Content uploaded by Rafael Mattos Dos Santos
Author content
All content in this area was uploaded by Rafael Mattos Dos Santos on Dec 06, 2014
Content may be subject to copyright.
Opportunities and developments on
the intensification of chemical and
geochemical processes by
gravity pressure vessel technology
Rafael M. Santos, Tom Van Gerven
KU Leuven, Dept. Chemical Engineering, Leuven, Belgium
Pol Knops, Keesjan Rijnsburger
Innovation Concepts B.V., Gorinchem, The Netherlands
Fourth European Process Intensification Conference
(EPIC 2013)
Outline
•Working principle
•History
•Opportunities under consideration
–Mineral carbon sequestration
–Asbestos remediation
–Oil sand tailings treatment
•Developments of Innovation Concepts
Working Principle
•Gravity pressure vessel (GPV) step by step
GPV 1
B
A
A: Incoming material
B: DownComer tube
Pressure increases
Pre-heating medium
0 meter
-1200 meter
GPV 2
B
A
A: Incoming material
B: DownComer tube
C: Gas injection
Exothermic reaction -> Energy production
C
C
C
C
C
C
D
GPV 3
B
C
C
C
A
D
A: Incoming material
B: Downcomer tube
C: Gas injection
D: Upcomer tube:
Releases energy to downcomer
Pressure decreases
Leaves the reactor
E
D
GPV 4
B
C
C
C
A
C
E
E
E
A: Incoming material
B: Downcomer tube
C: Gas injection
D: Upcomer tube:
E: Surrounding tube
Start-up heating (ignition).
Steady-state (autothermic) cooling
and energy harvesting.
Advantages
obuilt-in heat exchanger: heat conservation,
utilization and recovery.
ohydrostatic pressurization: low energy demand.
Advantages
oturbulent three phase flow: promotes heat and
mass transfer, autogeneous milling and
passivating layer erosion.
Advantages
oplug flow configuration: continuous process, no
moving parts.
ounderground installation: safe/inexpensive
reactor design.
Input Output
Low P Gas
Surface level
Underground
History
•Patent 4,272,383, McGrew (1981)
“Method and apparatus for effecting subsurface,
controlled, accelerated chemical reactions”
•Sewage Sludge Wet Oxidation:
–Longmont, Colorado (USA)
•Moved to Apeldoorn
–Apeldoorn (The Netherlands)
•VerTech process
•1992-2004 US 4,272,383
History
•VerTech Process
Throughput 120 m3/hr
Energy production
Recovery
9.5 MW(th)
50% @ 260 °C
Energy density 340 J/kg
Gas injection O2: 2.4 tonne/hr
Max. temp
Depth
270 °C
1200 m
Installation
•Conventional drilling:
Straight, 30”
Commissioning
•Identification:
–Accelerate reaction kinetics.
–Integrate and recover exothermic reaction heat.
–Valorize low value residues into products.
•Approach:
–Focus towards full scale installation.
–Build on existing R&D.
–Harvest past experience.
Opportunities
Opportunities
•Mineral carbon sequestration:
–Natural minerals: olivine, wollastonite, serpentine.
–Industrial residues: slags, ashes, tailings.
•Waste remediation:
–Asbestos containing-materials (mining tailings
and construction materials).
–Oil sand tailings.
Mineral Carbon Sequestration
•Olivine:
(Mg,Fe)2SiO4 + 2CO2 => 2(Mg,Fe)CO3 + SiO2
[∆H = -89 kJ/mol CO2]
•Wollastonite:
CaSiO3 + CO2 => CaCO3 + SiO2
[∆H = -87 kJ/mol CO2]
•Serpentine:
Mg3Si2O5(OH)4 + 3CO2 => 3MgCO3 +2H2O + 2SiO2
[∆H = -64 kJ/mol CO2]
•Reaction rate
T.A. Haug, 2010.
PhD Thesis
, NTNU.
S.J. Gerdemann et al., 2003. S
econd Annual Conference on Carbon Sequestration,
Alexandria, VA, USA.
Time (hr) pH
Temperature (°C) Pressure (atm)
Mineral Carbon Sequestration
•Reaction profile
Temperature profile
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Conversion
200
150
100
50
0
Temperature (°C)
Carbonation conversion profile
reactor length (m) reactor length (m)
0 500 1000 1500 2000 0 500 1000 1500 2000
heat
10 μm, 0.7 kg/kg
Mineral Carbon Sequestration
R.M. Santos et al. 2012.
11th International Conference on Greenhouse Gas Control Technologies
, Kyoto, Japan.
•Autothermic map
(a) 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
10 4% 5% 100% 99% 96% 92% 89% 85% 82% 79%
20 4% 4% 4% 85% 80% 76% 72% 68% 65% 62%
30 4% 4% 4% 4% 69% 65% 61% 58% 55% 53%
40 4% 4% 4% 4% 4% 57% 54% 51% 49% 47%
50 - - - - - 4% 49% 46% 44% 42%
60 - - - - - 4% 4% 42% 40% 39%
70 - - - - - 4% 4% 4% 37% 36%
80 - - - - - 4% 4% 4% 4% 34%
(b) 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
10 29 34 79 97 114 129 142 153 163 171
20 28 29 32 92 104 114 122 130 137 143
30 28 28 29 32 93 102 109 115 120 125
40 28 28 29 30 32 93 99 104 109 113
50 - - - - - 32 91 96 101 104
60 - - - - - 31 32 90 94 98
70 - - - - - 30 31 33 88 92
80 - - - - - 30 30 31 33 87
particle diameter (μm)
solids loading (kg,solids/kg,liquid)
solids loading (kg,solids/kg,liquid)
particle diameter (μm)
carbonation conversion
outlet temperature (°C)
Outlet carbonation conversion (%)
Mineral Carbon Sequestration
R.M. Santos et al. 2012.
11th International Conference on Greenhouse Gas Control Technologies
, Kyoto, Japan.
•Carbonation products
Fully carbonated olivine
Fresh milled olivine
Mineral Carbon Sequestration
amorphous silica (SiO2) magnesite (MgCO3)
Asbestos Remediation
•Chrysotile (white asbestos): Mg3(Si2O5)(OH)4
•Tremolite: Ca2Mg5Si8O22(OH)2
•Fibre cement (historical): 90% cement, 10% chrysotile
http://en.wikipedia.org/wiki/File:
Chrysotile_SEM_photo.jpg http://en.wikipedia.org/wiki/File:
Wellasbestdach-233-3354_IMG.JPG
Asbestos Remediation
•Oil sand tailings: sand, clay, water and residual
bitumen (‘tar’).
•MFT (Mature Fine Tailings) + O2 =>
TTT (Thermally Treaded Tailings)
•Aim:
–reduce settling time;
–oil and metals oxidation;
–reduce contaminants leaching;
–free water for re-use;
–autothermic process.
Oil sand tailings Treatment
http://en.wikipedia.org/wiki/File:
Syncrude_mildred_lake_plant.jpg
Oil sand tailings Treatment
P. Knops. 2011.
RemTech 2011
, Banff, Canada.
Temperature (°C)
350
300
250
Time (min)
60
30
60
30
60
30
% COD reduction
86.3%
85.3%
82.9%
81.2%
70.6%
69.6%
•COD reduction test
Oil sand tailings Treatment
P. Knops. 2011.
RemTech 2011
, Banff, Canada.
•Settleability test
Developments
•Split into various stages:
✔ Patent application
✔ Batch autoclave
✔ Research consortium
☐ Continuous autoclave
☐ Pilot reactor
☐ Full scale
•Batch rocking autoclave (now under testing)
Simulate GPV characteristics:
Tubular hydrodynamics.
Transient T and P.
Generate fundamental understanding:
Reaction rates.
Particle exfoliation.
Passivating layers.
Product mineralogy.
Developments
•Consortium agreement:
- Sibelco (olivine producer)
- Steel company (CO2 producer)
- Institute for Sustainable Process Technology (ISPT)
- KU Leuven
- Dutch University
- Innovation Concepts (technology holder)
Developments
Learn more about us:
set.kuleuven.be/mrc/sim2
www.innovationconcepts.eu