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IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 51, NO.

2, MARCH/APRIL 2015 1289

Cement and CO2: What is Happening


John Kline and Charles Kline

Abstract—Concrete is the second most widely used commodity TABLE I


globally, with estimated production at over 15 billion tons per year. AVERAGE K ILOGRAM OF CO2 R ELEASED
PER T ON OF C EMENT P RODUCED
It is estimated that 3.6 billion tons of cement was produced in 2012,
accounting for approximately 5% of the global anthropogenic
CO2 emissions. The Cement Sustainability Initiative (CSI), along
with the International Energy Agency (IEA), has developed a road
map for CO2 reductions in the cement industry. The IEA/CSI
“blue map” calls for a reduction of approximately 50% in the
specific CO2 emissions per ton of cement by 2050. The blue map
emphasizes continued progress in the three traditional levers for
CO2 reduction but also indicates that these three levers will only
achieve half of the targeted reduction. Many cement companies
are exploring additional ways to achieve CO2 reductions. This
paper reviews the progress to date and some of the many projects
underway in the cement industry.
Index Terms—Algae, biogenic fuels, carbon capture,
cement, clinker substitution, CO2 emissions, fuel efficiency,
oxy-calcination.

I. I NTRODUCTION
employed. Older cement plants have utilized the energy in-
C EMENT manufacture has a large CO2 footprint due to the
tremendous use of cement around the world. Concrete, the
end product of cement, has a relatively small carbon footprint
tensive wet process which must dry the slurried raw material
increasing the heat consumption and CO2 emissions. Modern
when compared on a like-to-like basis with other building plants often use a five-stage precalciner kiln system with an
materials. However, the vast quantities of concrete used around inline raw mill for maximum efficiency.
the world today make cement manufacture one of the leading The amount of clinker in the cement has a direct impact
sources of CO2 emissions. on the specific CO2 emissions per ton of cement produced.
Cement manufacturing emits CO2 from two principle mech- Many cement manufacturers are reducing the clinker content
anisms: the combustion of fuels required to meet the manufac- of their cement by adding in materials that have cement-
turing temperatures and the release of CO2 from the principle like or “cementitious” properties. These materials include fly-
raw material, limestone. Table I indicates the average amount ash, slag, and natural and artificial pozzolans. Reducing the
of CO2 released per ton of cement manufactured. clinker content of cement is often referred to as “clinker
The CO2 from calcination depends heavily on the quantity substitution.”
of limestone consumed in the cement manufacturing process.
This amount is relatively constant across most cement plants. It II. T HREE T RADITIONAL L EVERS FOR CO2 R EDUCTIONS
can be increased when cement plants waste dust and decreased F ROM C EMENT M ANUFACTURE
when alternative sources of calcium oxide are utilized, such as
slag, flyash, and/or bottom ash. A. Fuel Efficiency
The CO2 from combustion depends greatly on the system Fuel efficiency has steadily improved over the past 30 years
efficiency, which, in turn, depends mostly on the technology or so. The invention of the four-stage suspension preheater
was a step change in the evolution of energy efficiency in
Manuscript received February 9, 2014; accepted April 24, 2014. Date of cement production. The introduction of the precalciner allowed
publication July 16, 2014; date of current version March 17, 2015. Paper 2014- larger production rates from single kilns, leading to further
CIC-0068, presented at the 2014 IEEE-IAS/PCA Cement Industry Technical
Conference, National Harbor, MD, USA, April 13–17, and approved for
improvements in energy efficiency. Later, fifth and, sometimes,
publication in the IEEE T RANSACTIONS ON I NDUSTRY A PPLICATIONS by sixth stages of preheat were added, capturing even more of the
the Cement Industry Committee of the IEEE Industry Applications Society. heat from the combustion gases. Cooler technology improved
J. Kline is with Kline Consulting, Allentown, PA 18103 USA (e-mail:
johnpkline1@gmail.com). at the same time allowing greater recuperation of heat from the
C. Kline is with Kline Consulting, Montreal, QC H3H 1J1, Canada (e-mail: clinker coolers. Today’s five-stage precalciner kiln is consid-
charleshkline3@gmail.com). ered the best available technology (BAT) for fuel efficiency.
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org. Practically all new cement manufacturing facilities are now
Digital Object Identifier 10.1109/TIA.2014.2339396 incorporating this BAT technology. Older plants with long wet
0093-9994 © 2014 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
1290 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 51, NO. 2, MARCH/APRIL 2015

and long dry kiln are becoming less competitive and are being
gradually squeezed out of existence. This is allowing for a
steady decline in the specific heat consumption and therefore
CO2 emissions.

B. Biogenic Fuels
The use of combustible wastes as fuel for cement man-
ufacture began mostly as a method for achieving cost sav-
ings. As fossil fuels became scarcer, the price increased. The
unique combination of high combustion temperatures, aided
by excellent heat recuperation from clinker coolers, and the
relatively long residence times in cement kiln systems made Fig. 1. IEA/CSI blue map for CO2 emission reduction showing the three
them the world’s best incinerators. In addition, practically all of traditional levers.
the noncombustible ash becomes part of the cement produced.
TABLE II
Recognizing this, cement plants are often sought out as premier P ERFORMANCE OF S OME OF THE M AJOR P RODUCERS ON THE
sites for combustible waste utilization. T HREE M AIN L EVERS FOR CO2 R EDUCTION [1]–[5]
Cement producers around the world are steadily increasing
the amount of combustible wastes that they consume, thus sav-
ing tremendous amounts of fossil fuels while eliminating other
less efficient waste disposal methods. In many jurisdictions,
“biogenic” fuels are considered as CO2 neutral. Biogenic fuels
are considered as renewable fuels since their origins are in
replaceable materials, such as wood wastes, agricultural crop
wastes, etc. Not all alternative fuels are considered biogenic
fuels. For example, scrap tires are only considered to be around
20% biogenic, which approximates the amount of natural rub-
ber used in their manufacture.

C. Clinker Substitution
Clinker substitution—on the surface—appears to have the
largest potential impact on the cement’s CO2 footprint. How- TABLE III
C OMPARISON OF S OME R EPORTED C HEMISTRIES
ever, supplies of high-quality cementitious materials are not OF “N EW C LINKERS ” [6]–[13]
always available locally, and most have limited supply avail-
ability. Ground blast furnace slag makes an excellent clinker
substitute, but the quantity that is available is limited by the
amount of iron and steel production. Natural pozzolans are
usually found in volcanic areas and therefore not universally
available. Artificial pozzolans can be expensive to produce and
emit CO2 during production. Flyash is available in large quan-
tities in the major coal-consuming countries, such as China,
India, U.S., and Russia, but limited in availability in other parts
of the world. The International Energy Agency (IEA)/Cement
Sustainability Initiative (CSI) road map therefore places a limit
on clinker substitution at about 70% due to supply limitations in cement manufacture as pointed out previously. At the same
(Fig. 1). time, the basic formulation for Portland cement clinker has re-
mained relatively the same for the past 100 years. The increas-
ing pressure to reduce CO2 emissions is changing that. Many
D. Overall Status
of the major international cement producers are creating new
Table II demonstrates how the major cement producers are clinker formulas to reduce the amount of limestone required to
faring with these three traditional levers for CO2 reduction. make clinker and therefore reduce the CO2 emissions from the
raw materials. Table III summarizes some of these new clinker
formulations.
III. C LINKER R EFORMULATION (A N EW L EVER )
It can be seen that the lime content (CaO) is reduced in all of
The majority of CO2 (+/ − 60%) that is emitted in cement the new clinkers; thus, the CO2 emission expressed as loss on
production in a modern plant comes from the raw materials. ignition or LOI is reduced accordingly. The cement producers
Great strides have been made in reducing the heat consumption are claiming CO2 reductions per ton of clinker and cement in
KLINE AND KLINE: CEMENT AND CO2 1291

TABLE IV
C OMPARISON OF VARIOUS OXY-C OMBUSTION P ROCESSES
FOR C EMENT M ANUFACTURE

Fig. 2. Main groupings of carbon capture technologies.


ciner where 90% of the raw material CO2 is released as well.
The result is that 80% of the CO2 from cement manufacture is
the range of 20%–30% with these new clinkers. The majority released in the precalciner vessel. Oxy-combustion can be used
of the reduction comes from the reduced amount of limestone in the precalciner vessel if the corresponding preheater vessels
in the raw materials. Additional CO2 reduction is obtained by are separated from the kiln exhaust gases. This would require
having lower reaction temperatures required in the kiln which, a twin tower preheater design with all of the kiln feed being
in return, reduces the heat consumption. directed to one precalciner for oxy-combustion. The resulting
Although these new clinker formulas are in existence to- yield is on the order of 5 : 1 CO2 : O2 . This technology is
day, they will most likely not be commercially available for available today but not likely as a retrofit.
widespread usage for some time. The durability of the concrete Oxy-combustion can be used in both the kiln and the calciner
made with these new clinkers and their corresponding cements for existing systems or new systems with one or more preheater
will need to be established, and specifications will be adapted towers. In this case, oxygen and recirculated CO2 are utilized
as well. for combustion in both the kiln and the precalciner. Some of the
O2 /CO2 mixture will have to be used for cooling in the clinker
cooler in order to recoup the heat contained in the clinker when
IV. C ARBON C APTURE , U TILIZATION ,
it leaves the kiln. Total oxy-combustion will require a very good
AND S EQUESTRATION
sealing system in the cooler and where the rotating kiln shell
Additional CO2 reductions will need to be carried out contacts the stationary structures at both ends. Yields for total
through some form of carbon capture. The main categories for oxy-combustion in cement are estimated at 3.5 : 1 CO2 : O2 ;
carbon capture are shown in Fig. 2 and include precombustion however, this will depend very much on the ability to prevent
treatment, oxy-combustion, postcombustion treatment, and di- inleakage (Table IV).
rect processing (indirect calcination). The European Cement Research Academy (ECRA) has in-
Precombustion treatment removes the carbon from the fuel vested a considerable effort into exploring carbon capture tech-
before firing. Gasification processes are typically used to strip nologies applicable to the cement industry [14]. They have
out the carbon from the raw fuel with or without air injection. investigated most of the leading contenders over the past 5 years
The result is a hydrogen (H2 ) stream that is then fired in the and have been zeroing in on oxy-combustion. The ECRA
process. The combustion products from this technology are project is now in phase IV, in which detailed designs are
close to pure steam. However, this technology does not work being worked out for a pilot-scale installation of a total oxy-
well in cement manufacture as the majority of the CO2 is combustion system. Phase V will be the final stage of their work
developed in the process from the calcination of limestone. and should result in the construction and operation of a full-
Oxy-combustion aims to remove all of the nitrogen from the scale total oxy-combustion cement plant. The full-scale plant
combustion air. The fuel is fired in a mixture of pure oxygen should be in operation by 2020.
and recirculated CO2 from the exhaust gases. CO2 recircu- Indirect calcination takes advantage of the raw material CO2
lation is required to reduce the temperature of pure oxygen without the need for the high cost of separating the oxygen from
combustion. Combusting fuels in a pure oxygen atmosphere the combustion air. Indirect calcination releases the CO2 from
can create an intense flame and oxidize metals in proximity to the raw materials through indirect heating. Once limestone is
the oxygen fuel mix. Oxy-combustion has been considered for heated to the calcination temperature, CO2 will be released,
coal-fired power plants but has a very low yield (1.3). Yield just as water boils at a certain temperature. Indirect heat can
is expressed as the tons of CO2 released per ton of oxygen be applied through several means, none of which have been
consumed. commercially proven. These include the use of a heating agent
Cement manufacture represents a unique opportunity for (a ceramic material that can absorb and carry the heat from one
oxy-combustion as 60% of the fuel is combusted in the precal- area to another), microwaves, an arc type furnace, induction,
1292 IEEE TRANSACTIONS ON INDUSTRY APPLICATIONS, VOL. 51, NO. 2, MARCH/APRIL 2015

etc. Clinker itself has been proposed as one potential heating


agent readily available in cement plants.

V. P OSTCOMBUSTION T REATMENT
Precombustion treatment is not effective for cement due
to the process emissions. Oxy-combustion and especially
oxy-calcination are promising technologies due to their higher
yields; however, they are not easily retrofitted to existing ce-
ment plants. Therefore, there has been a lot of interest in
postcombustion or “tail-pipe” technologies. Postcombustion
technologies can be divided into four main categories: sorbent
scrubbing, membrane separation, cryogenic separation, and
direct utilization. The aim of the first three technologies is
to create a rather pure CO2 stream that can be either used
beneficially or sequestered (Fig. 3).
Carbon sequestration refers to the fixing of the CO2 in a more Fig. 3. Overview of “tail-pipe” solutions for CO2 capture.
or less permanent manner. The term is mostly used for pumping
CO2 into underground chambers where it hopefully remains which can be power intensive. Membrane life, especially in
in perpetuity. Sequestration was once felt to be the preferred conjunction with dust and acid gases, remains a challenge to
solution for reducing CO2 in the atmosphere. However, as more resolve.
work has been done on the subject, many issues have evolved. One plant in Northern Europe will install a sophisticated
In particular, leakage from sequestration sites could jeopardize carbon capture test facility. This facility will test an amine
life on the surface and water supplies below the surface. Carbon sorbent capture system, a solid sorbent capture system, and a
utilization is a term used when the CO2 is converted in a membrane capture system, more or less at the same time. All
product. three of the aforementioned systems will be installed at pilot
Sorbent scrubbing is one of the more popular technologies scale in an existing cement plant and use actual stack gas in
for CO2 capture as it has been utilized for a number of years the pilot units. As mentioned previously, carbonate looping will
for gas cleansing. The fundamental idea is that a sorbent is also be investigated in conjunction with a university but will not
used to strip the CO2 out of the exhaust gases. The CO2 be piloted at the cement plant.
saturated sorbent is then treated in a separate vessel to release Cryogenic systems typically use the triple point of CO2 ,
an almost pure CO2 stream. The treated sorbent is then re- where it is close to a gas, a solid, and a liquid under the
circulated back to the stripping vessel. Amines have been the right temperature and pressure conditions. The idea is to either
sorbent of choice in the past. Sorbent systems can be large liquefy or freeze the CO2 while keeping all undesirable gases
in size and therefore high in installed costs. A cement plant in either gas or liquid form. In this way, CO2 can be extracted
in California pioneered tests in amine adsorption in the recent as a liquid or a solid. Adding pressure and/or temperature
past and demonstrated capture ratios of 45%–90% of the CO2 would return the CO2 from a solid to a liquid phase or from
in the off gas. No further details of these tests are available a liquid to a gas phase. Liquid CO2 could then be transported
publicly. by truck or rail. Gaseous CO2 can be transported via pipelines
Some cement companies frown upon the idea of adding to use sites. Cryogenic systems utilizing liquid separation
complex chemical processes with their associated safety and have been used for air separation in the past and are fairly
health concerns into a cement plant. However, one variation well known. Solid CO2 systems are newer and show some
of the sorbent technology is the use of lime as the sorbent. promise. Both systems will be power hungry, and the solid CO2
This is not practical in other industries as the lime deteriorates extraction system will require further development to avoid
quickly over time and has a higher replenishment rate than plugging.
other sorbents, leading to high waste disposal as a secondary
issue. However, the spent lime sorbent can be a great cement
VI. C ARBON U TILIZATION
raw material. One cement plant in Taiwan has installed a pilot-
size unit for carbonate looping that is operating today and Carbon utilization technology covers a broad spectrum and
capturing 1 ton per hour of CO2 . Carbonate looping has been includes any process that converts the CO2 , whether concen-
considered by one cement manufacturer in the U.S., and it will trated or not, into another product. The use of exhaust gases to
also be explored as part of a carbon capture project in Northern grow algae and create biofuels is one example of a utilization
Europe. technology that is being widely explored. Any of the other tail
Membrane technology utilizes semipermeable membranes pipe technologies can be used to create a purer CO2 that could
that allow CO2 to pass through while blocking other gases. also be used to create products. However, the high operating
Membranes are fairly simple to install and operate but require and capital cost of these technologies indicates that only high-
a high surface area for large gas volumes. The CO2 transfer value products should be created. This could change as the
is often driven by a combination of vacuum and pressure technology evolves and costs come down.
KLINE AND KLINE: CEMENT AND CO2 1293

TABLE V in Texas. This process will utilize approximately 50% of the


L ISTING OF S OME K NOWN A LGAE P ROJECTS IN THE C EMENT I NDUSTRY
cement plant’s exhaust gas to create baking soda and other
chemical products. Ground was broken late in 2013, and this
plant should be on stream in 2014.
Another project has been announced at a cement plant in
Vancouver. This project is still in the laboratory pilot stage, but
it will use electrolysis of the CO2 off gas to create formic acid
and possibly generate fuel cell materials.

VII. S UMMARY AND C ONCLUSION


The tremendous use of concrete around the globe makes the
cement industry one of the leading sources of anthropogenic
CO2 emissions. Even though concrete has a very low carbon
A. Algae Projects footprint, that footprint needs to be improved further. The
major cement producers are pushing hard to meet self-imposed
Based on the number of projects planned and ongoing, it CO2 reduction targets today. They are taking full advantage
would appear as though the major cement producers believe of the three traditional levers: energy efficiency, biogenic fuel
that algae growth is one of the more promising technologies use, and clinker substitution. Indeed, many of the world’s
of the future. Table V gives information on some of the al- largest cement producers have developed new lower carbon
gae projects in the cement industry. Algae are tremendously clinker formulations. However, the progress with these levers
resilient life forms that can multiple rapidly and can be selected will not be enough to meet ambitious future CO2 reduction
to generate specific products such as bio-oil, plastics, and other targets.
hydrocarbons. They can be resistant to the other elements in the Carbon capture for the purposes of utilization or seques-
cement plant flue gas and live in just about any temperature and tration will be required as well. Many cement companies are
light condition, albeit lower light and temperature may inhibit already trialing potential capture technologies. It is too early to
growth rate. tell which technologies will take the lead in the future. Concerns
Algae seems to have the most promise; however, there are about the long-term viability of sequestration have reduced the
still many obstacles to overcome. Algae cultivation uses sun- global appetite for this type of technology. Enhanced oil field
shine or light from other sources to convert CO2 into hydrocar- recovery appears to be the only cost-effective sequestration
bons through photosynthesis. Algae ponds require large surface option today. Carbon utilization by virtue of the fact that it
areas and are best suited for warmer sunnier climates. Photo- creates products should be a preferred route. Additional break-
bioreactors bring artificial light to the algae, thus overcoming throughs in technology will be required before any technology
some of the pond issues; however, they require more energy. can become mainstream. Incentives to find solutions, either
Some projects are using microbes which do not require a light through taxes and/or grants, will most likely be required to
source to grow and reproduce. maintain and increase momentum.
All organisms, microbes and algae, need additional nutrients
to survive and thrive; some of these nutrients can be supplied R EFERENCES
by the NOx in the gases and minor elements that come with [1] HeidelbergCement. Heidelberg Sustainability Report 2011/2012,
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[10] P. Castan, “Pays de Thau: Un “ciment écolo” grâce à la bauxite locale!” Charles Kline received the B.A. (Hon) degree in
Midi Libre, Oct. 2013. [Online]. Available: http://www.midilibre.fr/ philosophy from the University of Calgary, Calgary,
2013/10/22/ce-nouveau-ciment-reduit-de-30-les-emissions-de-co2- AB, Canada, before attending Law at Queen’s Uni-
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CemNet, Nov. 2013. devotes his time to researching upcoming environ-
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Mater. Struct., vol. 47, no. 6, pp. 1055–1065, May 2013.
[14] European Cement Research Academy, communication bulletin “Carbon
capture technology: ECRA’s approach toward CCS,” Aug. 2012.

John Kline is the Principal at Kline Consulting,


LLC, Allentown, PA, USA, a consulting firm assist-
ing building material companies (start-ups to global
producers) to improve their operational and environ-
mental performance. He has over 40 years of expe-
rience in the mineral processing industry working
in research, sales, plant design, engineering, com-
missioning, and operations. He retired from Lafarge
in June 2012 after 21 years, with the last 18 years
in various international executive positions. He is
currently specializing in CO2 reduction technologies
and mercury abatement.
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