The Effects of Oxygen Enrichment on Clinker, Cement and Concrete Quality

Frederick Hommel St. Lawrence Cement, Catskill, NY ABSTRACT From 1/19-2/27/2000 the Catskill plant with the assistance of Air Products personal ran a trial test on enriching the kiln combustion air with pure oxygen to improve production and quality. This paper gives an overview of this test and describes how this effected the clinker, cement and concrete quality. INTRODUCTION Enriching combustion air with oxygen to improve clinker production was first suggested back in 19031. During the 1940s commercial attempts at enriching combustion air in blast and rotary kilns were tested in Germany and the USSR1. They found that upon the addition of oxygen that the flame shape became shorter and brighter2. Full commercial implementation of this technology in these countries was not enacted do to problems with refractory life 2. Commercial attempts in wet kiln were conducted in the early 6os by Union Carbide at Southwestern Cements Victorville, CA wet kiln. They found that a 1 to 2.3% oxygen enrichment level increase clinker production by 5% and specific fuel consumption decreased by 7%. Increasing clinker production beyond 5% was limited by their clinker cooler capacity. After modifying their clinker cooler they were able to increase the oxygen enrichment to 4% which increased production rates to 35% and decreased specific fuel consumption by 15% 2. In addition to the production increases and decreases in fuel consumption it was indicated that cement clinker quality improved. Particularly they found that the free CaO content decreased and the concentration of C3S increased2. The use of oxygen enrichment of the kiln combustion air since the 60s has been limited do to the high cost of oxygen. However in resent years the value of clinker has increased while the cost of oxygen has remained stagnate, making the use of oxygen enrichment again a possibility. The possibility of increasing clinker production and improving cement quality by oxygen enrichment was the main reason for trying this technology at the Catskill Plant. St. Lawrence Cement owns the Catskill Plant that is located on the banks of the majestic Hudson River approximately 100 miles north of New York City. The Catskill plant contains a single long wet kiln with an annual clinker production of 520000 metric tons. The kiln is 550 feet long 18x17 feet in diameter with an F L Schmidt grate cooler. The fuel is a mixture of coal and petroleum coke and is blown into the kiln by the direct-fired method. Currently the pet coke substitution rate for coal is around 12%. Wasted kiln dust is recycled back into the kiln by a dust scoop system located just after the chain section. The burning process, raw and finish grinding is semi-automated with the operation being handled from a central control room. From 1/19-2/27/2000 the Catskill Plant conducted a trial test to oxygen enrich the kiln combustion gas. The goal of this test was to see at least a 10% increase in production and a 10% decrease in specific energy consumption with improved cement quality via a oxygen enrichment in the range of 1 to 4%. The plan was to increase feed and speed while the volume of kiln gases decreased. Data showing how this process would change clinker, cement and concrete quality was very limited and so would be also investigated. Air Products provided the engineering and equipment needed to run the test. They worked side-by-side with our operators in the control room to develope operating ranges for the kiln operating parameters. For the trial period we were to pay Air Products $0.15/100 scf oxygen and $6.00/ton for clinker which exceeded our normal clinker production. INSTALLATION The outside installation consisted of a 9000-gallon tank of liquid oxygen with 8 ambient vaporizers located near the kiln (see Figure 1). Oxygen from this tank went to a controlling regulator which feed oxygen into a flow-controlling device located on the kiln deck. From this regulator, oxygen was injected into a stainless

steel lance that was located approximately 12 inches behind the nose of the coal pipe and was positioned towards the load quadrant of the kiln (see Figure 2). Heat generated by the injection of oxygen would radiate towards the load while the main body of the flame would act as a shield protecting the refractory and its coating from the intense flame generated by the oxygen enrichment. A safety interlock system was in place to guarantee that if there were a loss in fuel the oxygen enrichment would be shutoff automatically.
Standard Oxygen Enriched Flame Section of Flame Burner Fuel Oxygen Lance Clinke r Oxygen Load Firehood

Clinker Load

Front View Figure 1. View of a Typical Liquid Oxygen Storage System Figure 2. Diagram of oxygen enrichment in in the rotary kiln

Side View

QUALITY OBSERVATIONS Oxygen enrichment did effect the clinker quality. Clinker density increased and became harder to grind with increasing oxygen. Alites in general became larger and more rounded with increasing oxygen and some of the more rounded alites had a slight fringe around them (Graph 1). The large alites tended to be less reactive to 1% Nital etching solution and turned brown, however there was areas of very small crystals which were very reactive and changed to dark brown to blue. Alites remained bright under plane-polarized light and the birefringence improved slightly at 25000 scfh but decreased at higher oxygen levels. Belites tended to decrease in size and appear to be slightly more ragged with increasing oxygen, however they were very reactive to the 1% Nital solution and turned blue in this etching solution (see Figures3-7 & Table#1). Most of the belites had a fine twin lamellae structure and had a color of clear to pale yellow under transmitted light. Under plane polarized light the belites with no oxygen enrichment had a higher percentage of higher order color. Many clinkers throughout the test had very large nests of belites. The matrix surrounding the alite and belite crystals remained well differentiated for the entire test, however at times the distance between crystals were very narrow especially at the higher oxygen levels.

Figure 3 Clinker taken on 1-8-2000, no oxygen enrichment, alites and belites have sharp edges

Figure 4 clinker taken on 1-20-2000, oxygen enrichment rates at 25000 scfh, some crystals are slightly larger, both alites and belite continue to have sharp edging

Figure 5 clinker taken on 2-1-2000, oxygen enrichment rate at 30000 scfh, alites are larger and more rounded, belites are large and some have ragged edges

figure 6 clinker taken on 2-3-2000, oxygen enrichment rate at 350000 scfh, alites are large and rounded, belites are large with some ragged edges, liquid phase poor

Figure 7 clinker taken on 2-24-2000, oxygen enrichment rate at 40000 scfh, alites are very large, rounded and some have a belite fringe, belites are smaller and some have ragged edges

Clinker Crystal Size Polished Surface Method

80

70

60

Microns

Alite Length
50

Alite Width
40

Belite Width
30

20

10 0 10000 20000 30000 40000 50000

O2 Enrichment Rate scfh

Graph 1 7 and 28 day cement strengths improved and setting times lengthen until the oxygen level exceeded 30000 scfh. After exceeding the 30000 scfh the 7 and 28-day cement strengths decreased and the setting time shorten slightly. Water demand as measured by the Normal consistency test and cement cube flow stayed about the same throughout the test (see Table2 & Graph2). Graph 2
Cement Strengths
7000

6000

5000

PSI

4000

3000

2000

1000 0 10000

O2 Enrichment Rate scfh

20000 30000 40000

1 day cement strength 7 day cement strength

3 day cement strength 28 day cement strength

Concrete tests were fewer in number than the cement testing however they showed similar results to 28-day cement strengths. The 28-day concrete strengths improved with increasing oxygen enrichment until the oxygen level exceeded 30000 scfh. At 30000 scfh the 28-day strength decline. 7-day concrete strength did not improve but stayed the same (see graph3). Water demand as measured by the slump increased slightly higher upon the addition of oxygen, but then remained the same as oxygen increased.
Concrete Strengths

7000 6500 6000 PSI 5500 5000 4500 4000 3500 0 10000 20000 O2 Enrichment Rate scfh 30000 40000

7 day conc. Strength

28 day conc. Strength

Graph 3

BRICK & COATING OBSERVATIONS During the test maintaining a good coating was not a problem. After the trial test was completed the kiln was shutdown for our annual maintenance overhaul. The brick in the burning zone did not show signs of glazing which might be expected if excessive heat was produced. The brick however showed rounding of corners which is more indicative of material wear. The kiln was shutdown during the early part of the test do to a coal mill fire. At the time of that shutdown a ring was found at 106 ft with no coating between 80 and 100 ft. The Chemistry of the ring showed that it was regular coating with slightly higher SO3 and K2O. At the end of the test there was no ring and the coating was very good to the 90ft. Normally at a major shutdown there is a mud ring at the kiln feed inlet but this time there was none. KILN OPERATION OBSERVATION With the addition of the oxygen we expected to see the flame shorten and become brighter like an acetylene torch, however with our kiln that did not appear. Only the flame nearest to the oxygen lance increased in brightness. Kiln burning zone temperatures and secondary air did increase with additional oxygen but material and backend temperatures remained constant. The kiln draft decreased and the kiln amps increased as oxygen levels increased. Kiln operators adjusted the speed of the kiln by monitoring the heat profile, as the kiln got hotter they increased the speed. We did experience some persistence problems with maintaining constant fuel in the kiln. Wet coal gave us problems in the coal mill and so we experienced several times when the fuel and oxygen enrichment had to be shutdown. To maintain the heat profile, kiln operators tended to over burn the kiln. Another problem experienced during the test was that the oxygen lance would warp if it were not removed quickly enough when the oxygen was discontinued.

ENVIRONMENTAL OBSERVATIONS When the trial test was started it was thought that the NOx levels might increase. However after looking at the Nox readings the conclusion is that there was no change (see graph 4).

O2 trial at Catskill plant ppm NOx

1000 900 800 700

ppm NOx

600 500 400 300 200 100 0 1/10/00 1/12/00 1/14/00 1/16/00 1/18/00 1/20/00 1/22/00 1/24/00 1/26/00 1/28/00 1/30/00 2/11/00 2/13/00 2/15/00 2/17/00 2/19/00 2/21/00 2/23/00 2/25/00 2/27/00 1/4/00 1/6/00 1/8/00 2/1/00 2/3/00 2/5/00 2/7/00 2/9/00

ppm NOx

STDEV ppm NOx

O2 SCFH*f

Graph 4

SUMMARY OF TEST The clinker microstructure and visual inspection of the kiln indicate that the flame did not get shorter but remained a long flame. The clinker was over burned, but with increasing oxygen the kiln refractory was easier to coat. The kiln refractory was not damaged by excessive heat caused by the injecting of oxygen in the combustion gases. Coal mill problems increased instability within the kiln and frequent changes in oxygen enrichment also increased variations in clinker microstructure. Clinker and cement quality improved with some oxygen enrichment but decreased after a certain point. This exact point needs to be determined when the kiln is operating steadily and the tendency to over burn is minimized. Oxygen enrichment had no over all effect on raising NOx emission levels. Clinker production increased about 9% and the heat consumption decreased about 5% by the end of the test. Lowering the heat consumption was hampered do to a very high kiln feed moisture caused by poor weather conditions and lack of chain in the kiln. It is projected that enriching the combustion gases with oxygen will increase clinker production by 9% and save the plant $1.7 million per year. REFERENCES 1. 2. Use of Oxygen in Cement Clinker Burning, Zement Kalk Gips, Vol. 4, 140-145, 1967. Oxygen Enrichment of Combustion Air in Rotary Kilns, Regional Fall Meeting General Technical Committee, Portland Cement Association, Miami Beach, 1961.

Table #1 Clinker Analysis

O2 SCFH Fe2O3 SiO2 Al2O3 CaO MgO SO3 Na2O K2O TiO2 P2O5 Total Alki Free Lime C3S C2S C3A C4AF Li. Phase L.S.F Si Ratio Al Ratio CL density

0 3.68 22.47 4.14 65.72 1.60 0.37 0.23 0.61 0.23 0.21 0.63 0.13 60.72 18.70 5.90 11.19 21.58 92.96 2.72 1.24

25000 3.69 23.04 3.83 66.20 1.60 0.34 0.23 0.49 0.22 0.22 0.48 0.12 60.41 20.58 5.05 11.23 20.69 92.02 2.91 1.16 1267.8 50.76

30000 3.60 22.87 3.96 65.92 1.62 0.39 0.23 0.59 0.23 0.20 0.61 0.18 59.82 20.54 5.55 10.95 20.87 92.12 2.87 1.22 1248.1 49.74

35000 3.80 22.45 4.17 65.76 1.67 0.35 0.23 0.59 0.23 0.21 0.61 0.18 60.65 18.69 5.79 11.56 21.96 92.95 2.67 1.21 1248.9 53.48

45000 3.64 23.00 4.03 67.08 1.69 0.17 0.22 0.30 0.23 0.22 0.42 0.04 62.90 18.58 5.72 11.08 21.22 93.10 2.83 1.23 1259.8 60.00

1168.8 Grindability %retained 200 48.00

Transmitted, plane-polarized light Alite Avg Width(microns) Alite Avg Length a Alite Shape Alite Birefring Belite Size Belite Shape Belite Color Ohno Strength Index Refractory In Belite
c b

24.8 48.4 2.0 0.0081 35.5 1.0 1.3 6210 2.8

28.6 57.1 2.5 0.0085 42.6 1.5 1.3 6210 3.0

26.9 52.9 2.7 0.0076 35.2 1.3 1.2 6188 2.2

25.7 50.6 2.9 0.0075 33.9 1.7 1.2 6121 2.1

29.0 54.5 4.0 0.0086 35.0 3.0 2.1 5940 2.0

Polished Surface Method Alite Width Alite Length Belite Width

28.7 57.0 37.2

32.1 62.1 39.6

32.7 60.1 36.8

29.0 57.6 34.5

39.2 77.5 33.3

Table #1
a

Alite shape Index 1 Sharp edges 2 Some rounding of edges 3 Rounded edges 4 Very Rounded edges

c Belite shape Index Refractory in Belite Index 1 Sharp circular 1 None 2 Circular with slight ragged edges 2 Trace 3 Circular with some ragged edges 3 Some 4 Many with very ragged edges 4 A lot

Table #2 Catskill Kiln Oxygen Enrichment Test Cement & Concrete Analysis O2 SCFH Fe2O3 SiO2 Al2O3 CaO MgO SO2 Na2O K2O TiO2 P2O5 Total Alki Free Lime C3S C2S C3A C4AF Blaine 325 mesh NC Vicat Intial Set Vicat Final Set Cement Cube Flow 1 day cement strength 3 day cement strength 7 day cement strength 28 day cement strength Concrete Slump Unit Weight 7 day conc. Strength 28 day conc. Strength 0 3.51 21.61 3.89 64.28 1.65 2.54 0.23 0.58 0.22 0.20 0.61 0.30 56.2 19.7 5.47 10.68 3745 93.02 24.3 190 281 116 1815 3493 4427 6213 7350 3.50 21.30 3.84 64.22 1.66 2.57 0.23 0.51 0.22 0.21 0.57 0.30 58.5 17.0 5.40 10.65 3720 93.58 24.9 255 330 119 1820 4710 23125 3.65 21.12 3.81 63.38 1.61 2.65 0.23 0.59 0.22 0.20 0.61 0.20 56.3 18.2 5.05 11.09 3770 93.95 24.5 218 300 110 1750 3445 4725 6780 30972 3.61 21.14 3.81 63.65 1.60 2.56 0.23 0.58 0.21 0.18 0.61 0.28 57.7 17.2 5.02 11.00 3680 93.23 24.3 172 253 116 1817 3430 4280 6323 35063 3.56 21.48 3.96 64.06 1.63 2.67 0.23 0.62 0.22 0.20 0.64 0.38 55.3 19.9 5.59 10.83 3843 92.75 24.4 180 293 116 1943 3598 4238 6080 37500 3.51 21.21 3.79 64.31 1.61 2.50 0.23 0.51 0.22 0.21 0.57 0.34 60.0 15.6 5.25 10.68 3760 91.35 24.3 240 315 114 1560 3540 4460

3.8 149.8 4063 5277

3.5 152.9 3950 6310

3.5 150.6 4133 5843