SPL UTILIZATION IN CEMENT & STEEL INDUSTRY

Technical Report

Prepared by: Nitin Tiwari

Head Planning and Waste Management – Metal (Balco)

March -2016
 SPL UTILIZATION IN CEMENT & STEEL INDUSTRY

Technical Report

Table of Contents

1. Introduction - 2

2. Base Case: Recycling of SPL in Cement Kiln - 2

2.1 Production of Cement - 3
2.2 Use of SPL or Derivatives in Cement Kilns - 3
2.3 Fuel Savings - 4
2.4 Precedent for Using SPL in Cement Plants - 5

3. Advantages/Disadvantages of SPL - 6

4. Sustainability of using SPL - 6

5. Conclusion - 8

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 SPL UTILIZATION IN CEMENT & STEEL INDUSTRY

Technical Report

1. Introduction

This technical report is created to provide general information on processing of SPL.

There are a number of ways including direct charging in cement kilns as fuel substitute or
feed mix received after detoxification process can be used in various Steel & clay bricks
manufacturing. This technical report would shed light on SPL usage in Indian Industrial
scenario and creating awareness about its positivity with complete corporate responsibil-
ities in line with environmental norms. There are more aspects reviewed such as transpor-
tation and technical aspects that come with the implementation of each selected option.

SPL (Spent Pot Liner) : The Aluminium reduction Cell or “Pot” contains a lining of
Refractory Carbon blocks & bricks that contain Molten Cryolite and metal pool in around
960 degree Centigrade temperature. During pot under production ageing causes worn off
lining material along with impregnation with chemical compounds. Once the refractory &
carbon reaches to end of life, pot is taken out from Production & lining material is re-
moved as Spent Pot liner .In its raw form, Spent Pot liner varies in size from fine dust to
lumps of up to one meter. Its typically made up of a wide range of minerals & chemical
compositions because the different materials in the pot liner are mixed together during
removal from shut down pot.

2. Base Case: Recycling of SPL in a Cement Kiln

Other than disposal in a landfill this option is today the most widely used option by
aluminium producers worldwide. In this option we also consider the potential inclusion
of spent carbon butts with the shipment of SPL. The primary reason for the cement pro-
ducer to process the SPL is the heating value from the contained carbon. By adding the
spent butts the heating value increases substantially which makes it even more attractive
for a cement producer to take SPL.

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2.1 Production of cement

Cement clinker is produced via calcining of wet, semi-dry or dry solids counter-current
to hot gas flow in a rotary kiln. The raw materials for manufacture of cement clinker are
alumino silicates and iron oxides (from clays and shales) and calcium carbonate (from
limestone).

After blending and milling, the raw materials are added to the kiln counter-current to
the flow of hot gases from the burner, thereby being preheated and dried as they pass
down-wards through the cyclone preheater tower. The day reactions which occur within
the kiln to form clinker (the precursor to cement and the combination of lime (CaO) from
the limestone, and silica (SiO2), alumina (Al2O3) and iron oxide (Fe2O3) from the clays
and other additives, including ash from coal if this is used as fuel in the kiln. These com-
ponents react to form the complex compounds forming the clinker – tricalcium and dical-
cium silicates, tricalcium aluminate and tetra-calcium alumino-ferrite. This reaction typ-
ically proceeds at 14500C. After cooling, the clinker is ground with gypsum to form Port-
land cement.

Cement kilns are energy-intensive, consuming from 3.2 Gj/tone of clinker for a dry pro-
cess with suspension (cyclone) preheater to 5.5 Gj/tone for a wet process.

2.2 Use of SPL or Derivatives ( outcome after Detoxification) in Cement

kilns

SPL or its derivatives can be introduced into a cement kiln via either of the following.

 Injected as a powder alongside pulverized coal via the kiln burner (first cut SPL only);
 Injected pneumatically into the pre-heater end of the kiln (both first and second cut
SPL).
The benefits of using SPL or SPL derivatives in cement kilns as an alternate fuel and raw
material (AFR) have been well documented and essentially consist of the following:
1. First cut SPL contains sufficient carbon that it can be burnt as fuel and therefore reduce
the consumption of primary fuel in the kiln.
2. It has been found that fluoride is beneficial for reducing clinkering temperature by
fluxing action (from 14500C to 13500C). Due to the presence of large quantities of
lime and limestone within the kiln, virtually all gaseous fluoride is scrubbed from the
kiln exhaust and fixed in the clinker as fluorspar (CaF2).

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3. Ammonia and cyanide from the SPL act to reduce nitrous oxide (NOX) emissions from the
cement kiln by up to one-third, via the following reactions:
 Cyanide: 4HCN + 2NO2 + 3O2 -- 2H2O + 4CO2 + 3N2
 Ammonia: 4NH3 + 2NO2 + O2 -- 3N2 + 6H2O;
4NH3 + 6NO -- 5N2 + 6H2O.

4. Refractory materials (silica, alumina) in the first and second cut SPL can substitute for these
components in the cement kiln raw materials.

However, despite the above benefits to its use as AFR in a cement kiln, there is a limit to the rate
at which SPL can be used in the clinkering process due to its sodium content. Sodium is prob-
lematic for product quality, and will attack the kiln refractory lining. At one Brazilian cement
plant where SPL is processed, new less porous refractory lining had to be installed in the
kiln to accommodate the co-processing of SPL sodium. Blue Circle Southern Cement (BCSC)
in Australia have achieved a 12 month kiln refractory life which is close to the industry
standard of 15-16 months, despite using an SPL – derivative in their kiln at Waurn Ponds. Up
to 3wt% SPL in clinker has been used in some cases without exceeding clinker sodium spec-
ifications or having a detrimental effect on kiln refractories.

However, consistent sodium content in the SPL or SPL derivative is essential to avoid
problems with off-specification clinker. The same for the high fluoride content that increase
set times of the cement after pouring.

Based on the typical SPL compositions and a conservative sodium limit of 0.25% by weight for
clinker, the estimated cement kiln capacity required to wholly dispose of the SPL (both first and second
cut) as generated is 300,000 tonne per year (resulting in approximately 2% by weight of SPL in the
clinker). Blue Circle Southern Cement (BCSC) can tolerate up to 0.7%wt sodium in clinker, however
the tolerable addition rate of SPL –derived sodium must be considered on a case-by-case basis to vari-
ation in sodium levels in raw materials for cement kilns around the world.

2.3 The fuel savings expected from using SPL at this substitution rate are :
 Approximately 5% saving by reducing energy input from primary fuel by 160 MJ/tonne of clinker;
 Approximately 5% saving by lowering the clinker temperature by 1000C. However, this effect is de-
pendent on the sodium content of the clinker raw materials and how much additional sodium can be
tolerated with the SPL addition. The sodium limit may prevent addition of sufficient fluoride to see
this fluxing effect;
 The intake of spent anode butts will result in further, considerable savings on the energy input from
primary fuel.

This suggests a total energy saving of about 10% for a cement kiln using SPL with 55% carbon
content in the first cut material. This is consistent with trials of as SPL derivative at Adelaide

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Brighton Cement’s Birkenhead kiln in South Australia (2001-2003) wherein fuel savings of about
9% were reported (SPL only).

It is more likely that only first cut SPL will be attractive to cement kilns as an alternative fuel due
to its higher carbon content than second cut material. A cement kiln of 110,000 jtpa capacity would be
required to consume only the first cut SPL generated.

SPL will most likely require a certain minimum level of pre-treatment before it can be accepted for
use in a cement kiln, namely:

 Grinding to a suitable size (< ¼ inch in US plants for injection into the cement kiln. Carbon from
the SPL is mainly graphitic and much harder than coal. Thus SPL causes increased wear if it must
be pulverized to fuel via the cement kiln’s coal milling plant. Pre-milled SPL is therefore preferred
for introduction into cement kilns. The BCSC specification is for 90% < 90 micron sizing for SPL
derivatives;
 Mixing with other materials to enhance its calorific value (e.g. spent anode carbon dust, coal tar
pitch). Increasing the SPL fuel value without increasing its sodium content allows the cement kiln
to realize greater energy cost savings by using this material as an AFR.

2.4 Precedent for Using SPL in Cement Plants

SPL and SPL derivatives have been used in cement kilns as alternate fuel and raw materials (AFR)
over a number of years. Trials and continuing processing of treated SPL have been completed in
Australia:

 Cement Australia – Fisherman’s Landing Plant (Queensland):

SPL derivative from the Comalco COMTOR SPL treatment plant at Boyne Smelter Limited Glad-
stone. Ongoing since July 2004;
 Blue Circle southern cement (BCSC) – Waurn Ponds Plant (Victoria): SPL derivative “Hi-Cal 50”
from the Regain SPL treatment facility at Alcoa Aluminium Point Henry smelter Geelong. Ongoing
since January 1998;
 Adelaide Brighton Cement Birkenhead Plant (Sough Australia): SPL derivative from Regain pilot
plant at Tomago Aluminium Newcastle. Trial period 2001-2003;
 Cement Australia – Railton Plant (Tasmania): SPL from Comalco Bell Bay. Trial November 2006.

Information available in the public domain indicates that the Cement Australia Gladstone and
BCSC Waurn Ponds plants are currently the only cement kilns in Australia consuming pre-treated
SPL on an ongoing basis. Comalco Bell Bay Propose to send all freshly generated SPL from their
smelter to the Cement Australia Railton kiln in the future.

SPL is processed in cement kilns by Alcoa at two locations in Brazil, enabled by a 1998 decision
by the Brazilian government to license certain cement manufacturers to use SPL in their clinker
kilns. Alumar Sao Luis sends 13,000 TPA SPL to the Cimento Poty Ltd cement plant in Sobral

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Technical Report

where it is injected pneumatically into the base of the preheater tower. At Pocos de Caldas ap-
proximately 8,000 TPA SPL is disposed of in this manner.

3. Advantages/Disadvantages of SPL;

Advantages:

 Both first and second cut are processed in the cement kiln;
 SPL is fully detoxified in the kiln process. Residual emissions are well below acceptable limits;
 The carbon content lowers the requirement for normal fuel, which typically is coal. This off sets
costs for fuel;
 The fluoride content increase the flux and thus lowers the melting temperature of clinker. The kiln
can operate at a slightly lower temperature and thus reduces the net fuel consumption and the net
GHG intensity;
 This use of SPL has many good sustainable aspects. There is also much experience becoming
available to the cement producers.

Disadvantages:

 The sodium content of the SPL can be an issue and some cement plants cannot take SPL for this
reason;
 The composition of SPL varies considerably. It is hard for the plant operators to balance the intake
of the materials. Using raw SPL requires a good safety margin to deal with its variability;
 The fluoride can also have an unacceptable impact on clinker chemistry and ultimate set time;
 This option still requires transportation of a hazardous material between sites and sometimes over
considerable distances.

4. Sustainability of using SPL in cement kilns

The option of disposing of SPL either pre-treated or un-treated depends on a number of factors to be
sustainable in the long term:

1. Government legislation in the country of treatment/disposal to enable the use of SPL or its deriva-
tives in cement kilns.

2. Recognition by the public and other stakeholders that this is a mutually beneficial method by which
two industries can gain benefit: “one industry’s waste is another industry’s resource”.

3. Ongoing demand for cement clinker. Since cement is the second most widely utilized resource in
the world (behind water), it is almost impossible to imagine that the cement kiln process will

Cease to be an outlet of sufficient capacity for the treatment of SPL, although the development of con-
crete substitutes in the future may reduce the cement market to some extent.

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Technical Report

Table 1 : Global Sustainability review on SPL

TEST QUESTION FOR THIS OPTION SCORE

(1) This options, how does it Both first and second cut are ground and added to the clinker
improve on existing methods production process in the kiln. Cyanides are destroyed and
of disposal or processing of fluoride immobilized. Emissions are kept at a minimum.
SPL? And how does it replace The fluoride is beneficial by lowering the melting point of
clinker. The carbon replaces a fraction of the normal fuel 4
any other methods?
and reduces the GHG intensity.

(2) Can this improvement be Yes. On the basis that both first and second cut are used,
quantified or measured? 100% of the SPL is reused in the clinker material. Metals are
recycled. 5

(3) Are alternative materials or The use of SPL saves on regular fuel used in the cement kiln,
energy sources used that over- which in 54% of the cases is coal. The fluorides lead to
all, from a life cycle point of lower melting temperatures and save on fuel intake. This
view, make this method better lowers the energy intensity and directly leads to lower GHG
or worse? intensities.
The sodium may be a problem for cement producers. An- 4
other challenges is the variability in the SPL composition.
This is another challenge for the operators.
Transportation over a substantial distance is involved that
requires fuel and leads to incremental GHG allocations.
(4) How does this method It eliminates virtually all wastes. It does, however, still
eliminate wastes and if new require to transport a hazardous waste over road, by
wastes are created, are these ship or by rail. 4
easier or more difficult to deal
with?
(5) Is this method reducing the The SPL is fully recycled. Provided the cement meets
long term impact on environment all criteria then all future liabilities are taken away from
for other generations that follow the SPL.
Us? The use of SPL in cement is a practice from the last 5
to 10 years. Long term effects beyond 30 to 50 years 4
are not known yet.

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5. Conclusion

SPL a national Challenge & being hazardous waste should be looked through holistic
view rather as a business opportunity to make money. There are several aspects to consider
in determining the cost of treating SPL or its derivatives in cement or Steel industries. In
Indian context , with new thought coming in advocacy that SPL material having good
calorific value must be used for the saving of natural resources to avoid its fast depletion
rather wasting its fuel value through landfilling. As per authors view , it must be put in
CTO conditions for related industry to close the loop by using waste of one industry as
Resource for another as a governance. Regulators must promote such industrial tie up
promptly to attain better carbon foot prints is such industry through PAT Scheme.

Cost Related Global Inputs:

1. The cost of safely transporting the treated SPL – still classified as a hazardous waste, but
not a dangerous good-from smelter to a receptive cement kiln or Steel making Furnaces.
2. The liability insurance costs for transporting SPL off-site, to cover spillages during
transport.
3. The cost of a receiving, storage and kiln injection/feed system at the cement plant site, to
allow the SPL to be added to the kiln at a known and monitored rate. Given that this will
generally be < 1 – 2 tph, the cost of such a system will largely be governed by the quantity
of storage required at the cement plant to cover the time between SPL shipments from a
smelter. As an example, the cost for installing a receiving system (SPL delivered by 27
tonne possolanic tankers), 1500 M3 storage silo and pneumatic injection system at the Ci-
mento Potty cement kiln in Brazil was USD 0.3 Million (excl. crushing plant) in 2001.
Scaling for Indian operations the cost would be approximately the same in current dollars.
The cost of the SPL injection facility at BCSC Waurn Ponds – comprising a 50 tonne silo,
and variable speed screw feeder delivering material into the calciner end of the kiln was <
AUD 1 Million in 1998. In today’s costs this would be around USD 0.5 Million. In the
US, Alcoa spent up to 3 million USD to make two cement plants ready to process their
SPL.

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