IAPWS MEETING MARCH 14th 2005 Supercritical Properties and

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IAPWS MEETING MARCH 14th 2005 Supercritical
Properties and Geothermal Energy, Hydrogen,
Methanol and Metals/Minerals From Near Surface
Magmatic Systems Dr. Daniel W.H.
FraserDepartment of Mechanical and Industrial
Engineering, University of Manitobafraserdw_at_cc.um
anitoba.ca
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• The whole concept of a hydrogen economy, to
  counter climate change, requires finding large
  sources of clean energy to create hydrogen. An
  enormous amount of geothermal energy and
  additional methane, hydrogen and metals/minerals
  exist in hydrothermal fluids that originate from
  high temperature magmatically heated reaction
  zones.

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Tectonic Plate Spreading
The Pacific Rim Of Fire
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Hydrothermal Ocean Ridge FormationSpreading
Center-Iceland

• Mid-Ocean Ridges are places where the Earth's
  tectonic plates are gradually moving apart
• magma rises up to fill the gap
• magma provides an enormous heat source that
  creates many seafloor hotsprings (black smokers
  etc.) along these ridges undersea
• thermal capacity is orders of magnitude greater
  than conventional land based systems
• transports heat and chemicals into the ocean

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Mid-Atlantic Ridge - Iceland
Drill Site
Sub Continental Spreading Region
Active Volcanoes
Glacier

• Plates are moving apart at a rate of only 2
  cm/year
• Mid-Atlantic Ridge occurs on the island
• These systems bring the Magma close to the
  surface such as what occurs in an Island Arc
  System (Aleutians)

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Makushin
Proximity to the Ocean for Saline Fluids?
3-D Modelling AECL, Iceland, USNRC, U of M etc.

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Saline Hydrothermal Systems

• Seawater penetrates the ocean floor or land mass
  (e.g. Iceland and the Aleutians or Coastal
  Alaska?) through highly fractured zones
• Very different chemistry than conventional land
  based hydrothermal convection cells
• Much greater energy content and maximum
  temperature potential than conventional land
  based systems
• Can be highly permeable with no possible loss of
  water or pressure over time as occurs with
  conventional land based systems

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Reykjanes Drill Site
To plant
Injection For corrosion and plugging
prevention Patent Pending

Not to scale
Highly fractured basalt
magma
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Saline Hydrothermal Systems
? 100 km
NOTE SCALE
Ocean
P?gh
? 4000C
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Black Smoker

• Laden with metal sulfides that precipitate into
  suspended particulates on contact with the cold
  seawater
• Fluids also contain H2, CH4 and CO2
• Raw materials for Methanol Synthesis
• Similar fluids come from the Icelandic land based
  plant and many other worldwide locations (e.g
  Alaska, Africa etc.)

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Alvin
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Papua New GuineaBack Arc Spreading Centre
Steve Scott (U of T) Sub-Sea Mining Strategies
VENT CHIMNEY/SUFIDE DEPOSIT COMPOSITION 11 wt
Cu, 27 wt Zn, 230 ppm Ag and 200 ppm Au
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GASES, METALS AND MINERALS SOURCES SUPERCRITICAL
SOLUTIONS LAND BASED VERSUS OCEAN/SALINE BASED

• Meteoric Water (Conventional Plants)
• Fluids contain silicon, aluminum salts,
  potassium, trace minerals, CO2, H2 H2S
• Oceanic Water (Iceland Pilot Plant - First
  worldwide)
• Complex process Supercritical aqueous chloride
  fluids strip metals, minerals and create gases
  (H2 and H2S) in an interaction with magma at high
  T?
• As yet undetermined, juvenile fluids may
  contribute substantially to gas and mineral
  content

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HYDROGEN SOURCES

• Hydrogen may occur naturally in vent fluids
• water gas reaction using coke water ( gt600º C )
• C present in rock formations such as Basalt
• steam reforming process using natural gas and
  water ( gt600º C ) which could occur near the
  magma source
• possibly accounts for some of the dissolved
  hydrogen present in vent fluids (solubility
  increases with increasing pressure)

C(s) H2O(g)
          
CO(g) H2(g)
CH4(g) H2O(g)
          
CO(g) 3 H2(g)
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HYDROGEN SOURCES - CONT.

• Water gas shift may also occur
  H2O CO H2
  CO2
• H2 CO2 Methanol (high T Catalytic)
• Many teams are researching H2 and CH4
  concentrations in vent fluids and will also
  investigate the similar content in land based
  systems
• Very similar fluids exist in Oceanic source wells
  in Iceland, Alaska? and hydrothermal vents
• 101 ways to produce hydrogen or methanol!
• SWPO using cheap available thermal energy in
  Iceland or Alaska General Atomics (USA) is
  leading SWPO processes for H2 production

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Clean? Coal to Methanol
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Advanced CANDU-X Reactors

• University of Manitoba Research
• -Safety Issues (LOCA) Modelling Critical
  two-phase flow.
• -Heat Transfer To Supercritical Water(D. Fraser,
  UBC,U of M).
• -Natural Convection Loop SC CO2 and SCW (V.
  Chatoorgan and D. Fraser)
• -Experimental Critical Flow with SCW at
  stagnation- funding?
• -Collaboration with IDDP to test SCW power cycle
  components?

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Enhancement of heat transfer coefficients at and
near the critical region, G662 kg/m2.s, P24.4
MPa, q?195 kW/m2
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Buoyancy/Natural Convection Effects of SCW
Varying heat transfer coefficients at
both top and bottom surfaces, P24.4 MPa, G340
kg/m2.s, q?300 kW/m2  
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Economic Potential Of Metals
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SCW PROPERTIES

• Accounts for solubility variation
• May account for some self sealing mechanisms
  may cause increased pressures below such a
  formation
• Low density permits high wellhead pressures (at
  5000C the density is around 1/5 of seawater)

Accounts for high enthalpies
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PH 3
0.00C ambient temperature
P gt 22 MPa
?4000C
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Typical Metal/Salt Solubility
H2O Metal Cl
Binary System H2O Metal or Salt
Solubility
Solubility
420C
420C
420C
Temperature
High pressure oxidation leaching type region for
extractive metallurgy
Cl dramatically improves solubility
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Pseudo - critical temperature line,PCTL
very high solubility region

Regions where solubility can vary. Varying
minerals/metals behave differently
Supercritical Pressure
Conventional nuclear and geothermal
Fluid states within the very high solubility
region will transport minerals/metals dissolved
in solution and also suspended/dissolved in a
brine phase. The blue line represents the path a
black smoker fluid takes when exiting the chimney
(shock precipitation).
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Pseudo - critical temperature line,PCTL
very high solubility region
Drive the thermodynamic properties of the
solution along this path (blue).

Supercritical Pressure
Regions where solubility can vary. Varying
minerals/metals behave differently
Conventional nuclear and geothermal
As long as the fluid state is within the very
high solubility region it will transport the
minerals and metals dissolved in solution and
suspended/dissolved in the brine phase (some
precipitation may occur - see later slide).
Moving outside of this region will cause the
metals/minerals to precipitate out of solution.
The faster the fluid is brought out of this
region the more rapid the precipitation (shock
precipitation). This will occur most rapidly
along the blue path - across the PCTL. Solubility
can vary by orders of magnitude across the
pseudo-critical line.
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Blue Path.Drive the thermodynamic properties of
the solution along this path. This is identical
to what occurs at or near the exit section of
black smokers. Shock precipitation occurs while
crossing the pseudo-critical temperature line.
very high solubility region

Supercritical Fluid
Red Path. Path the fluid follows in a normal
well. Note that decreasing solubility is not well
demarcated (occurs over a wider variation of
properties). Hence, precipitation will occur over
a longer length of pipeline. This was seen in
Reykjanes well 9 although the starting point is
below supercritical. Solubility variation within
the superheated region, as one drops below the
critical pressure, is very poorly understood.
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Global Resource Potential
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Tectonic Plate Boundaries
Hawaii
Andes
Mid-Atlantic Ridge
Japan
East Africa Rift
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WORLD-WIDE SITES
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East Africa Rift
Erta Ale
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MIDDLE EAST
JORDAN
ISRAEL
EGYPT
RED SEA
A satellite view of the Sinai showing two arms of
the Red Sea spreading ridge, exposed on land.
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WORLD WIDE COLLABORATION
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NEPTUNE Canada, USA And Partners (Orion)
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ACKNOWLEDGEMENTS The author wishes to acknowledge
the permission of John Madden the former director
of Neptune (and its affiliates) as well as all
the people from the Icelandic consortium for the
use of some of their graphics in this
presentation.
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IDDP, NEPTUNE, ORION and ALASKA

• Iceland or Alaska (Unalaska?) pilot plant will
  provide an unprecedented opportunity to access
  saline based hydrothermal resources from land and
  potentially extract valuable metals/minerals and
  enormous energy potential.
• Understand the geochemistry of supercritical
  aqueous chloride solutions (e.g. black smokers).
  We can expect similar fluids from the land based
  saline wells.
• Understand the behavior of thermal convection
  cells- heat and mass transfer (modeling
  etc.)using state of the art 3-D codes.
• Quantify the material flux and composition from
  black smokers and wells in Iceland and Alaska.
• On land, use efficient SCW processes to produce
  H2 and Methanol or combine H2 and CO2 to methanol
  (high T catalytic) etc.
• Investigate other possible H2 carriers such as
  Ammonia NH3
• CO2 sources to produce methanol (high T catalytic
  reaction).
• Mining interests may predominate at first but lay
  the infrastructure for energy/hydrogen/ methanol?
  production.