Reducing Refining Cycle Times

to Extend Anode Furnace Campaign

Life at Kennecott Copper

Jun Enriquez, Ryan Walton, Adrian Deneys, Allen Chan,

Bryan Bielec and Viktor Kilchyk

Abstract Kennecott Utah Copper aims to extend anode furnace campaigns to more
than three years. As part of that goal improvements are sought on anode-furnace
tuyere-area refractory performance. Kennecott and Praxair developed high pressure
nitrogen refining for the Oxidation Stage which shortened anode furnace fire re-
fining cycles by up to two hours per cycle. Future developments include optimizing
the Reduction Stage’s steam-gas reforming and achieving coherent jet tuyereless
refining.

Keywords Anode furnace ⋅ Refining ⋅ Nitrogen

Introduction

Kennecott Utah Copper aims for three-year anode furnace campaigns to coincide
with scheduled acid plant turnarounds. Extending the anode furnaces’ campaigns is
an ongoing effort which includes multiple projects.
The end of the anode furnace campaign is determined by refractory wear in two
main areas. The areas are the furnace mouth and the tuyeres’ areas. The anode
furnaces historically underwent a partial repair every 18 months mainly to repair
refractory damage in either or both areas. Maintaining and extending the life of
these areas will reduce the frequency of repairs, thereby delivering an increase in
furnace campaign life.
This paper’s focus is on investigating factors to extend the tuyere-zone refractory
life. This includes shortening the refining cycle time, high pressure injection to

J. Enriquez ⋅ R. Walton
Rio Tinto/Kennecott Utah Copper, 11600 West 2100 South, Magna, UT 84044, USA
A. Deneys (✉)
Praxair Inc., 2430 Camino Ramon Suite 310, San Ramon, CA 94583, USA
e-mail: adrian_deneys@praxair.com
A. Chan ⋅ B. Bielec ⋅ V. Kilchyk
Praxair Inc., 175 E. Park Drive, Tonawanda, NY 14150, USA

© The Minerals, Metals & Materials Society 2018 519

B. Davis et al. (eds.), Extraction 2018, The Minerals, Metals & Materials Series,
https://doi.org/10.1007/978-3-319-95022-8_41
520 J. Enriquez et al.

achieve sonic flows, and coherent jet technology development. The anode furnace
mouth area is not described.
The work of Chibwe et al. [1] is acknowledged which informed this study.
Chibwe et al. cited reduced wall shear stress with sonic velocity injection. This is
thought to contribute to reduced tuyere-line wear and is one hypothesis supporting
higher pressure injection.

Literature Review on Nitrogen Anode Furnace Fire Refining

Chibwe et al.’s [1] work is of interest in this study owing to factors identified in the
sonic velocity injection regime. This offers the potential to improve the tuyere-zone
refractory wear profile. Chibwe et al. calculate wall shear stress on the tuyere side.
Sonic injection is associated with substantially lower tuyere-zone wall stress
compared to sub-sonic injection. Sonic injection is associated with a higher center
line jet velocity profile (deeper plume). This supported the goal of testing higher
pressure nitrogen injection.
Masterson [2] described blister copper refining at Kennecott from Peirce-Smith
converting (<200 ppm sulfur). Nitrogen refining data formed the basis for Fig. 1
calculated blow rate [3].
Goyal et al. [5] noted that nitrogen sufficiently desulfurized molten copper
containing sulfur with the emphasis of the study being on porous plugs.
Krag et al. [7] describe nitrogen to dilute air in semi-blister copper anode furnace
fire refining. Air was used to 2000 ppm sulfur. Then nitrogen was added to air for
“de-sulphurization partially by reaction with oxygen already dissolved in the melt.”

Time Required for 10 fold Reduction in Sulfur with N2 and Air

350
N2 Stir Time
300
Air Stir Time
250
Minutes

200

150

100

50

0
0 500 1000 1500 2000 2500 3000 3500 4000
Average Dissolved Oxygen PPM

Fig. 1 Predicted time for 10 fold reduction in sulfur with nitrogen versus air (258,000 scfh blow
rate, nitrogen at 20% efficiency with air at 25% efficiency [2]
Reducing Refining Cycle Times to Extend Anode Furnace … 521

One tuyere of 20.5 mm ID was used, with air at 36,480 scfh (960 Nm3/h) at
89 psig (5.9 bar). Oxygen efficiency was 20% for 60 min blow, for 0.02 wt% sulfur
incoming, with 0.70 wt% oxygen incoming, oxidized to 0.01 with 0.74% oxygen.
For poling natural gas flow was 41,040 scfh (1080 Nm3/h), at 30% efficiency for
120 min, finished at 0.1% oxygen. Nitrogen was proposed for 50% nitrogen con-
centration in the reducing gas (40% CH4 efficiency projected).

Shortening the Anode Furnace Refining Time

Shortening the refining cycle time comprises efforts on three parts of the tuyere
injection process: (i) non-blowing time, (ii) oxidation stage, and (iii) reduction
stage. Slag skimming is an additional important stage but is omitted owing to
infrequency. Efforts on (i), (ii), and (iii) include:
1. Avoiding delays (or non-blowing time delays). Cold blister copper is a main
reason for delays. Adjusting CoJet® system burner setpoints avoids cold blister;
2. Achieving a shorter Oxidation Stage (oxidation blowing period);
3. Achieving a shorter Reduction Stage (reduction blowing period).

Achieve a Shorter Oxidation Stage—Nitrogen Tuyere

Refining

Kennecott tested nitrogen in the anode furnaces’ Oxidation Stage in October 2015.
After initial successful results nitrogen was expanded to charges with higher
starting sulfur levels. By late 2016 nitrogen was used for 95% of charges, except
when starting sulfur was greater than 600 ppm and oxygen below 3000 ppm. Since
November 2016 that restriction was lifted.
Dissolved oxygen and sulfur react and the nitrogen carries the sulfur dioxide gas
out of the molten copper. Oxy-fuel burners (Praxair J/L and CoJet® burners)
combustion stoichiometry is important to control oxygen and blister copper tem-
perature prior to nitrogen refining.
Nitrogen is also used as a purge for the steam-natural gas Reduction Stage, for
slag skimming, porous plug stirring and during the Purge Fire mode during CoJet®
system use.
522 J. Enriquez et al.

Background

Praxair and Kennecott developed Submerged Melting and Refining Technology [2]
which described nitrogen for refining blister copper. Praxair proposed a nitrogen
blow profile [3] based on a nitrogen desulfurization efficiency of 20% from 1985
plant trials [2]. A tuyere injection rate of 258,000 CFH (4300 CFM)
[237,000 ncfm] 6790 Nm3/h was proposed to achieve a ten-fold sulfur reduction in
30–60 min. The suggestion to evaluate nitrogen arose during a meeting with
Tongling Copper who use nitrogen for anode furnace fire refining at 1000 Nm3/h
(38,000 scfh) and discussed this with Kennecott and Praxair in 2013.
In early 2014 Kennecott experienced an air-compressor outage. Having nitrogen
(and oxygen) as a back-up for tuyere refining became a further incentive to evaluate
high pressure nitrogen and oxygen for tuyere refining. While using rental air
compressors Kennecott observed higher pressure air enabled fewer tuyere plugging
events. Pipeline nitrogen, available at 90–120 psig (6–8 bar), was available to test
the hypothesis that higher pressures would reduce tuyere plugging events.

Nitrogen and Oxygen in Porous Plugs

Kennecott Utah Copper employs nitrogen porous plugs in the anode furnaces. It has
been known since the porous plugs were installed in 1994 [4] that nitrogen through
the porous plugs steadily removes sulfur [5]. The nitrogen flow rate is 500 ncfh per
porous plug and there are eight on one furnace and nine on the other. Kennecott also
conducted a trial on oxygen addition to the porous plugs on one furnace. The goal is
to use the fill-period to add oxygen to the blister copper for high-sulfur charges.

Baseline Conditions for Nitrogen Tuyere Refining

Flow and Pressure of Oxidation Air Supply

The oxidation air flow and refining times for the West Furnace and East Furnace
are shown in Fig. 2a and b. The East Furnace data was 6 February 2014 at
8:50–11:00 am, and the West Furnace on 5 February 2014 at 2:30–4:40 pm.
The steady state injection pressure for the West Refining furnace is 55 psig (at
the pressure transducer, pressure is lower at the tuyere owing to pipeline pressure
drop from the pressure transducer to the tuyere’s rear) peaking to 59 psig (tuyeres
plugging). Steady state pressure for the East Refining furnace was at 49–55 psig,
peaking at 57 psig. The East Anode Furnace pressure is lower owing to longer
distance from the air compressor to the East Furnace (more pressure drop in the
distribution piping).
Reducing Refining Cycle Times to Extend Anode Furnace … 523

(a) East Furnace

2000 80
1800
70
1600
60
1400
Air Flow, NCFM

1200 50
FI_527129, NCFM
1000 40
FI_527131, NCFM
800
30 PI_527129, PSI
600
20 PI_527131, PSI
400
200 10

0 0
0:00 0:28 0:57 1:26 1:55 2:24
Time, Minutes

West Furnace
(b) 2000 70
1800
60
1600
1400 50
Air Flow, NCFM

1200
40 FI_527052, NCFM
1000
30 FI_527054, NCFM
800
PI_527052, PSI
600 20
PI_527054, PSI
400
10
200
0 0
0:00 0:28 0:57 1:26 1:55 2:24
Time, Minutes

Fig. 2 East (a) and West (b) anode furnaces oxidation stage with 65 psig air compressor

Total air flows are 2300 cfm for the East Furnace and 2175 cfm for the West
Furnace. For a nominal 2 h oxidation period the total air is 2300 ncfm ×
120 min = 276,000 ncf per charge. Maximum flow is about 2400 ncfm, or
144,000 ncfh to both tuyeres.
Praxair modeled the adiabatic frictional flow for air through a single tuyere. At
pressures higher than 37 psig (at the tuyere’s rear) the calculated flow reaches sonic
velocity in the tuyere.
524 J. Enriquez et al.

Flow and Pressure for Steam-Natural Gas Refining

Steam and natural gas reduction was calculated with 5100 lb per hour steam and
[380–400 ncfm] 25,200 ncfh (723 Nm3/h) natural gas blow rate. The steam was
assumed to be at 500 °F (533 K).
Assumption for overall reduction reaction: CH4 + 4O = CO2 + 2H2O, where
O is dissolved oxygen in the molten copper. For the input rate of natural gas the
maximum theoretical rate of oxygen removal is calculated at 48 kg per minute
dissolved oxygen removed. For two charges studied the oxygen removal rate was at
33 and 20 kg/min giving corresponding oxygen removal efficiency at 68 and 42%
respectively. Another way to express this is as the steam-gas refining efficiency.
Other data on the same furnaces show reductant (or steam-gas refining) efficiency
up to 78%.
The adiabatic frictional flow calculation for the steam-gas reduction stage was
also modeled. At pressures above 35 psig at the back of the tuyere the calculated
flow reaches sonic velocity in the tuyere. The steam-natural gas reduction stage is
nominally 100 min of blow time (range 98 min on one furnace and 101 min on the
other). The main factor influencing the Reduction Stage blow time is the quantity of
dissolved oxygen which needs to be removed.
Measurements were made at the tuyere during one refining cycle. During the
Oxidation Stage the pressure was above the minimum calculated for sonic velocity
injection. During the Reduction Stage the pressure was below the minimum for
sonic velocity injection (Fig. 3).

Fig. 3 Kennecott-Praxair tuyere pressure measurement system

Reducing Refining Cycle Times to Extend Anode Furnace … 525

Theory

Sulfur removal from molten copper by nitrogen purging is as follows, where S and
O are sulfur and oxygen dissolved in the molten copper:

S + 2O = SO2
 
K = PSO2 ̸ aS ⋅ ðaO Þ2

According to Le Chatelier’s principle this reaction is driven to the right hand side
(formation of sulfur dioxide by removing dissolved sulfur and oxygen) by lowering
the partial pressure of the sulfur dioxide. The equilibrium constant is fixed by the
reaction temperature. As the sulfur dioxide partial pressure is lowered the sulfur and
oxygen activities must be reduced to maintain the equilibrium constant. The
nitrogen bubbles initially contain no sulfur dioxide. Adding nitrogen enables the
partial pressure of the sulfur dioxide to be lowest at the start of the reaction.
This therefore drives the reaction between dissolved sulfur and dissolved oxygen.
More detail on the proposed equilibria can be found in the literature [4, 6].

Energy Balance Effects

Nitrogen’s cooling effect is mitigated by the desulfurization reaction. Nitrogen is

injected at rates of up to 120 kg (4.3 kg mol) per minute. Dissolved sulfur and
dissolved oxygen react and the exothermic contribution to the energy balance
mitigates the temperature drop.
Nitrogen injected at up to 120 kg per minute can absorb 164 MJ as the nitrogen
is heated from 25 to 1220 °C. To cool 650 tonnes of copper by 1 °C (1 K) requires
337 MJ. Therefore nitrogen blown for ten minutes can cool the bath by 5 °C (5 K)
or 9 °F. During tuyere refining the burner is off. The steady state energy loss rate is
8 MMBtu/h or 2.43 MW. Therefore in 1 h the system loses 8435 MJ. In our case
the bath loses 25 °C (25 K) or 45 °F per hour when the end-wall burner is off.
Oxidation Stage energy balance is calculated for 22 ppm per minute sulfur
removal rate with nitrogen. The temperature rise (by the exothermic reaction) is
0.3 °C/minute (however this is offset by the vessel’s steady state energy loss of
0.43 °C per minute, for a net calculated change of 8 °C (14 °F) bath temperature
drop over an hour of nitrogen blowing. This temperature drop is acceptable for
nitrogen refining to be useful at Kennecott.
526 J. Enriquez et al.

Results

Two examples of nitrogen refining are illustrated in Fig. 4. In the first example (left
hand side of Fig. 4) air oxidation is followed by nitrogen refining. This may occur if
the starting sulfur concentration is high, then the operator can elect to refine with air
to desulfurize and impart oxygen to the molten copper. Nitrogen blowing then
reacts dissolved sulfur and oxygen and reduces sulfur while limiting any increase in
dissolved oxygen which could lengthen the Reduction Stage. In the second example
the dissolved sulfur and oxygen levels favor nitrogen refining alone and the
Reduction Stage follows directly after nitrogen refining.
Data from 2016 Kennecott anode furnace charges are summarized in Table 1,
from both the East and West anode furnaces. Nitrogen refining data was obtained
from 1 January 2016 to 6 September 2016. The data in Table 1 shows that nitrogen
refining removes sulfur and oxygen and limits the dissolved oxygen concentration
rise when air is used for the oxidation stage of copper refining.
The data plotted in Fig. 5 shows nitrogen refining slightly decreased dissolved
oxygen for longer blow periods (higher sulfur charges). This contrasts greatly with
the proportional increase in dissolved oxygen with air. Nitrogen refining offers this
unique characteristic. As sulfur and oxygen react in the molten copper the con-
centrations of both solutes decrease when nitrogen is used as the Oxidation Stage’s
reagent (Fig. 5). The average refining cycle time decrease over eight months is
shown in Fig. 6.

Observations

The oxygen mass supplied by tuyeres which reacted with sulfur is the same as the
sulfur mass removed. For three selected charges the mass fraction of oxygen
supplied by air reacting with sulfur was 176/900 kg supplied which gives a 19.5%
oxygen utilization for sulfur removal. The oxygen utilization efficiency for air
oxidation ranged charges studied ranged from 19 to 31%. This compares well with
Masterson’s value of 25% [2] oxygen utilization efficiency.
Oxygen accountability for this calculation is 1074 kg (picked up by cop-
per) +176 kg (as SO2(g)). The oxygen accountability is 138% (1250/900 kg). The
oxygen accountability may exceed 100% due to variations in chemical analysis,
sampling, charge mass, and or air ingress into the furnace during the blow.
Additional work is planned to better understand the potential that oxygen pickup is
occurring through air ingress during refining. The balance of the oxygen added
through tuyere injection using air is accounted for by increased dissolved oxygen in
the molten copper.
Reducing Refining Cycle Times to Extend Anode Furnace … 527

(a) 2000 West Furnace (Plot I), 11 January 2016 21:00

100
Nitrogen refining

1800 90

1600 80
Air oxidaƟon
1400 70
ReducƟon
Tuyere flow, NCFM

1200 60

Pressure, psig
1000 50

800 40

600 30

400 20

200 10

0 0
21:00 21:30 22:00 22:30 23:00 23:30 0:00 0:30 1:00
Time h:min
FI_527052, NCFM FI_527054, NCFM PI_527052, PSI PI_527054, PSI

West Furnace (Plot II), 13 January 2016 5am

(b) 2000 100
Nitrogen refining

1800 90

1600 80

1400 70
ReducƟon
Tuyere flow, NCFM

1200 60
Pressure, psig

1000 50

800 40

600 30

400 20

200 10

0 0
5:00 5:30 6:00 6:30 7:00 7:30 8:00 8:30
Time h:min
FI_527052, NCFM FI_527054, NCFM PI_527052, PSI PI_527054, PSI

Fig. 4 a and b: West Furnace 11th (a) and 13th January (b) 2016 195 and 142 min refining times
examples
528 J. Enriquez et al.

Table 1 Nitrogen refining compared to air

Oxidation HP nitrogen AIR
Total tuyere flow CFM 2400–2800 1600–2000
Tuyere pressure Psi 60–65 50–55
Blowing time minutes 40–75 40–110
Sulfur PPM Start 400–500 400–500
End 50–110 90–110
Oxygen PPM Start 4000–4400 2800–4800
End 2300–4460 4460–5850
Reduction—team and natural gas
Steam #/hour 5100 5100
Natural gas % 17–20 17–20
CFM 380–400 380–400
Sulfur PPM Start 50–110 90–110
End 20–40 20–40
Oxygen PPM Start 2300–4460 4460-5850
End 1000–1500 1000–1500
Average refining time hours 2.3 2.7
Average cycle time hours 3.5 4.4

Fig. 5 Change in oxygen concentration with nitrogen refining compared to air

New Development—Praxair CoJet® Refining Application

Praxair and Kennecott entered into a joint development project to develop CoJet®
coherent jet technology for copper anode furnace fire refining. The project was
justified on the economic benefit of increased scrap melting [8]. The process
Reducing Refining Cycle Times to Extend Anode Furnace … 529

Refining Cycle Time (Hours) Refining Cycle Time (Hours)

East West 7.0
Baseline* 6.0 5.2 6.0
Jan 2016 5.0 4.3 5.0
Feb 5.0 4.9 4.0
Mar 4.6 4.8 3.0
Apr 5.4 4.4 2.0
May 4.1 4.4 1.0
Jun 5.1 4.6
0.0
July 5.2 3.9
Aug 3.7 3.1
YTD 4.7 4.2 East West
* Baseline data: August 2014 - March 2015

Fig. 6 Refining cycle time trend with nitrogen refining shows up to two hours savings per cycle
with nitrogen refining for August 2016 monthly composite data compared to the air baseline

technology was also used for bulk furnace accretion removal [9] and for several scrap
melting campaigns [10]. Coherent jet fire refining was trialed in 2008 and again in
2011 [10]. In 2015 Kennecott encountered a failure in the tuyere supply piping on
one furnace. Kennecott implemented CoJet® system refining for the Oxidation Stage
as a temporary solution. The CoJet® system use for this function successfully avoided
long refining times. During 2017 the operators used the coherent jet system during
refining on an as-needed tool to process high sulfur charges. This practice was
adopted for daily production in early 2018. The practice uses the Generation II
Praxair Coherent Jet lance system customized for Kennecott’s installation.
In 2015 Praxair developed a third generation coherent jet lance for copper
smelting (shown in Fig. 8). Praxair customized the new lance design for the
Kennecott process. The lance incorporated features from the CoJet® lances tested
for refining in 2008, 2011, and 2015 with additional features. The goal for
implementing the new lance is to achieve CoJet® tuyereless refining to extend the
campaign life. The new prototype lance was deployed in November 2016. It
operated until January 2017 when the prototype lance developed a leak. The lance
was taken out of service and a new lance design formulated using learnings from
the prototype lance. The new lance design is slated for commissioning in mid-2018.
As illustrated in Fig. 7 the zone of coherent jet gas injection is moved
approximately five feet away from the tuyere-zone to the center of the molten
copper bath. This aims to move the wear zone far away from the tuyere area.
Thereby seeking to extend the anode furnace campaign life by reducing the time the
tuyere-zone is subject to mechanical agitation. The new lance is shown in Fig. 8
during large-scale laboratory trials.
530 J. Enriquez et al.

Fig. 7 Tuyere nitrogen injection preliminary computational fluid dynamic result (at left);
Contrasted with rendition on Praxair coherent jet injection; Image at right based on preliminary
conceptual rendition as graphical illustration and does NOT depict actual jet penetration

Fig. 8 Coherent jet lance during laboratory testing at the Praxair technology center

Conclusions

1. Nitrogen refining was tested at Kennecott Utah Copper’s anode furnaces and
was adopted for production in 2016 and is used on more than 95% of charges.
2. Nitrogen injection is in the sonic velocity regime and enables rapid sulfur re-
moval without increasing dissolved oxygen concentration; this thereby shortens
the Reduction Stage.
3. Sulfur removal rates with nitrogen are higher than with 65 psig air from the air
compressor system.
4. Nitrogen use is about 342 cf/ton (8 Nm3/tonne) of blister copper (depends on
chemistry).
5. For oxidation with air the oxygen utilization efficiency for sulfur removal is
19–30%. The balance of the oxygen is absorbed in the copper and raises the
Reducing Refining Cycle Times to Extend Anode Furnace … 531

dissolved oxygen concentration which increases the length of the Reduction

Stage.
6. For steam-gas reduction the reductant utilization efficiency (assuming complete
reaction) was calculated for three charges and ranged from 42 to 68%.
7. Nitrogen refining contributed to reducing the overall refining cycle time by
1–1.3 h per charge during 2016 and by up to 2 h saved for August 2016 (Fig. 6).
8. The reduction in the refining cycle time translates to reduction in tuyere-line
agitation which is consistent with the goal to extend the anode furnace campaign
life to three years.
9. Coherent jet (CoJet®) refining aims to further extend tuyere-line refractory life
by injecting refining gases in the center of the molten copper bath (about six feet
away from the tuyere line).

Acknowledgements To Mike Riley for assistance with the FlowFac tuyere sonic velocity cal-
culation and for assistance with the steam and natural gas calculation, and to Ian Masterson for the
nitrogen refining blow calculation, and to Rodney Jones for Thermo software.

References

1. Chibwe DK, Akdogan G, Bezuidenhout GA, Kapusta JPT, Bradshaw S, Eksteen JJ (2015)
Sonic injection into a PGM Peirce Smith converter: CFD modelling and industrial trials.
J South Afr Inst Min Metall 115:349–354
2. Masterson I (1985) L-1352 final report, submerged combustion and refining development
program with Kennecott Minerals Corporation. Praxair internal report
3. Masterson I (2014) Private communication. Praxair e-mail to Kennecott Utah Copper, 28 Oct
2014
4. Filzwieser W, Caulfield R (2003) The COP KIN system part II-performance and benefits-a
world wide overview. In: Proceedings of copper-Cobre 2003, Santiago, 30 Nov–3 Dec 2003,
pp 363–376
5. Goyal P, Themelis NJ, Zanchuk WA (1982) Gaseous refining of anode copper. J Met 22–28
6. Newman CJ, Collins DN, Weddick AJ (1999) Recent operation and environmental control in
the Kennecott Smelter. In: George DB, (Pete) Chen WJ, Mackey PJ, Weddick AJ
(eds) Proceedings of Copper 99-Cobre 99 international conference, volume V—smelting
operations and advances. The minerals, metals, and materials society, pp 29–45
7. Krag P, Imrie W, Berkoe J, Vos R, Maciejewski J (1993) Anode furnace practice for
high-sulphur blister, converting, fire refining and casting. Min Met Mater Soc 255–267
8. Deneys A, Enriquez A (2009) Scrap melting in the anode furnace and the development of
coherent jet technology in copper refining. In: Kapusta J, Warner A (eds) International
Peirce-Smith converting centennial. The minerals, metals and materials society, pp 321–338
9. Enriquez A, Nexhip C, Poplar G, Deneys A (2010) An update on Praxair coherent jet
technology in anode refining at Kennecott Utah Copper. In: Copper-Cobre 2010 Proceedings,
GDMB, Hamburg, pp 2327–2339
10. Enriquez A, Nexhip C, Krippner D, Wright K, Deneys AC, Ma Y, Manley S (2010) An
update on Kennecott Utah Copper’s use of Praxair’s coherent jet technology in anode fire
refining-developments since 2010. In: Proceedings of Copper-Cobre 2013, Santiago, Chile,
pp 279–296