An overview of Future Cements
An overview of the alternative mineral binder systems
including novel concrete technologies addressing
practical supply chain and economic issues including
energy
17/03/2016
www.tececo.com
www.propubs.com
1
Why Future Cements?
The Techno Process
Primary Production Process Build, & Manufacture Use Dispose
Underlying Molecular Flows
Primary
Production
Methane
NOX &
SOX
Heavy
Metals
CO2
etc.
Embodied
& Process
Energy
Process,
Build
&
Manufacture
NOX &
SOX
Heavy
Metals CO2
etc.
Embodied
& Process
Energy
Use
NOX &
SOX
Heavy
Metals
CO2
etc.
Lifetime
Energy
Dispose
or Waste
Methane
NOX &
SOX
Heavy
Metals
CO2
etc.
Process
Energy
Portland Cement Production
Part of the Problem and/or Potential Solution?
20,000,000,000
18,000,000,000
16,000,000,000
14,000,000,000
World Production PC
12,000,000,000
10,000,000,000
Tonnes CO2 from unmodified PC
8,000,000,000
World Production Concrete
6,000,000,000
Calculated Proportion Aggregate
4,000,000,000
2,000,000,000
Assumptions - 50% non PC N-Mg mix and Substitution by Mg Carbonate Aggregate
Percentage by Weight of Cement in Concrete
Percentage by weight of MgO in cement
Percentage by weight CaO in cement
Proportion Cement Flyash and/or GBFS
1 tonne Portland Cement
Proportion Concrete that is Aggregate
CO2 captured in 1 tonne aggregate
CO2 captured in 1 tonne MgO (N-Mg route)
CO2 captured in 1 tonne CaO (in PC)
2009
2006
2003
2000
1997
1994
1991
1988
1985
1982
1979
1976
1973
1970
1967
1964
1961
1958
1955
1952
1949
1946
0
Source USGS: Cement Pages
15.00%
6%
29%
50%
0.864Tonnes CO2
72.5%
1.092Tonnes CO2
2.146Tonnes CO2
0.785Tonnes CO2
Criteria for New Cements
Criteria
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
Speed and Ease of Implementation
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Good
Bad
Future Cement Contenders
PC and Derivatives
PC
PC
PC
Modified
Ternary
Blends
(50% PC)
Process
Convent
ional
Permea
ble
Block
formula
tion
Split
Process
– Lime
then
clinker
Split
Process
– Lime
(with
capture
)then
clinker
Decarbonati
on CO2
(tonnes CO2
/ tonne
Compound)
Emissions
(if no kiln
capture–
tonnes CO2
/ tonne
Compound)
Net Emissions
(Sequestration)
(tonnes CO2 /
tonne
Compound,
Assuming 100%
carbonation 1
year)
Example of
Cement Type
Apply to
.370
0.498
.868
.004
Ordinary
.864 Portland
Cement
.370
0.498
.868
.144
Ordinary
.724 Portland
Cement
Most dense
concretes
Most dense
concretes
Most dense
concretes
.40 ?
.40?
.004
Split process
lime with
.40?.
recapture then
clinker
.185
.185
.002
Terniary mix
.183 with MgO
additive.
1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA20Jan2011.xls
2. http://www.tececo.com/files/newsletters/Newsletter93.php
Comment
Notes
Cements
Based on
Process CO2
(tonnes CO2
/ tonne
Compound)
Absorption
(tonnes CO2
/ tonne
Compound,
Assuming
100%
carbonation
1 year)
Most dense
concretes
No
supplementary
cementious or
pozzolanic
materials
No
supplementary
cementious or
pozzolanic
materials
No
supplementary
cementious or
pozzolanic
materials
1
1
1
2
The Global Warming Problem
Global Carbon Flows
After: David Schimel and Lisa Dilling, National
Centre for Atmospheric Research 2003
The global CO2 budget is the balance of CO2
transfers to and from the atmosphere. The
transfers shown below represent the CO2
budget after removing the large natural
transfers (shown to the right) which are
thought to have been nearly in balance
before human influence.
Woods Hole Carbon Equation (In billions of metric tonnes)
Atmosp
heric
increase
3.2 (±0.2)
= Emissions from
fossil fuels
6.3 (±0.4)
+
Net emissions
from changes in
land use
2.2 (±0.8)
-
Oceanic
uptake
2.4 (±0.7)
-
Missing
carbon
sink
2.9 (±1.1)
From: Haughton, R., Understanding the Global Carbon Cycle. 2009, Woods Hole Institute at http://www.whrc.org/carbon/index.htm
Net Atmospheric Increase in Terms
of Billions of Tonnes CO2
Using the Figures from Woods Hole on the Previous Slide
Atmospheric
increase
=
3.2 (±0.2)
Emissions from
fossil fuels
+
6.3 (±0.4)
Net emissions from
changes in land use
-
2.2 (±0.8)
Oceanic
uptake
-
2.4 (±0.7)
Missing
carbon sink
2.9 (±1.1)
Converting to tonnes CO2 in the same units by multiplying by 44.01/12.01, the ratio of
the respective molecular weights.
Atmospheric
increase
11.72 (±0.2)
=
Emissions from
fossil fuels
23.08 (±0.4)
+
Net emissions from
changes in land use
8.016 (±0.8)
-
Oceanic
uptake
8.79 (±0.7)
-
Missing
carbon sink
10.62 (±1.1)
From the above the annual atmospheric increase of CO2 is in the order of 12 billion metric
tonnes.
How Much Man Made Carbonate
to Solve Global Warming?
If a proportion of the built environment were man made carbonate, how
much would we need to reverse global warming?
MgO + H2O => Mg(OH)2 + CO2 + 2H2O => MgCO3.3H2O
40.31 + 18(l) => 58.31 + 44.01(g) + 2 X 18(l) => 138.368 molar masses.
44.01 parts by mass of CO2 ~= 138.368 parts by mass MgCO3.3H2O
1 ~= 138.368/44.01= 3.144
12 billion tonnes CO2 ~= 37.728 billion tonnes of nesquehonite
or
MgO + H2O => Mg(OH)2 + CO2 + 2H2O => MgCO3
40.31 + 18(l) => 58.31 + 44.01(g) + 2 X 18(l) => 84.32 molar masses.
CO2 ~= MgCO3
44.01 parts by mass of CO2 ~= 84.32 parts by mass MgCO3
1 ~= 84.32/44.01= 1.9159
12 billion tonnes CO2 ~= 22.99 billion tonnes magnesite
CaO + H2O => Ca(OH)2 + CO2 + 2H2O => CaCO3
56.08 + 18(l) => 74.08 + 44.01(g) + 2 X 18(l) => 100.09 molar masses.
CO2 ~= CaCO3
44.01 parts by mass of CO2 ~= 100.09 parts by mass MgCO3
1 ~= 100.09/44.01= 2.274
12 billion tonnes CO2 ~= 27.29 billion tonnes calcite (limestone)
Modified PC 50% Ternary PC Mix
with N-Mg Route Mg Carbonate Aggregate
20,000,000,000
World Production PC
18,000,000,000
Tonnes CO2 from unmodified PC
World Production Concrete
16,000,000,000
Calculated Proportion Aggregate
14,000,000,000
CO2 Captured in Mg Carbonate Aggregate
12,000,000,000
Net tonnes CO2 in Cement less Additions
Net Sequestration
10,000,000,000
8,000,000,000
The addition of 6 - 10% MgO
replacing PC in high substitution
mixes accelerates setting.
6,000,000,000
4,000,000,000
2,000,000,000
Assumptions - 50% non PC N-Mg mix and Substitution by Mg Carbonate Aggregate
Percentage by Weight of Cement in Concrete
Percentage by weight of MgO in cement
Percentage by weight CaO in cement
Proportion Cement Flyash and/or GBFS
1 tonne Portland Cement
Proportion Concrete that is Aggregate
CO2 captured in 1 tonne aggregate
CO2 captured in 1 tonne MgO (N-Mg route)
CO2 captured in 1 tonne CaO (in PC)
2009
2006
2003
2000
1997
1994
1991
1988
1985
1982
1979
1976
1973
1970
1967
1964
1961
1958
1955
1952
1949
1946
0
Source USGS: Cement Pages
15.00%
6%
29%
50%
0.864Tonnes CO2
72.5%
1.092Tonnes CO2
2.146Tonnes CO2
0.785Tonnes CO2
Modified PC 50% Ternary Mix with
N-Mg Route Mg Carbonate Aggregate
•
•
•
•
•
•
•
25-30% improvement in strength
Fast first set
Better Rheology
Less shrinkage – less cracking
Less bleeding
Long term durability
Solve autogenous shrinkage?
Criteria
Good
Energy Requirements and Chemical Releases, Use >50% replacements and still set like “normal”
Reabsorption (Sequestration?)
concrete!
Speed and Ease of Implementation
Rapid adoption possible
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Bad
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php
Excellent until fly ash runs out!
Uses GBFS and fly ash and nanufactured
nesquehonite based aggregate
Excellent all round
High thermal capacity
Excellent
No issues
Future Cement Contenders
Mg Group
MgO
7501000oC
<750oC
<450oC
<450oC
Conven
tional
MgCO3
+ TecKiln
MgCO3.
3H2O
Conven
tional
MgCO3.
3H2O
+TecKiln
Silicate
route
.403
Decarbonati
on CO2
(tonnes CO2
/ tonne
Compound)
1.092
.056
.693
.038
Emissions
(if no kiln
capture–
tonnes CO2
/ tonne
Compound)
1.495
.056
1.092
1.784
.038
Absorption
(tonnes CO2
/ tonne
Compound,
Assuming
100%
carbonation)
Net Emissions
(Sequestration)
(tonnes CO2 /
tonne
Compound,
Assuming
100%
carbonation)
Example of
Cement Type
Apply to
Comment
Notes
Cements
Based
Process
on
Process
CO2
(tonnes
CO2 / tonne
Compound)
-1.092
Sorel &
Magnesium
.403
Phosphate
cements.
-1.092
Eco-cement
concrete, pure
-1.036 MgO concretes
Novacem
concretes
TecEco,
Cambridge &
Novacem
-2.184
Eco-cement
concrete, pure
-.399 MgO concretes
Novacem
concretes?
TecEco,
Cambridge &
Novacem
-2.184
Eco-cement
concrete, pure
-2.146 MgO concretes
Novacem
concretes?
TecEco,
Cambridge &
Novacem
N-Mg route
University of
Rome
Novacem
After Klaus
Lackner?
1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA20Jan2011.xls
Historic and
Mg Phosphates
Conventional
potentially v.
Oak Ridge
green.
spin offs.
TecEco EcoCement
Force
carbonated pure
MgO
Mg Solvay
process
University of
Rome, initial
absorption is
1.092
1
1
1
1
Magnesium Phosphate Cements
• Chemical cements that rely on the precipitation of insoluble magnesium
phosphate from a mix of magnesium oxide and a soluble phosphate.
• Some of the oldest binders known (dung +MgO)
• Potentially very green
– if the magnesium oxide used is made with no releases or via the nesquehonite
(N-Mg route) and
– a way can be found to utilise waste phosphate from intensive agriculture and
fisheries e.g. feedlots. (Thereby solving another environmental problem)
Criteria
Good
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
The MgO used could be made without releases
Speed and Ease of Implementation
Rapid adoption possible
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Economies of scale issue for MgO to overcome
With technology could use waste phosphate reducing
water pollution
Excellent all round
High thermal capacity
No issues
Bad
There is not much phosphate on the planet
If barrier overcome (see below)
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php. Must find a way to extract phosphate from
organic pollution.
Sorel Type Cements and Derivatives
Sorel Type Cements and Derivatives are all nano
or mechano composites relying on a mix of ionic,
co-valent and polar bonding.
There are a very large number of permutations
and combinations and thus a large number of
patents
Criteria
Good
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
The MgO used could be made without releases
Speed and Ease of Implementation
More could be used
Barriers to Deployment
Cost/Benefit
Economies of scale issue for MgO to overcome
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Excellent except
Thermal
High thermal capacity
Architectural
Safety
No issues
Audience 1
Audience 2
Bad
If barrier overcome (see below)
Not waterproof even with modification.
Not waterproof
Not waterpoof, salt affect metals
Magnesium Carbonate Cements
• Magnesite (MgCO3) and the di, tri, and pentahydrates known as
barringtonite (MgCO3·2H2O), nesquehonite (MgCO3·3H2O),
and lansfordite (MgCO3·5H2O), respectively.
• Some basic forms such as artinite (MgCO3·Mg(OH)2·3H2O),
hydromagnestite (4MgCO3·Mg(OH)2·4H2O) and dypingite
(4MgCO3· Mg(OH)2·5H2O) also occur as minerals.
• We pointed out as early as 2001 that magnesium carbonates are
ideal for sequestration as building materials mainly because a
higher proportion of CO2 than with calcium can be bound and
significant strength can be achieved.
• The significant strength is a result of increased density through
carbonation (high molar volume increases) and the
microstructure developed by some forms.
Future Cement Contenders
Mg Group
MgO
7501000oC
<750oC
<450oC
<450oC
Conven
tional
MgCO3
+ TecKiln
MgCO3.
3H2O
Conven
tional
MgCO3.
3H2O
+TecKiln
Silicate
route
.403
Decarbonati
on CO2
(tonnes CO2
/ tonne
Compound)
1.092
.056
.693
.038
Emissions
(if no kiln
capture–
tonnes CO2
/ tonne
Compound)
1.495
.056
1.092
1.784
.038
Absorption
(tonnes CO2
/ tonne
Compound,
Assuming
100%
carbonation)
Net Emissions
(Sequestration)
(tonnes CO2 /
tonne
Compound,
Assuming
100%
carbonation)
Example of
Cement Type
Apply to
Comment
Notes
Cements
Based
Process
on
Process
CO2
(tonnes
CO2 / tonne
Compound)
-1.092
Sorel &
Magnesium
.403
Phosphate
cements.
-1.092
Eco-cement
concrete, pure
-1.036 MgO concretes
Novacem
concretes
TecEco,
Cambridge &
Novacem
-2.184
Eco-cement
concrete, pure
-.399 MgO concretes
Novacem
concretes?
TecEco,
Cambridge &
Novacem
-2.184
Eco-cement
concrete, pure
-2.146 MgO concretes
Novacem
concretes?
TecEco,
Cambridge &
Novacem
Nesquehonite
route University
of Rome
Novacem
After Klaus
Lackner?
1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA20Jan2011.xls
Historic and
Mg Phosphates
Conventional
potentially v.
Oak Ridge
green.
spin offs.
TecEco EcoCement
Force
carbonated pure
MgO
Mg Solvay
process
University of
Rome, initial
absorption is
1.092
1
1
1
1
TecEco Eco-Cements (Tec-Kiln)
Eco-Cements are blends of one or more hydraulic cements and
relatively high proportions of reactive magnesia with or without
pozzolans and supplementary cementitious additions. They will only
carbonate in gas permeable substrates forming strong fibrous
minerals. Water vapour and CO2 must be available for carbonation
to ensue.
Eco-Cements can be used in a wide range of products from foamed
concretes to bricks, blocks and pavers, mortars renders, grouts and
pervious concretes such as our own permeacocrete. Somewhere in
the vicinity of the Pareto proportion (80%) of conventional concretes
could be replaced by Eco-Cement.
Left: Recent Eco-Cement blocks made, transported and erected in a week.
Laying and Eco-Cement floor. Eco-Cement mortar & Eco-cement mud
bricks. Right: Eco-Cement permeacocretes and foamed concretes
Criteria
Good
Bad
Energy Requirements and Chemical Releases, The MgO used could be made without releases and
Reabsorption (Sequestration?)
using the N-Mg route
Speed and Ease of Implementation
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Easily implemented as no carbonation rooms etc
reqd.
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php.
We need carbon trading!
Economies of scale issue for MgO to overcome
A vast array of wastes can be incorporated
Excellent
Engineered thermal capacity and conductivity.
Need to be handled gently in the first few days
TecEco Eco-Cements (Tec-Kiln, N-Mg route)
Scope for Reducing Energy Using Waste Heat?
Initial weight loss below 100" consists almost entirely of water (1.3 molecules per
molecule of nesquehonite). Between 100 and 1500C volatilization of further water
is associated with a small loss of carbon dioxide (~3-5 %).
From 1500C to 2500C, the residual water content varies between 0-6 and 0-2
molecules per molecule of MgC03. Above 3000C, loss of carbon dioxide becomes
appreciable and is virtually complete by 4200C, leaving MgO with a small residual
water content.
Energy could be saved using a two stage calcination process using waste energy for the
first stage.
Nesquehonite courtesy of Vincenzo
Ferrini, university of Rome.
Dell, R. M. and S. W. Weller (1959). "The
Thermal Decomposition of Nesquehonite
MgCO3 3H20 And Magnesium Ammonium
Carbonate MgCO3 (NH4)2CO3 4H2O."
Trans Faraday Soc 55(10): 2203 - 2220.
Criteria
Good
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
The total process uses two
Speed and Ease of Implementation
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Easily implemented as no carbonation rooms etc
reqd.
Bad
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php.
We need carbon trading!
Economies of scale issue for MgO to overcome
A vast array of wastes can be incorporated
Excellent
Engineered thermal capacity and conductivity.
Need to be handled gently in the first few days
Moleconomic Flows – N-Mg Process
The Nesquehonite Route
The annual world production of HCl is about 20 million tons,
most of which is captive (about 5 million tons on the
merchant market).
The Tec-Reactor Hydroxide
Carbonate Capture Cycle
• The solubility of carbon dioxide gas in seawater
– Increases as the temperature approached zero and
– Is at a maxima around 4oC
• This phenomenon is related to the chemical nature of CO2 and
water and
• Can be utilised in a carbonate – hydroxide slurry process to
capture CO2 out of the air and release it for storage or use in a
controlled manner
Gaia Engineering
Portland Cement
Manufacture
CaO
Industrial CO2
Brine,
Sea
water,
Oil
Process
water,
De Sal
Waste
Water
etc .
N-Mg
Process
TecEco
Tec-Kiln
MgO
MgCO3.3H2O
Clays
TecEco
Cement
Manufacture
GBFS
Fly ash
Fresh
Water
EcoCements
NH4Cl or HCl
Building
components &
aggregates
Other wastes
TecCements
The N-Mg Process
HCl
NH3 and a small amount of CO2
CO2
H2O
Tec-Kiln
Mg rich water
Ammoniacal Mg rich water
MgCO3.3H2O
MgO
MgO
Mg(OH)2
Steam
MgCO3.3H2O
Filter
Filter
NH4Cl and a small amount of NH4HCO3
A Modified Solvay Process for Nesquehonite
Future Cement Contenders
Process
CO2
(tonnes CO2
/ tonne
Compound)
Decarbonati
on CO2
(tonnes CO2
/ tonne
Compound)
Emissions
(if no kiln
capture–
tonnes CO2
/ tonne
Compound)
Absorption
(tonnes CO2
/ tonne
Compound,
Assuming
100%
carbonation)
Net Emissions
(Sequestration)
(tonnes CO2 /
tonne
Compound,
Assuming
100%
carbonation)
Cements
Based
on
Process
CaO
Conventi
onal
.453
0.785
1.237
.785
C3S
Conventi
onal
?
0.578
>0.578
?
>0.578
C2S
Conventi
onal
?
0.511
>0.511
?
>0.511 Belite cement
Chinese & others
3
C3A
Conventi
onal
?
Tri calcium
>0.594 aluminate
cement
Increased
proportion
3
C4A3S
Conventi
onal
Chinese & others
3
Geopolymer
Alliance,
Geopolyer
Institute,
University
Melbourne
4
Geopoly
mers
Flyash +
NaOH
?
?
0.16
0.594
0.216
>0.594
>0.216
?
Carbonating
.453
lime mortar
Calcium
? sulfoaluminate
cement
0.16
Apply to
Comment
Calera, British
Lime Assn &
many others
Small net
sequestration
with TecEco
kiln
Notes
Example of
Cement Type
1
3
1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA20Jan2011.xls
3. Quillin, K. and P. Nixon (2006). Environmentally Friendly MgO-based cements to support sustainable construction - Final report, British Research Establishment.
4. http://www.geopolymers.com.au/science/sustainability
CaO-Lime
Criteria
Good
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
The CaO used could be made without
Speed and Ease of Implementation
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Easily implemented as no carbonation rooms etc
reqd.
Good
Engineered thermal capacity and conductivity.
An irritating dust
Bad
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php.
We need carbon trading!
Geopolymers
Criteria
Good
Energy Requirements and Chemical Releases,
Reabsorption (Sequestration?)
Low provided we do not run out of fly ash
Speed and Ease of Implementation
Barriers to Deployment
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering
Thermal
Architectural
Safety
Audience 1
Audience 2
Process issues to be overcome
Good but inconsistent
Engineered thermal capacity and conductivity.
Caustic liquors
Bad
Permissions and rewards systems see
http://www.tececo.com/sustainability.permissions_rewa
rds.php.
We need carbon trading!
Other Contenders
• Belite cements suffer from a slower setting rate
which could be accelerated with more aluminates
rather than alite. MgO works to some extent as well
althougth as yet we have not done enough work
• Sulfoaluminate type cements have a low energy
requirement.
Barriers to Market - Patents
Fierce competition whilst the
world heats up reminds me of
Nero.
Perhaps a more co-operative
approach is more appropriate.
We face after all common supply
chain, economic and technical
issues.
We should jointly be marketing
to governments as new
technologies are essential as the
potential for emissions
reduction and sequestration is
enormous
http://www.google.com/patents?id=hhYJ
AAAAEBAJ&printsec=abstract&zoom=4#v
=onepage&q&f=false
Barriers to Market
– Lack of Carbon Trading
TecEco have been held up by unrelenting patent attacks, unfair competition from
universities and a lack of carbon trading. There are still some easily overcome supply
chain and economy of scale issues however we have invented our way through most
of them.
The Concept of a Carbonate Built Environment
13th July 2002 – Fred Pearce in New Scientist about TecEco
magnesium cement technology:
“THERE is a way to make our city streets as green as the
Amazon rainforest. Almost every aspect of the built
environment, from bridges to factories to tower blocks, and
from roads to sea walls, could be turned into structures that
soak up carbon dioxide- the main greenhouse gas behind global
warming. All we need to do is change the way we make cement.
All we have to do is change the way we do things and do what a big old tree does
– make our homes out of CO2