Measurements of the Quality of Cement Produced from Looped Limestone

Charles Dean, Prof. Denis Dugwell and Dr. Paul Fennell* Department of Chemical Engineering and Chemical Technology, Imperial College London. Funded by EPSRC

IEA GHG Solid Looping Cycles Network, Vienna 2011.

*p.fennell@imperial.ac.uk

Presentation Outline

Background to the Project Objectives Methods Some Results

Benefit to Cement Manufacture of Using Spent Sorbent

kg / tonne clinker

Assuming energy demand of 3.7GJ/tonne clinker, pet coke use at calciner and bituminous coal at kiln.
Data taken from: Alsop, P. A., 2007, Cement Plant Operations Handbook

Benefit to Cement Manufacture of Using Spent Sorbent

kg / tonne clinker

Therefore possible to mitigate ~ cement CO2 emissions by using spent sorbent from Ca-loop.

Assuming energy demand of 3.7GJ/tonne clinker, pet coke use at calciner and bituminous coal at kiln.
Data taken from: Alsop, P. A., 2007, Cement Plant Operations Handbook

Cement Chemistry Overview

CaO is used to produce calcium silicates upon hydration these crystals form an interlocking microstructure which provide the bonding strength.

KILN REACTIONS 900-1200 2CaO+SiO2 2CaO.SiO2 Belite > 1 yr strength CaO + Clay Calcium Aluminates (Interstitial phases)
1250-1500 CaO+2CaO.SiO2 3CaO.SiO2 Alite < 1 yr strength

Final Proportions: ~ 60 % Alite, ~ 25 % Belite, ~ 15 % interstitials.

The Role of Trace Elements in Cement

Formation of calcium silicates strongly influenced by trace elements in clinker:

e.g. Effect of MgO

e.g. Effect of ZnO

Some elements are beneficial between certain limits, detrimental outside of those limits. e.g. MgO > 2 %.

Objectives of the Project

To identify chemical changes in sorbent (concentration of trace elements) upon repeated cycling under different conditions.
Repeated cycling will lead to chemical and physical changes in the sorbent. In particular combustion products and ash from fuel use in calciner will potentially be retained in the sorbent.

To relate chemical changes in sorbent to possible changes in cement quality/composition.

In this project, cement quality is being inferred from alite production (as the most prevalent phase).

Objectives of the Project

To identify chemical changes in sorbent (concentration of trace elements) upon repeated cycling under different conditions.
Repeated cycling will lead to chemical and physical changes in the sorbent. In particular combustion products and ash from fuel use in calciner will potentially be retained in the sorbent.

To relate chemical changes in sorbent to possible changes in cement quality/composition.

In this project, cement quality is being inferred from alite production (as the most prevalent phase).

Research Methodology
1. Produce sorbent using different fuels and numbers of cycles. 2. Analysis of sorbent (ICP). 3. Production and analysis of clinkers (XRD).

Sorbent Production and Analysis

Sorbent Production 3kW Spouted Bed Reactor

Bed Temperature (C)

Time (s)
Fluidising gas Fuel

15 % CO2 (balance air), 5 l/m, Longcal P25 limestone, 425 500 . 2g coal / cycle based on modeling work (essentially is amount reqd at calciner based on 30 % split fuel use).

CO2 concentration

Sorbent Production RDF Fuel Feeding System

Methods: Trace Element Analysis of Fuels & Sorbent

Sorbent prepared for ICP hot nitric acid digestion followed by filtration. Efficacy of digestion checked using standard reference materials.
SRM 1d - Limestone
2500 Sample Conc. (ppm) 2000 1500 1000 500 0 Mg Fe K Ref. S Exp. Sr Mn P

SRM 1547 Biomass (Peach Leaves)

[Units ppm]

Clinker Production and Analysis

Clinker Production

Once sorbent is removed from reactor: Homogenised with other oxides in DI water then dried. Pressed into a brick using 100 atm pressure. Then fired in tube furnace at 1500C for 2hrs.

Clinker Production

The brick is then pushed directly from the furnace into an air cooled chamber 25 l/m applied evenly across brick until ambient temp. This is to prevent decomposition of alite to belite which can take place if clinker is allowed to cool at its own rate.

Methods Qualitative Assessment of Clinkers

First, qualitative assessment of phases present in the clinker indicates that correct phases are present.
Intensity (counts)

Alite
6400

Interstitial phases
3600

Belite
1600

400

Blue Belite Green Alite Pink - Interstitial

0 25 30 35 40

Methods Quantitative Assessment

% alite is achieved by mixing clinker samples with corundum (Al2O3) in 1:1 ratio. This enables changes in alite peaks to be converted to % by comparing to corundum peak (using RIR value taken from ICDD database).
Intensity (counts)

2500

1600

900

400

100

0 26.5 27.0 27.5

Xa = (Ia/Ic)*(Irelc/Irela)*(Xc/RIR)
28.0 28.5 29.0 29.5 30.0 30.5

2Theta ()

Main Results % Alite

Main Results - % Alite No Fuel & La Jagua Coal

All results average of 3 replicate experiments

No Fuel
100 90 80 70 60 50 40 30 20 10 0

2 g / cycle

% Alite

10 No. Cycles

15

C. Dean, D. Dugwell, and P.S. Fennell. Energy & Environmental Science, 2011. 4(6): p. 2050-2053.

Sorbent trace element levels after 5 cycles

5 cycles, La Jagua Colombian coal 2 g / cycle Average of 3 replicate experiments

B Ti Zn Ba Cr Cu Ni Mg Mn Sr

La Jagua ppm 13.88 69.77 6.17 80.34 2.97 31.50 2.89 114.31 6.57 56.85

Longcliffe ppm 0.00 0.35 0.00 12.00 2.50 4.50 0.35 1500.00 45.00 135.00

5cyc Sorbent ppm 9.73 6.60 5.14 27.99 47.26 10.64 0.30 1295.29 57.54 112.82

Elements Detrimental to Alite Formation

* *
Elements Beneficial to Alite Formation

Increase in most elements. However largest increase is Ba and Cr. (Decrease in Mg and Sr assume that other increases over-ride these losses).

Sorbent trace element levels after 5 and 1 cycle

5 cycles, La Jagua Colombian coal 2 g / cycle Average of 3 replicate experiments

B Ti Zn Ba Cr Cu Ni Mg Mn Sr

La Jagua ppm 13.88 69.77 6.17 80.34 2.97 31.50 2.89 114.31 6.57 56.85

Longcliffe ppm 0.00 0.35 0.00 12.00 2.50 4.50 0.35 1500.00 45.00 135.00

5cyc 1cyc Sorbent Sorbent ppm ppm 9.73 9.81 6.60 0.00 5.14 4.87 27.99 47.26 10.64 0.30 1295.29 57.54 112.82 6.59 3.82 13.76 0.00 1399.19 43.98 84.23

Drop in the level of trace element concentrations after 1 cycle indicates that most elements are first lost before being replenished. This could explain drop in % alite upon repeated cycling without fuel.

Conclusions on cement from cycled sorbent

Repeated cycling without fuel - appears to impact negatively on alite production. Trace element results after 1 cycle indicate that this could be due to loss of impurities / trace elements. For the case of La Jagua repeated cycling appears to improve alite formation. Trace element results after 5 cycles indicate this could be due to replenishment of impurities from fuel, esp. Ba and Cr.

However further work needed esp. producing clinker from raw materials containing a more realistic baseline of trace elements (i.e. clay) to see if repeated cycling with fuel takes trace element concentrations past any tipping points.

Further Results Trace Element Partitioning

Partitioning of Trace Elements

Partitioning of Trace Elements

Partitioning of Trace Elements after 5 cycles: RDF

% Recovered in Solid Streams 450 400 Heavier elements closer to 100 %. More volatile elements lost. Contamination from Ti and Cu.

350
% Recovered 300 250

200
150 100

50
0 Ti Ti Cu B V Al Ba Cr Mn Fe Na K S Zn Sr Ni Mo Mg Pb P Co Cd As Sb Average of 3 repeats

Partitioning: Implications for Cement Manufacture

- Sorbent - Fly Ash - Fines - Lost

Na
+148 %

K
+43 %

RDF Trace Element Conc. RDF 18,000ppm! 20,000ppm!

S
+ 579 %

Conclusions on RDF trace element partitioning

Heavier elements / elements with lower boiling points tend to reside in sorbent and therefore potentially also in the cement. Volatile elements tend to collect in fines / fly ash or exit as gas.

Partitioning shows that Na, K and S could cause problems in use of RDF-derived sorbent, both in cement application (i.e. aggregate/concrete) and in Ca-loop / cement plant operation.
Climafuel feeding: contamination issues need resolving before producing cement!

Thankyou Questions