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Beneficial Use of Carbon Dioxide in Precast Concrete Production
Beneficial Use of Carbon Dioxide in Precast Concrete Production
Beneficial Use of Carbon Dioxide in Precast Concrete Production
Final Report
For the period October 1, 2010 –March 30, 2014
WORK PERFORMED UNDER AGREEMENT
DE‐FE0004285
SUBMITTED BY
Yixin Shao
McGill University
817 Sherbrooke Street West
Montreal, Quebec H3A 2K6
June 26, 2014
PRINCIPAL INVESTIGATOR
Yixin Shao
514‐398‐6674
Email: yixin.shao@mcgill.ca
Subcontractor: 3H Company
1500 Bull Lea Road, Suite R1
Lexington, KY 40511
SUBMITTED TO
U.S. Department of Energy
National Energy Technology Laboratory
Darin Damiani – FPM/COR
1
DISCLAIMER
This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for
the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed,
or represents that its use would not infringe privately owned rights. Reference herein to any specific
commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does
not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States
Government or any agency thereof. The views and opinions of authors expressed herein do not
necessarily state or reflect those of the United States Government or any agency thereof.
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ABSTRACT
The feasibility of using carbon dioxide as feedstock in precast concrete production is studied. Carbon
dioxide reacts with calcium compounds in concrete, producing solid calcium carbonates in binding
matrix. Two typical precast products are examined for their capacity to store carbon dioxide during the
production. They are concrete blocks and fiber‐cement panels. The two products are currently mass
produced and cured by steam. Carbon dioxide can be used to replace steam in curing process to
accelerate early strength, improve the long‐term durability and reduce energy and emission. For a
reaction within a 24‐hour process window, the theoretical maximum possible carbon uptake in concrete
is found to be 29% based on cement mass in the product. To reach the maximum uptake, a special
process is developed to promote the reaction efficiency to 60‐80% in 4‐hour carbon dioxide curing and
improve the resistance to freeze‐thaw cycling and sulfate ion attack. The process is also optimized to
meet the project target of $10/tCO2 in carbon utilization. By the use of self‐concentrating absorption
technology, high purity CO2 can be produced at a price below $40/t. With low cost CO2 capture and
utilization technologies, it is feasible to establish a network for carbon capture and utilization at the
vicinity of carbon sources. If all block produces and panel producers in United States could adopt carbon
dioxide process in their production in place of steam, carbon utilization in these two markets alone
could consume more than 2 Mt CO2/year. This capture and utilization process can be extended to more
precast products and will continue for years to come.
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TABLE OF CONTENT
ABSTRACT 3
EXECUTIVE SUMMARY 5
1. INTRODUCTION 7
2. EXPERIMENTAL METHODS 8
2.1 Design and fabrication of CO2 chambers for blocks and panels 8
2.4 Performance evaluation 11
2.5 Self‐concentrating absorption process for CO2 recovery 13
3. RESULTS AND DISCUSSION 15
3.1 Theoretical maximum possible carbon uptake at early age 15
3.2 Concrete block carbonation 16
3.3 Fiber‐cement panel carbonation 18
3.4 Durability performance evaluation of carbonated products 20
3.5 CO2 recovery using self‐concentrating absorption technique 25
3.6 Utilization cost analysis 26
4. CONCLUSIONS 28
5. LIST OF FIGURE CAPTION 29
6. REFERENCES 29
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EXECUTIVE SUMMARY
Concrete is the most used man‐made material on the Earth. In North America the consumption of
concrete has exceeded one ton per capita per year. Precast concrete shares abut 20‐30% of the market.
Based on Freedonia Group prediction, the annual sales of precast concrete in United States can reach
US$11.3 billion in 2015. The precast products include blocks, bricks, artificial stones, panels, pipes, slabs,
and general precast building components. The typical feature of precast products is that they are
produced in factory under controlled environment so that proper curing can be performed to improve
the quality. To accelerate the production cycles and promote full hydration, atmospheric steam curing
is usually applied. Some products are even produced at high pressure (autoclave) steam curing. This
steam curing process can be replaced by carbon dioxide curing. Concrete is reactive with carbon dioxide.
It is the calcium compound in cement binder that reacts with carbon dioxide to form calcium
carbonates. If this reaction can be introduced at early age during curing, the reaction products are
beneficial to strength and durability improvement. Carbonation reaction is a carbon dioxide uptake
process and can be used for carbon capture, utilization and storage (CCUS).
This report is to summarize a study on beneficial use of carbon dioxide in making two typical precast
products: concrete blocks and fiber‐cement panels. They are mass produced and require steam curing.
The objective of the project is to develop a process to maximize the carbon uptake and minimize the
energy consumption. The criterion used in optimization is that the utilization cost shall not exceed
$10/tCO2, at the same time the carbon uptake is maximized. The project has also examined the
feasibility of using self‐concentration absorption technology to produce low cost CO2 for concrete
utilization. The challenge is if the carbon dioxide can be made below the benchmark price of $50/tCO2.
A carbonation process is developed using either static system or dynamic system. In static carbonation,
the concrete products are preconditioned by initial hydration presetting and then placed in a carbon
dioxide chamber for reaction. In dynamic system, the fresh products can be placed directly in chamber
and CO2 gas is circulated to simultaneously perform preconditioning and carbonation. Both systems are
effective to reach targeted carbon uptake. The major difference is in that static system consumes much
less energy than the dynamic system. If the cost of the utilization is limited to $10/tCO2, static system
has shown advantages although it takes longer time for production cycle. To achieve the project target,
static system was used in most of the study.
To maximize the carbon uptake in precast concrete, it is necessary to know he maximum possible
uptake capacity within 24h process window. It is accomplished by a theoretical analysis. Using reaction
equations and cement powder solution carbonation tests, it is found that the maximum possible carbon
dioxide uptake by cement in concrete is about 29.1% after 18h initial hydration. It is based on cement
content used in concrete.
Carbonation curing of concrete blocks and cement panels are therefore carried out to push for
maximum possible uptake. For concrete blocks, if carbonation is performed by only 2‐4 hours after 18h
hydration presetting, the carbon uptake reaches 15‐18% and the strength of carbonated concrete is of
close value to hydrated reference. The short carbonation after prolonged hydration does not increase
5
the strength. However if carbonation can be extended to 24h or 48 h, the carbon uptake can be
enhanced to 17‐24% and strengths at both early age and late age are increased significantly. Higher gas
pressure and longer curing time will promote more carbonation reaction. Even after 48 h carbonation,
the theoretical limit is still not reached. For panel carbonation, carbon uptake capacity is higher. For
carbonation of only 0.5h, carbon uptake can reach 17‐20%. For 24h prolonged carbonation, the panel
can take 30% of carbon dioxide, a theoretical limit. The corresponding strengths are comparable to or
better than that of commercial panel products.
The results show that durability improvement is more significant than strength gain. The comparison of
stress strain curves shows that the carbonated concrete is not more brittle since the carbonation
reaction happens at early age and is followed by a subsequent hydration. Because of this nature of the
process, the concrete resistance to freeze‐thaw cycles, ettringite sulfate attack and thaumasite sulfate
attack is greatly improved. It is attributed to the densified cement matrix and reduced pore size.
Utilization cost is performed based on the developed process. It is found that the key components that
require energy are the hydration presetting and residual gas disposal. Hydration presetting is basically a
drying process and is therefore associated with relative humidity (RH) of the working environment.
Digital fan was used to quantify the energy needed for fan drying. For RH in a range of 20‐60%, the
energy cost will be below $5/tCO2 for fan drying. For high humid condition, more energy may be
required to dry the product within 24h process window. This is the main source of energy consumption
and can be improved by using more energy efficient fan system. To reduce the energy consumption in
residual gas disposal after carbonation, a chamber with self‐cleaning is designed and tested. If the free
space in chamber can be reduced to minimum, carbon dioxide injected can be fully consumed leaving no
residual gas to dispose. Therefore, the main cost in utilization in static system is the presetting drying. At
industry scale production, this cost can be much reduced. It is conclusive that carbon utilization in
concrete carbonation can be performed under $10/tCO2.
To implement large scale concrete carbonation for CCUS, low cost carbon dioxide is the key to success.
Self‐concentrating absorption (SCA) technology is examined for its capacity to produce CO2 below
benchmark price of $50/tCO2. The cost analysis is based on the DOE NETL Baseline. The results show
that phase transitional self‐concentrating absorption technology for carbon capture can meet and even
exceed DOE goal – less than 35% increase of cost of electricity or less than $40 USD/ton CO2 with 90%
CO2 captured from post combustion flue gas.
With $40/tCO2 for capture and $10/tCO2 for utilization, it is possible to make concrete block
$0.018/block for curing. It is based on the assumption that each block can take 0.36kg CO2. It is
corresponding to 20% uptake by cement mass. If carbon credit of $10/t can be claimed, the final cost is
$0.014/block. It is comparable to the cost by steam using natural gas. If CO2 cost can be further reduced,
the carbonation process can gain profit, in addition to environmental and technical advantages.
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1. INTRODUCTION
In comparison to cast‐in‐place concrete, precast concrete products offer a number of advantages
including superior strength and durability, design flexibility, aesthetic versatility, minimal environmental
impact, faster construction and reduced life cycle costs. Precast concrete is considered a green building
material and can qualify for LEED credits. Annual sales volume of precast concrete in USA is predicted to
reach US$11.3 billion in 2015. The products cover a wide range of applications from blocks, bricks,
panels, veneers to pipes, slabs, beams and columns. Precast concrete plants are geographically
distributed almost everywhere in the world and often located in the vicinity of CO2 sources such as
power plants and cement plants. This provides an opportunity for precast concrete plants to beneficially
utilize the captured carbon dioxide through the carbonation curing of precast products.
Carbonation curing is a chemical reaction between cement binder and carbon dioxide at early age right
after the precast products are formed. It can occur, in the presence of moisture, between cement
anhydrate phases (C3S or C2S) and carbon dioxide in a fresh concrete immediately after formation. Its
reaction is described by Eqs. 1 and 2 [1]. Carbon dioxide curing can also take place between hydration
products, such as calcium hydroxide (Ca(OH)2 ) and calcium silicate hydrate (3CaO∙2SiO2∙3H2O, or C‐S‐H),
and carbon dioxide in a partially cured concrete within 24 hours. The reaction is then governed by Eqs. 3
and 4. In both cases, the reaction products are primarily calcium carbonates and calcium silicate
hydrates [2].
2(3CaO∙SiO2) + 3CO2 + 3H2O → 3CaO∙2SiO2∙3H2O + 3CaCO3 (1)
2(2CaO∙SiO2) + CO2 + 3H2O → 3CaO∙2SiO2∙3H2O + CaCO3 (2)
Ca(OH)2 + CO2 → CaCO3 + H2O (3)
3CaO∙2SiO2∙3H2O + 3CO2 → 3CaCO3 + 2SiO2 + 3H2O (4)
As indicated by Eqs 1‐4, carbonation curing of concrete is a CO2 sequestration process. Gaseous carbon
dioxide is converted to thermodynamically stable calcium carbonate which is embedded in calcium
silicate hydrate. It was estimated that, at full carbonation at which all CaO reacts with CO2 to form
CaCO3, the CO2 uptake by ordinary Portland cement is 50% by cement mass [3], i.e. one ton of cement
can consume half a ton of carbon dioxide to form one and a half ton of solid calcium carbonate.
However, this theoretical maximum is not possible to achieve in a densely formed concrete product.
Carbon uptake is also dependent on the product formulation and its associated process.
This project is to examine two typical precast concrete products: concrete masonry blocks and fiber‐
cement panels. Concrete masonry blocks are ideal candidate products for carbon sequestration since
they are mass produced, porous in nature, and require steam curing. The North American market for
blocks is predicted to increase to 4.3 billion units in 2014 [4]. Cement bonded cellulose fibre panels
have been developed to replace asbestos cement boards and are well accepted in the North America
7
construction market. The panel is formed by slip casting, dewatering, laminating and autoclaving. This
autoclave curing could be possibly replaced by CO2 curing to provide both accelerated strength and
carbon sequestration. The annual production of fiber‐cement panels is estimated to be 0.26 billion m2
(2.8 billion ft2) for standard size of 1.2m x 2.4m (4’x8’) and a thickness of 12 mm (0.5”) [5]. These two
typical products share a common feature: they both require steam curing. While the blocks are usually
cured under atmospheric steam, fiber‐cement panels are treated with autoclave high pressure steam.
The substitute of steam with carbon dioxide not only facilitates carbon sequestration, but can
substantially reduce energy consumption as well.
This report is to present a study on carbonation curing of concrete blocks and fiber‐cement panels, using
carbon dioxide to replace traditional steam and facilitate carbon utilization. The objectives are to
maximize the carbon uptake in the two products and minimize the energy consumption. The criterion
used in optimization of the process is that the performance of carbonated concrete shall be comparable
to or better than the traditional products and the carbon utilization cost shall not exceed $10/tCO2. To
implement large scale production using carbonation process, the cost of recovered CO2 gas becomes
critical. Cost analysis of CO2 recovery using 3H self‐concentrating absorption technique is also
performed.
2. EXPERIMENTAL METHODS
2.1 Design and fabrication of CO2 chambers for blocks and panels
To reduce process emission and energy consumption in traditional steam process, carbon dioxide is
proposed to replace steam. Two CO2 chambers are designed and fabricated as reactors and used in this
project.
Fig 1 shows schematic block carbonation setup for masonry block CO2 curing process. Fig 1a is for static
carbonation and Fig 1b for dynamic carbonation. In static carbonation (Fig 1a), once the blocks are
placed in chamber, CO2 gas is injected to a constant pressure 1 ‐5 bar (14 – 72 psi) and reaction takes
place for 2‐4 hours. In dynamic carbonation, the gas is injected and circulated by a pump to facilitate the
forced diffusion at low pressure of 1 bar (14 psi) and for 2‐4 hours. The difference between the two
setups is in that the static process is energy free but requires longer process time including 18h
presetting and the dynamic process is fast, requires no presetting, can work with fresh product, but
requires energy for gas circulation. Although carbonation of 2‐4h is mostly studied, prolonged
carbonation of 24 h or 48 h is also investigated for maximum possible carbon uptake in extreme
condition.
8
(a) (b)
Fig 1: Block carbonation setup. (a) Static carbonation. (b) Dynamic carbonation.
(a) (b)
Fig 2: Block CO2 chambers. (a) Single block CO2 chamber; (b) Multiple‐block CO2 chamber
The block CO2 chambers for full scale blocks (20 cm or 8”) are displayed in Fig 2. Fig 2a is for single block
and can be used for both static and dynamic process. If gas is injected to desired pressure and
circulation pump is turned off, it is static setup. Fig 2b is for multiple blocks (3‐6 full‐scale blocks) for
static process. To achieve project target of $10/tCO2 in utilization, static system is preferred although
both systems are effective to reach the carbonation uptake.
The schematic of panel CO2 chamber is shown in Fig 3a and the setup in Fig 3b. The setup is used for
both panel making process and panel carbonation process. To make the fiber‐cement panels of 30 cm x
60 cm x 1.2 cm (1’x2’x0.5”), the mix is first cast in the mold in panel clave and compressed to form a 12
mm (0.5”) thick panel. The dewatering process is conducted by air pressure to remove extra free water.
After the dewatering, the panel is removed from the chamber and preconditioned to remove certain
amount if free water. Then the panel is placed back into the same chamber and the CO2 gas is injected
to constant pressure 1‐5 bar (14‐72 psi) and for a specified duration (0.5‐4 h). The system can run either
static or dynamic carbonation.
9
(a) (b)
Fig 3: Panel carbonation setup. (a) Schematic of chamber; (b) Setup of panel carbonation.
2.2 Preparation of blocks and panels for testing
Experimental program was carried out in two steps for both blocks and panels. First the process
parameters were determined by testing with smaller concrete slab samples. The slab dimension is of 7.6
cm x 12.7 cm x 3.8cm (3”x5”x1.5”) for block study and of 7.6 cm x 12.7 cm x 1.2 cm (3”x5”x0.5”) for
panel study. The process parameters are then applied to full scale block (20 cm x 20 cm x 40 cm or
8”x8”x16”) and large scale panel (30 cm x 60 cm x 1.2 cm or 1’x2’x0.5”). Full scale blocks were made in
laboratory by a manual block machine and the large fiber‐cement panel was prepared using setup in Fig
3a to simulate full size (1.2 m x 2.4 m or 4’x8’) commercial panels.
The mixture proportions of both products were formulated following the industry practice. For 20cm
(8”) blocks, the composition included cement = 1.6kg (3.5 lb) (10% by mass), water = 0.9 kg (2 lb), coarse
aggregates = 5.5kg (12.3 lb), fine aggregates = 8.3 (18.5 lb). The total weight of one 8” block was 16 kg
(36 lb). For 30 cm x 60 cm x 1.2 cm (1’x2’x0.5”) fiber cement panels, it used 2.1 kg (4.8 lb) cement (73%
by mass), 0.5 kg (1.1 lb) Water and 0.27 kg (0.6 lb) cellulose fibers. The total weight of one panel was 2.9
kg (6.5 lb). In addition to the traditional recipes, effort was made to incorporate nano‐calcite crystals in
concrete mix design to promote calcium carbonate precipitation and increase the carbon uptake
capacity. The laboratory products are shown in Fig. 4.
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(a) (b)
Fig. 4: Laboratory concrete products for CO2 storage. (a) Concrete blocks; (b) Fiber‐cement panel
2.3 CO2 uptake quantification
Three methods are used to quantify carbon uptake by carbonation [6‐7].
(1) Mass gain method determines CO2 uptake by comparing the mass of concrete before and after
carbonation. The carbonation‐induced water loss is collected using absorbing paper and added to the
mass after carbonation since it is part of the original mass. The CO2 uptake is then compared with dry
cement used in the product to obtain the percent CO2 uptake.
(2) Mass curve method determines CO2 uptake using recorded mass with the origin at the time of gas
injection. A mass curve of the closed‐loop system in Fig. 1 was recorded until the end of the process.
Data collected by mass gain and mass curve methods are two simultaneous measurements from the
same process and therefore are comparable. They are independent from carbon content in original
cement and are the average of entire concrete batch.
(3) Pyrolysis thermal analysis method is also used to determine CO2 uptake in concrete. After
compression tests, large pieces of concrete, 60±5 gram each, were collected to represent typical surface
and core. The concrete pieces were then crashed into size of millimeters and ignited in a furnace. The
mass loss between 450‐1000Ԩ is the CO2 loss representing the average carbon dioxide content in
concrete. The difference of CO2 contents between carbonated and hydrated reference concretes
determines CO2 uptake by carbonation. Percent CO2 uptake is defined based on dry cement mass.
2.4 Performance evaluation
After carbonation, compressive strengths of carbonated and hydrated concretes are tested using small
samples at two ages: immediately after carbonation and 27 days after carbonation. For carbonation of
two hours (2C), the strengths were comparable to references by steam or hydration. However in
prolonged carbonation up to 24 hours (24C) or 48 hours (48C), the strengths of carbonated concretes
were compared with its own hydration references at the same age. Strengths of full size blocks were
also tested at two different ages. To examine the effect of carbonation on brittleness of the final
11
product, the stress and strain curves of concretes after 28 days subsequent hydration were obtained
and compared between carbonation and hydration.
Freeze‐thaw test was conducted on 28‐day after concrete block carbonation following ASTM C1262
procedure. The concrete samples were half submerged in 3% (by weight) sodium chloride saline solution
and were subjected to freeze‐thaw cycle with 6h freezing at ‐18 oC (0 oF) and 18h thawing at 22 oC (72
o
F). The mass loss was recorded versus the cycles.
To investigate ettringite sulfate resistance of carbonated concrete, mortar bar (25×25×285 mm or
1”x1”x11”) tests were performed following ASTM C1012. The bars were cast of a mortar mix with
cement to sand ratio of 1:2.75 by mass and a water to cement ratio of 0.36. Three identical bars were
cast for each curing regime: steam curing, conventional hydration curing and carbonation curing. For
conventional hydration curing, the mortar bars were sealed in container for 28d hydration. For steam
and carbonation curing, mortar bars were treated first by steam or CO2 and then sealed in plastic bag
for subsequent hydration of 28 days. After early age special curing and 28 days subsequent hydration,
mortar bars were immersed in a 5% sodium sulfate solution. The length change of the bars was
monitored on a weekly basis.
X‐Ray Diffraction analysis was also performed on powder samples collected from mortar bars to
determine the calcium hydroxide. Two specimens per batch were used to confirm the obtained results.
The XRD patterns were obtained after 1 and 28 days compressive strength tests using a Philips PW1710
Powder Diffractometer (Cu, K radiation, X'celerator proportional detector, scan interval 5‐60o, 0.02o
and 0.5 seconds per step).
To understand the role of carbonation in microstructure development, SEM analysis was performed.
Quantitative image analysis of backscattered scanning electron microscope (BS‐SEM) pictures was used
[8‐9] to compare the porosity of the CMU samples by different curing methods. Finely polished sections
were obtained from cut samples of the carbonated, steam‐cured and conventionally hydrated
concretes. For the carbonated concrete, samples included the heavily carbonated surface and the less
carbonated or non‐carbonated core. The intensity of BS‐SEM images is proportional to the atomic
number. Therefore concrete pores could be identified as the darkest regions, due to lack of a material to
scatter the radiated electrons. To quantify the porosity, the binary images were obtained by excluding
the grey level greater than 50 on a 255 scale [8‐9]. The area ratio of the dark pixels in the binary image,
representing the porosity, was calculated for each BS‐SEM image.
The durability tests of carbonated concrete subject to sulfate exposure at low temperature were also
performed. These tests were designed to investigate if the calcium carbonates produced during
carbonation had negative effect on the concrete resistance to thaumasite sulfate attack. Serving in
sulfate‐rich environment at low temperature such as 5oC, concrete containing calcium carbonates is
vulnerable to thaumasite formation which could significantly decrease the strength and reduce the
durability. It had occurred to Portland limestone cement. Portland limestone cement (PLC) is considered
as successful example of sustainable development in cement industry. Because of the high content of
limestone (15% or higher), the limestone cement is deteriorated by significant mass loss due to
12
decomposition of CSH binder. That is the reason why limestone cement is not allowed for sulfate rich
environment applications such as underground structures and near‐shore construction. The limit on the
use of limestone cement raised question if carbonation generated calcium carbonate will behave
similarly to limestone in cement. The only difference is that in carbonated concrete, carbonates are in
situ produced while in limestone cement, carbonates are added by intergrinding the cement with
limestone. It is therefore necessary to find out the limit to carbonated products. Thaumasite sulfate
tests were then conducted. Four batches of cement paste cubes (25mm x 25 mm x 25mm or 1”x1”x1”)
were prepared for tests: (1) Hydrated OPC (ordinary Portland cement) with 5% calcium carbonates as
additive; (2) Carbonated OPC with 16% calcium carbonates as combination of the added and produced;
(3) hydrated PLC (Portland limestone cement) with 15% calcium carbonates as additive; (4) carbonated
PLC with 26% calcium carbonates as combination of the added and produced. The hydrated and
carbonated cubes were further cured in sealed condition for 28 days and then submerged in 5% MgSO4
solution at 4oC for thaumasite sulfate tests.
2.5 Self‐concentrating absorption process for CO2 recovery
To facilitate concrete carbonation for carbon storage and performance enhancement, a low cost CO2 is
essential. 3H Company has developed a proprietary self‐concentrating absorption technology to recover
CO2 from flue gas. One of the important components of this project is to examine if the self‐
concentrating absorption technology can reduce the carbon capture cost below DOE benchmark,
$50/tCO2. Flue gas was captured from cement plant and shipped to 3H Company for recovery. The same
technology was also applied to capture CO2 from residue gas of 50% CO2concentration after the
carbonation process. Based on the process, the cost analysis was performed.
The Bench Top Simulator (BTS) was built and used to evaluate the chemical and mechanical workability
of 3H Self‐concentrating amine absorption technology through small scale continuous operation of the
absorption and regeneration functions. 3H will move the technology to the pilot scale to verify the
application of self‐concentrating amine absorption technology in precast concrete production. The BTS
will confirm chemistry in the rich and lean mixtures and provide a preview of fluid handling challenges. It
is anticipated that the BTS will be sized to fit in a laboratory, that the system will be closed from
atmosphere that appropriate provisions will be made at the laboratory to manage working fluids pre
and post test. A custom‐made packed absorption column of the Bench Top Simulator has been built as
shown in Fig. 5.
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(a)
(b)
Fig. 5: The customized packed absorption column. (a) Schematic and (b) Setup
The packed absorption column is a custom‐made device for the absorption of carbon dioxide from a gas
mixture. It is made of a 147 cm (58 inch) tall, 8.9 cm (3.5 inch) diameter jacketed glass tube. The tube
jacket used to maintain temperature control of the absorption process and consists of a 11.4 cm (4.5
inch) diameter glass tube. The tubes are concentrically mounted and secured at each end by 15.2 cm (6
inch) diameter Teflon flanges. Stainless steel 3/8 inch tubing and Swagelok fitting are used throughout
for all liquid and gas transport lines. The whole assembly is supported by a square steel frame 8 feet in
height and mounted on casters for mobility. A Polyscience temperature controlled re‐circulating water
bath maintains the absorption column temperature. The 3.5 inch diameter absorption tube contains an
8 inch tall stainless steel riser that serves as a base to support packing that consists of ¼ inch lengths of
¼ inch diameter polyethylene tubing. The packing stands 44 inches in height from the bottom of the
riser platform. The riser provides space at the bottom for the gas introduction and CO2‐rich absorbent
collection. The absorbent is housed and maintained at a constant temperature in a stainless steel 5.56
liter (1 feet tall with 6 inches in diameter) reservoir located 1 feet above the column. The reservoir
temperature is regulated by a precision K‐type thermocouple controlled heater. The absorbent enters
the column from the bottom of the reservoir through the top flange and is evenly distributed by a
gravity fed spray nozzle with a flow rate control valve. The exact liquid flow rate is determined by the
amount of liquid accumulated in certain period. Precise temperature control of the absorbent is
maintained by K‐type thermocouple controlled heating tape wrapped around the column entrance
tubing. The gas mixture is admitted through the bottom flange through a K‐type thermocouple and
injected 2 inches below the bottom of the column packing. The gases mixtures are proportioned by
flow‐meters. The carbon dioxide is adjusted to have a fixed input concentration (15% CO2 balanced with
N2) by volume flow and verified by an Alpha Omega Series 9510 carbon dioxide analyzer. The scrubbed
gas mixture is collected and measured for carbon dioxide content through the top flange by using an
Alpha Omega Series 9510 carbon dioxide analyzer. The CO2‐rich absorbent is collected at the bottom of
the column by a funnel shaped liquid settler located in the bottom flange, where the CO2‐rich absorbent
is separated into two phases, CO2‐rich phase (not CO2‐rich absorbent) and CO2‐lean phase. The CO2‐lean
phase is re‐circulated to the top reservoir by a fluid metering pump. The CO2‐rich phase is drained from
the bottom flange for the samples of gas‐liquid equilibrium tests. Temperatures of the input and output
liquids and gases are measured with K‐type thermocouples directly.
14
3 RESULTS AND DISCUSSION
3.1 Theoretical maximum possible carbon uptake at early age
To maximize the carbon uptake by concrete products, it is necessary to know the theoretical limit. In
concrete products, it is the Portland cement that is CO2‐reactive. If cement is fully reacted with carbon
dioxide, the CO2 uptake will reach 50% by cement mass [3]. In real products, this full carbonation cannot
be reached because of the short reaction time and the densely‐packed microstructure that will limit the
reaction efficiency. Therefore a fundamental study was carried out to investigate the maximum possible
carbon uptake within 24 hour process window after concrete products were cast formed. If a hydration
presetting of 18 h is involved, four reactants can make contribution to carbon uptakes due to their
carbonation reactions at early age. Their chemical reactions are given in Eqs 1‐4. The maximum possible
carbon uptake within 24 h process window is estimated based on the four reactions.
Table 1 summarizes the theoretical prediction of phase changes due to hydration and carbonation. After
18h initial hydration, clinker phases (C3S, C2S, C3A, C4AF) are reduced and hydration products (Ca(OH)2,
C‐S‐HHyd) are produced (column three). If four reactants (Ca(OH)2, C‐S‐HHyd, C3S, C2S) are assumed to be
reactive with CO2 at this early age and for a short period of time, full carbonation after initial hydration
presetting of 18 hours will allow CO2 uptake to reach 29.1% by cement mass (column six) [10‐12].
Cement powder solution test was carried out to verify the theoretical maximum possible value. Cement
powder was mixed in water for 18h and CO2 gas was injected to the solution. After 24h carbonation in
solution, the cement powder was collected and analyzed by its CO2 content. In this ideal test condition
where cement particles were completely suspended and reacted fully with CO2 in a prolonged time of
24h, the uptake was 28.5% by dry cement mass. The theoretical prediction of 29.1% as maximum
possible carbon uptake by cement is in good agreement with experiment. The theoretical prediction
indicates maximum possible carbon uptake in early carbonation curing is about 29% based on cement
mass. This will serve as a reference for concrete carbonation.
15
Table 1: Theoretical prediction of phase changes in hydration and carbonation
Carbonation Carbonation
Initial After 18h Full Full
Phase without after 18h
cement Hydration Hydration carbonation
hydration hydration
CO2 uptake (%) 0 0 0 19.7 29.1 52.6
C3S(%) 59 34 0 0 0 0
C2S(%) 20 18 0 0 0 0
C3A(%) 7 3 0 7 3 0
C4AF(%) 8 6 0 8 6 0
Ca(OH)2, % 0 12 30 0 0 0
C‐S‐HHyd (%) 0 21 64 0 0 0
C‐S‐HCarb(%) 0 0 0 64 44 0
CaCO3(%) 0 0 0 45 66 120
SiO2 gel(%) 0 0 0 0 6 20
3.2 Concrete block carbonation
Concrete block carbonation was conducted with different process parameters to push for maximum
possible carbon uptake. Table 2 shows the CO2 uptake results. Batches C1‐C7 were tested using small
samples and C8 was full‐size single block. Longer carbonation time (48h) and higher gas pressure could
enhance CO2 uptake. In batch C7, it is possible to reach theoretical maximum by carbonation of 48h at 2
bar (29 psi), although 48h carbonation is not economically practical. Full size block (C8) processed at 5
bar (72.5 psi) pressure and 4h carbonation could reach carbon uptake by 22%. This process is practically
feasible with reaction efficiency of 75%.
Table 2: Effect of pressure and duration on CO2 uptake in concrete block carbonation
Initial hydration = 18h, Time = carbonation time, and Pressure= carbonation pressure, RH =20%.
16
The compressive strengths of carbonated and hydrated concrete are shown in Table 3. For 2‐hour
carbonation (18H+2C), the strengths were comparable to steamed or hydrated references either
immediately after carbonation (20h) or 28 days after subsequent hydration (28d). Short carbonation
after hydration presetting did not increase the strength. However the prolonged carbonation did
enhance the strength significantly. For 24h or 48h carbonation, both short term (42h) and the long
term (28d) strengths were increased in comparison to steam and hydration references. Higher degree
of carbonation usually produces high strength of concrete, although prolonged carbonation might not
be economically feasible. Hydrate blocks were not as strong as the carbonated slab of small samples.
This was because the manual block machine was not effective in making sufficient compact pressure.
Table 3: Compressive strength of carbonated and hydrated concretes
After initial curing After 28 days subsequent
ID (MPa) hydration (MPa)
C1 (18H+2C) 10.5±0.4 (20h) 22.8±1.7
C2 (18H+2C) 11.4±1.6 (20h) 21.7±0.7
C3 (18H+2C) 11.4±1.2 (20h) 19.6±2.9
C4 (18H+24C) 22.4±0.4 (42h) 35.5±1.0
C5 (18H+24C) 24.2±1.0 (42h) 34.5±1.6
C6 (18H+24C) 26.1±1.3 (42h) 33.3±2.2
C7 (18H+48C) 28.8±1.4 (66h) 33.6±1.7
Steamed (18H+2ST) 12.2±0.6 (20h) 21.6±1.0
Hydrated 10.7±1.7 (20h) 20.5±2.7
Hydrated 12.9±0.9 (72h) ‐‐‐‐
C8 (block, 18H+4C) 10.7±1.7 (22h) 13.2±1.9
Hydrated block 6.8±1.6 (22h) 11.8±1.2
H=hydration, C=carbonation, ST=steam, 18H+2C = 18h hydration + 2h carbonation. (1 MPa=145 psi)
The results presented in Tables 2 and 3 are obtained from static carbonation (Fig 1a) which is energy
free after the pressurized gas is delivered for the production. Dynamic carbonation with forced diffusion
is also performed using setup in Fig. 2a for both small samples and full size blocks. Carbonation uptake is
in the same order of magnitude. Dynamic carbonation does not significantly increase the carbon uptake.
Nevertheless it can work directly with fresh concrete without initial presetting hydration. The circulation
of the gas can remove the surface free water in concrete and replace it by carbon dioxide. The
production cycle is therefore reduced which can have economical benefit. However circulation
consumes energy, especially for full scale production this circulation can be expensive. To meet the
project target of $10/tCO2 for utilization, the following project will adopt static carbonation to reduce
the process cost.
Three‐block carbonation was also carried out in chamber shown in Fig 2b. It is ideal for static
carbonation but can be used for dynamic forced diffusion carbonation with circulation. The carbon
uptake results are similar to the data presented in Table 2 from single block tests. The chamber used in
Fig 2b resembles the full scale chamber used in block production. The results obtained indicate that the
laboratory experiments can be scaled up to full production.
Nano calcite particles were investigated for their role to enhance carbon uptake as carbonate seeds in
concrete carbonation. Commercial product of calcite powder with average diameter of 700 nanometer
was used as cement replacement at a calcite to cement ratio of 5% by mass. Static carbonation was
17
performed by 2 hours and 24 hours. The results show for short period of carbonation by 2 hours, both
carbon uptake and compressive strength were reduced because of the addition of calcite powder. This
was possibly attributed to the reduction of cement content, leading to a reduced carbon reactivity by
the matrix. However the prolonged carbonation up to 24 hours, nano calcite particles can increase both
uptake and strength due to the additional reaction by calcite. By industry practice, carbonation of 24h is
not economically beneficial. The seeding effect by nano calcite was not obvious in short carbonation
process.
3.3 Fiber‐cement panel carbonation
Fiber‐cement panels are investigated as second product to store carbon dioxide during carbonation. The
mixture proportion of industry recipe was used. The slurry mix of fiber cement was prepared using
cement/water=1:3.3 and fiber/cement=12.3%. The panel was formed by compression at a compact
pressure of 0.7 MPa (101.5 psi). The pressure was slowly added to squeeze out the extra free water
required for slurry process. Bleached kraft cellulose fiber with diameter of 30 micron (0.00118 in) and
length of 3mm (0.118 in) was used. All the fibers were soaked in tap water over night before being used
in mixtures. Two kinds of samples were prepared in this study. Small slab samples were used for process
parameter study. Based on the optimized process from small sample tests, large panels with dimension
of 30 cm x 60 cm x1.2 cm (1’×2’×0.5”) were made for the durability tests (freeze‐thaw and wet‐dry
cycling test) and energy calculation in comparison to commercial products.
Table 4 shows the process parameters studied. They include molding pressure, carbonation time and
carbonation pressure. Molding pressure was kept constant of 0.7 MPa except B5 where 7 MPa pressure
was used to gain high strength panel. Carbonation time was varied from 0.5 h to 24 h and carbonation
pressure was 5 bar except B2 which was processed under 2 bar. B1‐B7 were small panels and B8 the
large one. Batches B6 and B7 were hydration references.
Table 4 Process parameters for fiber‐cement carbonation
Molding Carbonation Specimen
Initial curing, Carbonation
ID pressure, MPa pressure, bar dimension
h time, h
(psi) (psi)
B1 0.7 (101.5) 18 0.5 5 (72.5) 3”x5”x0.5”
B2 0.7 (101.5) 18 0.5 2 (29) 3”x5”x0.5”
B3 0.7 (101.5) 18 4 5 (72.5) 3”x5”x0.5”
B4 0.7 (101.5) 18 24 5 (72.5) 3”x5”x0.5”
B5 7 (1015) 18 0.5 5 (72.5) 3”x5”x0.5”
B6 0.7 (101.5) 18 0 0 3”x5”x0.5”
B7 0.7 (101.5) 0 0 0 3”x5”x0.5”
B8 0.7 (101.5) 18 0.5 5 (72.5) 1’x2’x0.5”
Initial curing: T=25 oC, RH=25%, (1”=2.54 cm)
Carbon uptakes by fiber‐cement panels are displayed in Table 5. They are based on cement content used
in the panel. In addition to mass gain and mass curve methods, chemical titration method was also used
to quantify the carbon content. It was found that 24 h carbonation at 5 bat (72 psi) gas pressure could
promote carbon uptake up to 30%, the theoretical maximum possible limit. At the same gas pressure,
0.5h carbonation reached 20.7% carbon take. Higher gas pressure seemed to be effective to enhance
carbon reactivity. High compact pressure (B5) did not reduce the uptake capacity. The results from small
18
sample tests were representative of large panel (B8) properties and therefore could be used to predict
large scale production. The optimized process was likely to have 4h carbonation at gas pressure of 5 bar
(72 psi) to reach 23.4% uptake.
Table 5 CO2 uptake by fiber‐cement panels
Uptake, %
ID Titration
Mass gain method Mass curve method Average
method
B1 20.1±0.2 20.4 21.5 20.7±0.2
B2 17.5±0.1 17.9 16.5 17.3±0.1
B3 23.2±0.6 24.0 23.1 23.4±0.6
B4 29.8±0.3 30.5 29.9 30.1±0.3
B5 18.3±0.5 18.7 20.1 19.0±0.5
B8 20.5±0.2 20.9 19.9 20.4±0.2
The flexural strengths and compressive strengths of fiber‐cement panels after hydration and
carbonation are summarized in Table 6. Carbonation had considerably increased the early age strength.
After 28 days subsequent hydration after carbonation, the carbonated panels had shown slightly
increased strength in comparison to hydrated reference and could be comparable to commercial
product. Both batches B4 and B5 had shown higher strength than commercial products. B4 was process
by 24h carbonation at a compact pressure for forming of 0.7 MPa (101psi) and B5 by only 0.5h
carbonation but formed at a compact pressure of 7 MPa (1015 psi). The former had shown an uptake by
30.1% while the latter an uptake by 19%. For large panel production, it is possible to achieve carbon
uptake of 20% in 0.5h carbonation at a gas pressure of 5 bar (72 psi). It is clear the high degree of
carbonation can promote high carbon uptake and high strength in final panel products.
Table 6 Strength of fiber‐cement panels
Flexural Strength, MPa Compressive Strength, MPa
No.
Early age 28d Early age 28d
B1 8.3±0.3 (18.5h) 12.2±0.2 11.2±0.4 (18.5h) 15.8±0.1
B2 7.6±0.1 (18.5h) 11.5±0.7 8.9±0.8 (18.5h) 13.6±0.7
B3 9.3±0.2 (22) 13.1±0.6 11.4±0.1 (22h) 14.6±1.2
B4 10.6±0.5 (42h) 15.7±0.1 15.0±0.3 (42h) 18.9±0.2
B5 11.0±0.2 (18.5h) 15.6±0.3 14.7±0.4 (18.5h) 18.5±0.1
B6 2.1±0.3 (18.5h) 8.9±0.8 2.8±0.8 (18.5h) 10.2±0.4
B7 3.0±0.2 (18.5h) 11.3±0.5 3.2±0.6 (18.5h) 12.4±0.4
C.P. / 14.7±1.7 / 14.1±1.1
B8 6.5±0.5 (18.5h) 8.5±0.3 10.5±1.5 (18.5h) 12.1±0.5
Note: 1 MPa = 145 psi; C.P.=Commercial product reference
19
3.4 Durability performance evaluation of carbonated products
In addition to carbon uptake and strength gain, durability performance of carbonated products is also
evaluated. There is concern that carbonation might increase the brittleness of the products. To examine
the effect of carbonation on brittleness of the product, the full stress‐strain curves in compression were
compared. The typical stress‐strain curves of the carbonated, steam‐cured and hydrated concretes are
shown in Fig. 6. In each batch, different curing regimes did not noticeably change the stiffness and
ductility. It is conclusive that carbonated concrete products are not more brittle.
Fig 6: Stress‐strain curves for carbonated and hydrated concretes
Fig. 7 shows block concretes before and after freeze thaw cycling in a saline solution between 20oC and ‐
18oC at a cycle rate of 24h per cycle. After 10 cycles, carbonated concrete still maintained the shape, the
hydrated reference lost most of its mass and the steamed reference was reduced to a mush. Fig 8
displays the quantitative mass loss. At 10 cycles, carbonated concrete lost 30% mass, hydrated concrete
lost 50% and steamed concrete was completely disintegrated at about 7 cycles. At 15 cycles, hydrated
concrete was also reduced to mush while carbonated concrete still maintained part of the solid shale
until 18 cycles. This test is based on ASTM C1262 which is a severe test for concrete retaining wall and is
not required for concrete blocks. It is used for comparison. The carbonated concrete had shown twice as
high as freeze‐thaw resistance in comparison to steamed concrete.
To understand the contribution by carbonation, quantitative SEM analysis of cement paste in concrete
was conducted. It was the capillary pore structure in paste that was modified by the carbonation
reaction and may have influence on freeze thaw performance. Fig. 9 shows typical back scattered (BS)
SEM micrographs of concretes at 100 times magnification. The digital images of the micrograph after
image analysis representing the porous area are also presented. Comparing the features of paste
porosity of the carbonated and the steamed samples revealed that the refinement of capillary porosity
on the surface of carbonation‐cured concrete was noticeable. At least 15 BS‐SEM images were analyzed
and averaged for each curing scheme in order to ensure the statistical significance of the analysis.
Table 7 presents the summary of the capillary porosity by the BS‐SEM image analysis technique. The
porosity measured by this technique excluded the entrapped air voids, since the BS‐SEM images were
intentionally chosen to avoid cavities greater than 500 µm. Nevertheless, the quantified porosity
inevitably included the isolated air voids. Although the BS‐SEM porosity measurement technique took
into account a fraction of ITZ porosity related to fine aggregates, the corresponding ITZ on coarse
20
aggregate surface could not be quantified due to the sampling procedure. Therefore, the absolute
values reported correspond to the porosity of the paste, rather than the total porosity of the concrete.
In other words, the measured values underestimate the porosity due to the exclusion of the entrapped
air voids in the image.
Fig 7: Concrete blocks after freeze‐thaw exposure
Fig 8: Mass loss in concretes subject to freeze thaw cycling
21
Fig 9: Capillary porosity in concrete (18H+2C) by quantitative SEM analysis
Table 7: Capillary porosity of block concrete by BS‐SEM analysis
The BS‐SEM analysis suggested that the surface of carbonated concrete was significantly less porous
than the steam‐cured and the seal‐cured concrete. The porosity of the carbonated surface zone was
6.8%, while the value in the steam cured concretes was 13.9%. The core of the carbonated concrete and
22
the seal‐hydrated concrete had similar porosities (9.9% and 9.8%, respectively). The measured porosity
was not the same on the surface and in the core in carbonated concrete. The porosity in the core of the
carbonated concrete was considerably higher than the heavily carbonated surface zone. The difference
between the core and the surface porosity reflected the non‐uniformity of the pore structure in the
carbonation‐cured concretes. The refinement induced by the carbonation appeared to contribute to the
freeze‐thaw resistance improvement. The refined micro‐capillary pores in the carbonated concrete
reduced the freezable water, enhancing the frost resistance.
Resistance to ettringite sulfate attack was investigated for concrete to serve in a sulfate rich
environment. Fig. 10 compares the length increases due to expansion of mortar bars submerged in 5%
sodium sulfate solution at 20oC according to ASTM C 1012. Carbonated concretes showed significant
improvements in sulfate resistance, exhibiting lower sulfate induced expansion compared to steam
cured and hydration cured references. This reduced expansion is possibly due to the significantly
reduced calcium hydroxide content and its related ettringite formation. It was confirmed by XRD
analysis. Fig. 11 shows XRD patterns of concretes after 4h carbonation (0H+4C), after 18h hydration and
4h carbonation (18H+4C), and after 18h hydration, 4h carbonation and 27 day subsequent hydration
(18H+4C+water spay). The powder samples were collected from the surface of the concrete. It was
obvious that carbonation after 18‐hour initial curing eliminated totally the calcium hydroxide in concrete
even after 28 days subsequent hydration. In comparison, the freshly carbonated (0H+4C) and the
hydration reference had shown significant calcium hydroxide component. At the same time strong peaks
were observed as calcium carbonates in carbonated concrete. It was indicative that the improved
sulphate resistance in the carbonated concrete was attributed to the elimination of calcium hydroxide
by carbonation.
Fig. 10: Length increase of 28‐day mortar bar prisms due to sulfate exposure
23
1: Calcite- CaCO3 2: Tricalcium Silicate - Ca3SiO5
3: Dicalcium Silicate - Ca2SiO4 4: Calcium Hydroxide - Ca(OH)2
1
3 2
1 2 1 2
0H+4C 4 1 1
18H+4C
Hydration reference
5 10 15 20 25 30 35 40 45 50 55 60
2 Theta
Fig. 11: XRD pattern of carbonated and hydrated concretes
Fig. 12: After 10‐month low‐temperature sulfate exposure
24
Fig 12 shows the test results of low temperature sulfate exposure of paste samples. After 10 months
immersed in 5% magnesium sulfate solution at low temperature of 4oC, the hydrated Portland limestone
cement (PLC) cement containing 15% of calcium carbonates experienced considerable mass loss and
strength reduction due to thaumasite formation. The CSH binder was significantly decomposed.
However, the carbonated PLC containing much higher carbonate content (26%) was seen intact and
maintained perfect shape. The carbonated (ordinary Portland cement (OPC) containing the same
amount of carbonates (16%) as the hydrated PLC had shown excellent resistance to thaumasite sulfate
attack. It is conclusive that carbonation treatment makes concrete products more resistant to low
temperature sulfate attack. It is possibly attributed to the carbonation surface densification and the
reduced pH value of pore solution. This sulfate tests are crucial to demonstrate that carbonation
treatment is an effective method to produce sulfate resistant concrete products which are suitable for
applications in foundation structures and near‐shore buildings.
3.5 CO2 recovery using self‐concentrating absorption technique
Flue gas was captured from Holcim Canada Jolliet cement plant in Montreal area. One flue gas cylinder
containing 14kg (32 lb) flue gas in mass at 12 MPa (1750 psi) was shipped to 3H Company at Lexington,
KY, in May 2011 for the laboratory investigation to perform CO2 recovery using self‐concentrating
absorption technology. There was about 2,2 kg (5 lb) CO2 in the cylinder. The setup for flue gas capture
from cement kiln chimney is shown in Fig. 13. A simple system including a cooling fan and a gas
compressor was employed. To get three cylinders filled up with flue gas to 13.8 MPa (2000 psi) for each,
it tool about 6‐8 hours to accomplish. The CO2 concentration in flue gas was recorded at the stack. It was
about 16% (Fig. 13b). Because of the difficulty of collecting more flue gas from cement plant, especially
due to the regulation and safety concern, it was suggested flue gas be simulated in laboratory using
blend gas with same concentration in later tests.
(a)
(b)
Fig. 13: Capture of flue gas at cement plant. (a) Setup for capture; (b) CO2 concentration in flue gas
The flue gas collected from cement plant and the gas cylinder was shipped to 3H’s laboratory by UPS.
After the flue gas was cooled and compressed into gas cylinder, the CO2 concentration was reduced to
14%. The flue gas was connected to absorption/regeneration system for CO2 capture shown in Fig. 5.
During the absorption, the emitted gas was monitored for CO2 concentration to make sure 90% of CO2 in
flue gas was captured. The released CO2 from regeneration cell past through a condenser to condensate
the water and absorbent. The captured CO2 with purity higher than 99% balanced with moisture was
25
collected into a big plastic bag that was pre‐vacuumed. Then captured CO2 was pressurized into a small,
pre‐vacuumed cylinder from the plastic bag for use in precast concrete production. Finally, about 0.5 kg
(1 lb) of CO2 was collected into gas cylinder. In original flue gas cylinder, there was about 2.2 kg (5 lb)
CO2. Because of the lack of experience in gas compression, most of the recovered CO2 was lost during
compression. Because the flow rate of produced CO2 did not match the flow rate by compressor, there
was gas loss during compression. The other reason was that there was not enough gas for compressor
to compress. Nevertheless once captured, CO2 gas had a purity of 99% and was no difference from
commercial gas. Therefore McGill University team continued the laboratory work on concrete
carbonation using commercial CO2 gas.
The 3H proprietary self‐concentrating absorption technology was also used to recover CO2 from residual
gas created in carbonation chamber. At the end of carbonation, there is residue CO2 in chamber and
should be recovered before the chamber can be opened. It can be accomplished by using the same self‐
concentrating absorption recovery technology. The residual gas has a CO2 concentration of 50%. Two
stages of CO2 recovery from residual gas of both block and panel CO2claves for recycling were designed.
In first stage, the CO2 concentration in residual gas from both block and panel CO2claves was reduced
from 50% to about 14 – 15%. In second stage, the CO2 concentration in residual gas will be further
reduced to below 1.5% that is the same CO2 concentration of the flue gas after scrubbed. Since the
carbon capture in second stage, reducing the CO2 concentration in residual gas from 14 – 15% to below
1.5%, is the same requirement with the carbon capture from flue gas, which is studied in previous
subtasks. The focus in the first stage is to reduce CO2 concentration in residual gas from 50% to about 14
– 15%.
The experiment was designed to simulate the first stage of CO2 recovery from residual gas of both block
and panel CO2 chamber for recycling. The residual gas containing 50% CO2 from both block and panel
CO2 chamber flowed into 3H’s carbon capture system. After CO2 removed in first stage from residual
gas, the captured CO2 gas will be released from the carbon capture system with the purity of CO2 above
99%. The released CO2 gas will be used for precast concrete production again. The residual gas after CO2
removed in first stage will be forward to carbon capture system again for further reduction of CO2 to
below 1.5%.
The experimental program was divided into two parts, Batch Mode absorption and Continuous Mode
absorption, in order to minimize the cost of the experiment. The purpose of batch mode experiment is
to obtain the suitable operation conditions to capture CO2 from flue gas. The purpose of continuous
mode experiment is to obtain the overall operation conditions and system performance. After the
system is justified with blend gas of 15% CO2 and 85% N2, the CO2 recovery is performed on flue gas
sent by McGill University.
3.6 Utilization cost analysis
Cost analysis is performed on concrete block carbonation and fiber‐cement panel carbonation. There
are six steps involved in carbonation process for both products. They are shown in Fig 14.
26
4 5 6
1 2 3
Residual gas Water Subsequence
Molding Presetting Carbonation
disposal compensation hydration
Fig 14: Static carbonation process
After mold casting, the concrete products underwent a presetting hydration in open air to remove the
free water for gas diffusion and carbonate precipitation. The preconditioned products were then placed
in carbonation chamber for curing for a specified time. After carbonation was done, the residual gas in
the chamber would be collected before the chamber could be opened. The carbonated products were
then water sprayed to surface saturation to compensate the water loss due to the open air presetting
and sealed for subsequent hydration. Of the six steps, only Step 2 (hydration presetting) and Step 4
(residual gas disposal) may require additional energy especially for carbonation.
Hydration presetting is a drying process and is based on relative humidity (RH) of the area for presetting.
For RH of 25% and 50%, it is possible to use low speed wind to achieve desired capillary porosity for
targeted carbon uptake (20‐30% based on cement mass). The cost is less than $5/tCO2 utilized. For high
humid environment such as RH of 80%, more energy efficient fan drying is needed to generate wind at
desired speed at low cost. The important factor that can reduce the cost is the low wind speed which
consumes less energy and also prevents concrete from cracking, although low wind fan drying may take
longer time for process.
Residual gas disposal in step 4 can be conducted using 3H self‐concentrating absorption technology. It is
fast and efficient as far as industry production is concerned. However it requires capital investment and
operational cost which could make the total utilization costs exceed the limit. Therefore a self‐cleaning
process is developed to dispose the residual CO2 from the chamber. It is based on compact design
concept. In a carbonation process with self‐cleaning function, the chamber is designed in such a way
that the quantity of CO2 gas injected is just enough to reach the target uptake (i.e. 20% or 30% based on
cement mass). Once the gas reaches the desired quantity, the valve is closed and the reaction between
concrete and CO2 continues. This is a self‐absorbing and self‐cleaning process. It was successfully
approved in block carbonation and panel carbonation. For block carbonation, it took 8 hours to
complete the reaction and the CO2 content in residual gas was nearly zero at the end of the process. For
panel carbonation, the same concept was tested. It took about 2 hours to reach the zero carbon in
residual gas. Panel is more reactive than block because it contains more cement. Therefore panel
production is a lot easier to perform self‐cleaning. It is clear that residual gas disposal can be integrated
into carbonation reaction with controlled gas quantity and sufficient time for reaction. It is effective if
the chamber is designed to have the right free space to solid concrete ratio so that the residual gas to be
processed is reduced to minimum. In this case, residual gas disposal can be done with no cost.
It is clear that the majority of the cost for utilization comes from the presetting drying of the products.
This step is necessary to create capillary space for carbonates precipitation. An energy efficient drying
27
process shall be investigated to reduce the cost. Solar energy is a clean energy source that can be used
to power the fan drying system or used directly in drying itself.
4 CONCLUSIONS
In conclusion, it is possible to perform CO2 utilization through concrete curing process with less than
$10/tCO2. An efficient fan drying system is the key to success for large scale production. The CO2 capture
cost can be reduced to $40/tCO2. With $40/tCO2 for capture and $10/tCO2 for utilization, it is possible to
make concrete block $0.018/block for curing. It is based on the assumption that each block can take
0.36kg CO2. It is corresponding to 20% uptake by cement mass. If carbon credit of $10/t can be claimed,
the final cost is $0.014/block. It is comparable to steam by natural gas. If CO2 price can be reduced to
$30/t with carbon credit of $10/t, it will cost $0.0072/block. It is possible to have profit. The CO2 capture
cost is a determining factor for the carbon utilization in industry production. At 20% carbon uptake rate,
the concrete block industry and fiber‐cement panel industry alone can jointly sequester about 2 Mt
CO2/year. The technology can apply to more concrete products and will continue for many years to
come.
3H Company had conducted in‐house research of cost analysis based on the DOE NETL Baseline. The
cost analysis study consists of two parts: (1) DOE 30% MEA Baseline Process study and (2) comparison of
DOE 30% MEA Baseline Process with 3H Process. Cost analysis of DOE 30% MEA baseline was carried out
first to calibrate the system and then cost analysis of 3H process was repeated using the same
procedure for comparison. The results showed that 3H’s Phase Transitional Absorption Technology for
carbon capture met and exceeded DOE goal – less than 35% increase of cost of electricity or less than
$40 USD/Ton CO2 with 90% CO2 captured from post combustion flue gas.
In addition to environmental benefit of carbon utilization in precast concrete products, the process also
demonstrates technical advantages. If short carbonation is performed in 2‐4 hours, the strength gain is
not significant. However if carbonation can be extended to 24 hours or 48 hours, not only the carbon
uptake can be promoted to theoretical maximum of 30% based on cement mass, the strength can be
considerably enhanced as well. In comparison to strength gain, the improvement in long term durability
is more attractive. Carbonated concretes have shown significant increase in resistance to freeze‐thaw
cycling and sulfate attack due to carbonation treatment.
It is suggested demonstration project be prepared with concrete block carbonation first because of the
mass and the market. The block plant which is running the steam curing using old autoclave is the ideal
plant to start with. There is no need in capital investment for the demonstration project. Steam can be
replaced directly by carbon dioxide and the process can run at 1‐5 bar pressure. The missing link is the
low cost CO2. 3H self concentrating absorption technology is effective in low cost CO2 production.
However the capital cost of the setup is so high that it seems not possible to have the production in near
future. Commercial gas still is the option for demonstration project.
28
5 LIST OF FIGURE CAPTION
Fig 1: Block carbonation setup. (a) Static carbonation. (b) Dynamic carbonation.
Fig 2: Block CO2 chambers. (a) Single block CO2 chamber; (b) Multiple‐block CO2 chamber
Fig 3: Panel carbonation setup. (a) Schematic of chamber; (b) Setup of panel carbonation.
Fig. 4: Laboratory concrete products for CO2 storage. (a) Concrete blocks; (b) Fiber‐cement panel
Fig. 5: The customized packed absorption column. (a) Schematic and (b) Setup
Fig 6: Stress‐strain curves for carbonated and hydrated concretes
Fig 7: Concrete blocks after freeze‐thaw exposure
Fig 8: Mass loss in concretes subject to freeze thaw cycling
Fig 9: Capillary porosity in concrete (18H+2C) by quantitative SEM analysis
Fig. 10: Length increase of 28‐day mortar bar prisms due to sulfate exposure
Fig. 11: XRD pattern of carbonated and hydrated concretes
Fig. 12: After 10‐month low‐temperature sulfate exposure
Fig. 13: Capture of flue gas at cement plant. (a) Setup for capture; (b) CO2 concentration in flue gas
Fig 14: Static carbonation process
6 REFERENCES
[1] Young, J.F., Berger, R.L. and Breese, J. (1974). “Accelerated curing of compacted calcium silicate
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