
0.3600
4290.00
0.2100
0.09 %
5 avril 2006 - 23
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Value recovery through production of road construction materials
River sediment sample treated by the NOVOSOL® process for the ‘test’ road study
Road construction material sample containing 40% treated river sediment
Leaching results (x30402.2)
Phosphated and calcinated river sediments
from pilot units A and B
“Sand/cement road
construction material
(base course) containing
40% NOVOSOL
sediments”
Inert material *
Composition
mg/kg
dry matter
Lixiviation H2O L/S = 10
mg/kg
dry matter
Lixiviation H2O L/S = 10
en mg/kg
matières sèches
Lixiviation H2O L/S = 10
en mg/kg
matières sèches
16720.00
5530.0000
6000.00
Fraction soluble
As
21.30
< 0.10
< 0.1000
0.50
Cd
8.30
< 0.02
< 0.0200
0.04
Cr
122.50
< 0.05
0.3000
0.50
Hg
0.23
-
< 0.0005
0.01
Cu
82.30
< 0.02
< 0.0200
2.00
Ni
70.30
< 0.05
< 0.0500
0.40
Pb
552.30
1.40
0.0500
0.50
Zn
1853.80
0.42
< 0.0500
4.00
* Council Directive 1999/31/EC of 26 April 1999 on the landfill of waste
5 avril 2006 - 24
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Value recovery through production of road construction materials

Construction in December 2005 of a test road (100m2) comprising a
sand/cement base course prepared with 30% NOVOSOL®-treated river
sediments
The environmental impact (analyses of leachate collected beneath the
‘test’ road) and the mechanical performance of this road will be
monitored for at least 1 year and 3 years at most.
5 avril 2006 - 25
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Construction of the ‘test’ road at Dombasle
Base course (25cm thick) made of cement-stabilized sand containing
30% NOVOSOL®-treated river sediments
Detail of membranes
5 avril 2006 - 26
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Construction of the ‘test’ road at Dombasle
1- spreading and collecting of
samples for molding
Base course (25cm thick) made of cement-stabilized
sand containing 30% NOVOSOL®-treated river
sediments
2- initial compaction
with vibrating roller
3- compaction
with P1 tires
4- final screeding
e= 0.25 m
5 avril 2006 - 27
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.3. Study of process and value recovery from products
Value recovery through production of road construction materials
Characteristics of the material* used to construct the ‘test’ road
(cement-stabilized sand comprising 30% NOVOSOL®-treated river sediments)
Leaching x 30402.2
SEQ – Ground water
Road leachates
Samples kept at the laboratory
Composition
mg/kg
Drinking water production,
acceptable quality
After 7 days
After 28 days
mg/l
mg/l
Obtained after
10 days
mg/l
Obtained after
2 months
mg/l
mg/l
As
20.7
0.015
0.015
0.0008
0.0008
0.010
Cd
13.3
0.020
0.020
0.0010
0.0010
0.005
Cr
120.0
0.020
0.040
0.0020
0.0020
0.050
Hg
0.1
0.001
0.001
0.0001
0.0001
0.001
Cu
73.3
0.020
0.030
0.0030
0.0010
0.200
Ni
63.3
0.030
0.050
0.0050
0.0050
0.020
Pb
500.0
0.005
0.005
0.0070
0.0050
0.010
Zn
1667.0
0.090
0.050
0.0050
0.0050
5.000
* cas de percolation contaminée par de la chaux répandue sur la route
* Composition of the material (cement-stabilized sand)
- Limestone 0/6 mm
63%
- NOVOSOL®-treated sediments 30%
- ROC SG hydraulic binder
7%
5 avril 2006 - 28
3.2. THE NOVOSOL® PROCESS AS APPLIED TO POLLUTED SEDIMENTS
3.2.4. Marketing strategy
Solvay grants access to the NOVOSOL® technology by selling patent
licenses for the use of the process.
A separate license is granted for each individual project. Licenses are
therefore time-limited and concern a limited geographic area.
5 avril 2006 - 29
3.2. APPLYING THE NOVOSOL PROCESS TO CONTAMINATED SEDIMENTS
3.2.4. Marketing elements
Main economic data
for an industrial unit with a treatment capacity of 100 000 m3/year raw sediments
50% H2O, representing 150 000 tonnes/year dry material
OPTION 1 – Production of dried phosphated sediments + landfilling
Investment
k€
Novosol A
Cost/tonne (2)
€
3500
Landfilling (3)
Total
23.5
60
75
3500
Cost / ton raw sediments 50% H2O
OPTION 2 – Production of sand (1) for reuse in road construction
Annual Cost
k€
Investment
k€
for 150000 t : 3525
for 90000 t
(4)
Cost/tonne (2)
€
Novosol A
3500
23.5
: 5400 Novosol B
6750
11500
90
80
8925 Total (6)
10275
15000
Annual Cost
k€
for 150000 t : 3525
for 82560 t
(5)
: 7425
6600
10950
10125
59.5
68.5
73
67.5
Assumptions :
(1) Option 2 produces a material described as “Sand” by road manufacrurers
(2) Novosol A : per tonne raw material, excluding the profit margin of the Novosol operator
(3) Current landfilling costs – estimated trend
(4) Landfilled material with a 20% water content
(5) Material with a 10% water content before calcination
(6) Road manufacturer takes the sand at zero cost
5 avril 2006 - 30
INDUSTRIAL ECOLOGY- NOVOSOL® / FOAM
Mineral residues
Combustible waste
Sediments with 50 %
H2O
pump
H3PO4
Refuse-derived
fuel (RDF)
pump
Flying ash
Gas
treatment
Mineral fine
shredder residues
Dried sludge
Gas
treatment
NEUTREC
from wastewater
treatment plant
Others
Others
Unit A
Phosphatation - Drying
Unit B
Calcination
End product for reuse in
road – brick - concrete
5 avril 2006 - 31